Morphological Analyses of Some Micro- and Nanofibrils from Birch and Wheat Straw Sources

<div><p>The morphological properties of nano- and microcellulose depend on the source of the particles, the preparation methods, and the processing conditions. In this study, two different kinds of microfibrillated (MFC) and nanofibrillated (NFC) celluloses were produced from wood and non-wood cellulose pulps through mechanical methods without using any chemicals. The morphological properties of the samples and feasibility of different analysis methods were investigated using a novel chromatographic washer, a field emission scanning electron microscope (FESEM), a laser diffractometer (LS), a rotational viscometer, X-ray diffractometry (WAXD) and, additionally, the degree of polymerization (DP) was assessed. The analyses showed that the formed non-wood cellulose fibrils were shorter than the wood cellulose fibrils, but wheat straw pulp comminuted to nanofibrils more easily. The low hemicelluloses content of wheat straw pulp caused the flocculation of the nanofibrils formed in homogenization. All of the analytical methods reflect morphological differences between the micro- and nanocellulose materials.</p></div

Acidic Deep Eutectic Solvents As Hydrolytic Media for Cellulose Nanocrystal Production

In this study, a new method to fabricate cellulose nanocrystals (CNCs) based on DES pretreatment of wood cellulose fibers with choline chloride and organic acids are reported. Oxalic acid (anhydrous and dihydrate), p-toluenesulfonic acid monohydrate, and levulinic acid were studied as acid components of DESs. DESs were formed at elevated temperatures (60–100 °C) by combining choline chloride with organic acids and were then used to hydrolyze less ordered amorphous regions of cellulose. All the DES treatments resulted in degradation of wood fibers into microsized fibers and after mechanically disintegrating, CNCs were successfully obtained from choline chloride/oxalic acid dihydrate-treated fibers, whereas no liberation of CNCs was observed with other DESs. The DES-produced CNCs had a width and length of 9–17 and 310–410 nm, respectively. The crystallinity indexes (CrIs) and carboxylic acid content of the CNCs were 66–71% and 0.20–0.28 mmol/g, respectively. CNCs exhibited good thermal stabilities (the onset thermal degradation temperatures ranged from 275–293 °C). The demonstrated acidic DES method exhibits certain advantages over previously reported CNC productions, namely, milder processing conditions and easily obtainable and relatively inexpensive biodegradable solvents with low toxicity (compared, e.g., to ILs)

Thiol-Silylated Cellulose Nanocrystals as Selective Biodepressants in Froth Flotation

The extraction of various minerals is commonly conducted through froth flotation, which is a versatile separation method in mineral processing. In froth flotation, depressants are employed to improve the flotation selectivity by modifying the wettability of the minerals and reducing their natural or induced floatability. However, the environmental impact of many current flotation chemicals poses a challenge to the sustainability and selectivity of the ore beneficiation processes. To mitigate this issue, cellulose, particularly nanocelluloses, has been explored as a potential alternative to promote sustainable mineral processing. This study focused on silylated cellulose nanocrystals (CNCs) as biodepressants for sulfide minerals in froth flotation. CNCs containing thiol silane groups or bifunctional CNCs containing both thiol and propyl silanes were synthesized using an aqueous silylation reaction, and their performance in the flotation of chalcopyrite and pyrite was investigated in the presence of a sodium isobutyl xanthate collector. The results showed that the modified CNCs exhibited preferential interaction between chalcopyrite, and the flotation recovery of chalcopyrite decreased from ∼76% to ∼24% in the presence of thiol-grafted CNCs at pH 6, while the pyrite recovery decreased only from ∼82% to ∼75%, indicating the efficient selectivity of thiol-silylated CNCs toward chalcopyrite depression

Amphiphilic Cellulose Nanocrystals from Acid-Free Oxidative Treatment: Physicochemical Characteristics and Use as an Oil–Water Stabilizer

A chemical pretreatment for producing cellulose nanocrystals (CNCs) with periodate oxidation and reductive amination is reported. This new functionalization of cellulose fibers dispenses an alternative method for fabricating individual CNCs without the widely used acid hydrolysis process. CNCs can be directly modified during the pretreatment step, and no additional post-treatments are required to tune the surface properties. Three butylamine isomers were tested to fabricate CNCs with amphiphilic features. After mechanical homogenization, CNCs occurred as individual crystallinities without aggregation where high uniformity in terms of shape and size was obtained. The elemental analysis and 1H NMR measurement show that iso- and n-butylamine attach the highest number of butylamino groups to the cellulose fibers. Linking the alkyl groups increases the hydrophobic nature of the CNCs, where water contact angles from self-standing films up to 110.5° are reported. Since these butylamino-functionalized CNCs have hydrophobic characteristics in addition to the hydrophilic backbone of cellulose, the stabilization impact on oil/water emulsions is demonstrated as a potential application

Enhancement of the Nanofibrillation of Wood Cellulose through Sequential Periodate–Chlorite Oxidation

Sequential regioselective periodate–chlorite oxidation was employed as a new and efficient pretreatment to enhance the nanofibrillation of hardwood cellulose pulp through homogenization. The oxidized celluloses with carboxyl contents ranging from 0.38 to 1.75 mmol/g could nanofibrillate to highly viscous and transparent gels with yields of 100–85% without clogging the homogenizer (one to four passes). On the basis of field-emission scanning electron microscopy images, the nanofibrils obtained were of typical widths of approximately 25 ± 6 nm. All of the nanofibrillar samples maintained their cellulose I crystalline structure according to wide-angle X-ray diffraction results, and the crystallinity index was approximately 40% for all samples

Pickering Emulsions and Hydrophobized Films of Amphiphilic Cellulose Nanofibers Synthesized in Deep Eutectic Solvent

Herein, a dual-functioning deep eutectic solvent system based on triethylmethylammonium chloride and imidazole was harnessed as a swelling agent and a reaction medium for the esterification of cellulose with n-octyl succinic anhydride (OSA). The modified or amphiphilic cellulose nanofibers (ACNFs), synthesized using three different OSA-to-anhydroglucose unit molar ratios (0.5:1, ACNF-1; 1:1, ACNF-2; and 1.5:1, ACNF-3), were further converted into nanofibers with degree of substitution (DS) values of 0.24–0.66. The ACNFs possessed a lateral dimension of 4.24–9.22 nm and displayed surface activity due to the balance of hydrophobic and hydrophilic characteristics. The ACNFs made stable aqueous dispersions; however, the instability index of ACNF-3 (0.51) was higher than those of ACNF-1 (0.29) and ACNF-2 (0.33), which was attributed to the high DS-induced hydrophobicity, causing the instability in water. The amphiphilic nature of ACNFs promoted their performance as stabilizers in oil-in-water Pickering emulsions with average droplet sizes of 4.85 μm (ACNF-1) and 5.48 μm (ACNF-2). Self-standing films of ACNFs showed high contact angles for all the tested DS variants (97.48–114.12°), while their tensile strength was inversely related to DS values (ACNF-1: 115 MPa and ACNF-3: 49.5 MPa). Aqueous dispersions of ACNFs were also tested for coating fruits to increase their shelf life. Coatings improved their shelf life by decreasing oxygen contact and moisture loss

Strong, Self-Standing Oxygen Barrier Films from Nanocelluloses Modified with Regioselective Oxidative Treatments

In this work, three self-standing nanocellulose films were produced from birch pulp using regioselective oxidation and further derivatization treatments. The modified celluloses were synthesized using periodate oxidation, followed by chlorite oxidation, bisulfite addition, or reductive amination with amino acid taurine, which resulted in dicarboxylic acid cellulose (DCC), α-hydroxy sulfonic acid cellulose (HSAC), and taurine-modified cellulose (TC), respectively. The nanocelluloses were fabricated by mechanical disintegration using high-pressure homogenization. Mechanical and barrier properties of the nanocellulose films were characterized. Two (2,2,6,6-tetramethyl-piperidin-1-yl)­oxyl (TEMPO) oxidation-based nanocellulose films were also produced, and their properties were compared to the periodate-based nanocellulose films. All of the periodate-based nanocellulose films showed high tensile strength (130–163 MPa) and modulus (19–22 GPa). Oxygen barrier properties of the films were superior to many synthetic and composite materials; in particular, the nanofibrillated DCC films had oxygen permeability as low as 0.12 cm³ μm/(m² d kPa) at 50% relative humidity. Compared to films of TEMPO-oxidized nanocelluloses, all of the periodate-based nanocellulose films had similar or even better mechanical and barrier properties, demonstrating versatility of periodate oxidation to obtain nanocellulose films with adjustable properties. Also, for the first time, amino-acid-based cellulose modification was used in the production of nanocellulose

Nanostructured and Advanced Designs from Biomass and Mineral Residues: Multifunctional Biopolymer Hydrogels and Hybrid Films Reinforced with Exfoliated Mica Nanosheets

Transforming potential waste materials into high-value-added sustainable materials with advanced properties is one of the key targets of the emerging green circular economy. Natural mica (muscovite) is abundant in the mining industry, which is commonly regarded as a byproduct and gangue mineral flowing to waste rock and mine tailings. Similarly, chitin is the second-most abundant biomass resource on Earth after cellulose, extracted as a byproduct from the exoskeleton of crustaceans, fungal mycelia, and mushroom wastes. In this study, exfoliated mica nanosheets were individualized using a mechanochemical process and incorporated into regenerated chitin matrix through an alkali dissolution system (KOH/urea) to result in a multifunctional, hybrid hydrogel, and film design. The hydrogels displayed a hierarchical and open nanoporous structure comprising an enhanced, load-bearing double-cross-linked polymeric chitin network strengthened by mica nanosheets possessing high stiffness after high-temperature curing, while the hybrid films (HFs) exhibited favorable UV-shielding properties, optical transparency, and dielectric properties. These hybrid designs derived from industrial residues pave the way toward sustainable applications for many future purposes, such as wearable devices and tissue engineering/drug delivery

Comprehensive NMR Analysis of Pore Structures in Superabsorbing Cellulose Nanofiber Aerogels

Highly porous cellulose nanofiber (CNF) aerogels are promising, environmentally friendly, reusable, and low-cost materials for several advanced environmental, biomedical, and electronic applications. The aerogels have a complex and hierarchical 3D porous network structure with pore sizes ranging from nanometers to hundreds of micrometers. The morphology of the network has a critical role on the performance of aerogels, but it is difficult to characterize thoroughly with traditional techniques. Here, we introduce a combination of nuclear magnetic resonance (NMR) spectroscopy techniques for comprehensive characterization of pore sizes and connectivity in the CNF aerogels. Cyclohexane absorbed in the aerogels was used as a probe fluid. NMR cryoporometry enabled us to characterize the size distribution of nanometer scale pores in between the cellulose nanofibers in the solid matrix of the aerogels. Restricted diffusion of cyclohexane revealed the size distribution of the dominant micrometer scale pores as well as the tortuosity of the pore network. T2 relaxation filtered microscopic magnetic resonance imaging (MRI) method allowed us to determine the size distribution of the largest, submillimeter scale pores. The NMR techniques are nondestructive, and they provide information about the whole sample volume (not only surfaces). Furthermore, they show how absorbed liquids experience the complex 3D pore structure. Thorough characterization of porous structures is important for understanding the properties of the aerogels and optimizing them for various applications. The introduced comprehensive NMR analysis set is widely usable for a broad range of different kinds of aerogels used in different applications, such as catalysis, batteries, supercapacitors, hydrogen storage, etc.</i