Cellulose Nanocrystals Particles Research Articles

Screening of Miscanthus Genotypes for Sustainable Production of Microcrystalline Cellulose and Cellulose Nanocrystals

Miscanthus spp. has been regarded as a promising industrial plant for the sustainable production of bio-based materials. To assess its potential for microcrystalline cellulose (MCC) and cellulose nanocrystals (CNCs) production, 50 representative clones of M. sinensis and M. floridulus were selected from a nationwide collection showcasing the extensive diversity of germplasm resources. Descriptive analysis indicates that the dry biomass weight of M. floridulus is advantageous whereas M. sinensis demonstrates higher MCC and CNCs yields as well as a smaller CNCs particle size. Correlation analyses indicated that MCC yield is solely influenced by the cellulose content whereas the yield of CNCs is affected by both the cellulose content and CrI. Comparative analyses of the chemical composition, physical features (degree of polymerization, crystalline index, particle size distribution and zeta potential), and scanning electron microscopy indicated that the MCC and CNCs extracted from M. sinensis and M. floridulus exhibited remarkable stability and quality. Additionally, the CNCs derived from M. sinensis and M. floridulus exhibited a distinctive ball-shaped structure. Notably, machine learning has demonstrated its efficacy and effectiveness in the high-throughput screening of large populations of Miscanthus spp. for predicting the yield of MCC and CNCs. Our results have also laid the theoretical foundation for the exploration, cultivation, and genetic breeding of M. sinensis and M. floridulus germplasm resources with the purpose of MCC and CNCs preparation.

Ultrasonication-induced re-dispersion of freeze-dried cellulose nanoparticles for improving strength and durability of PAN polymer matrix

Cellulose nanocrystals (CNCs) have acquired considerable attention owing to their noteworthy properties, including high crystallinity, biodegradability, high specific surface area, and excellent mechanical characteristics that alter the inherent features of the polymer matrix upon reinforcement. Typically, CNCs undergo freeze-drying or spray-drying to facilitate handling and dispersion in a hydrophobic polymer medium. Unfortunately, these drying procedures compromise the intrinsic nano-scale properties of CNCs. Therefore, achieving a uniform re-dispersion of dried CNCs is imperative to attain the desired characteristics in the polymer composite. This study specifically focuses on achieving a homogeneous re-dispersion of freeze-dried CNCs within a waste polyacrylonitrile (PAN) matrix through a simple ultrasonication treatment. The enhanced mechanical properties of the PAN polymer matrix validate the impact of ultrasound energy on re-dispersing CNCs. A noticeable improvement in the tensile properties of the composite polymer film is observed when CNC particles are well-dispersed in the PAN matrix. This observation is substantiated through SEM imaging, XRD, and FTIR data of both neat PAN and PAN–CNC composite films. The results affirm that particle dispersion plays a crucial role in augmenting the tensile properties of PAN composite films.

Parameters influencing electrospun nanofiber diameter of polylactide incorporated with cellulose nanofibrils and nanocrystals

The main purpose of this study was to investigate effects of various electrospinning parameters on the morphology and diameter of cellulose nanofibril (CNF) filled polylactide (PLA) nanofibers. For this purpose, first of all effects of three important electrospinning parameters; polymer solution concentration, solution feeding rate and collector distance to feeding tip were studied. Then, effects of using higher amount of CNF, effects of using cellulose nanocrystal (CNC) particles, and effects of adding potassium chloride salt were also investigated. It was observed that when optimum electrospinning parameters were determined, then it was possible to obtain almost “bead-free” morphology and “finest” average diameter of 232 nm for PLA/CNF electrospun fibers. Increasing values of feeding rate and collector distance parameters resulted in bead formation and thicker diameters. On the other hand, increasing CNF amount, using CNC particles and adding KCl salt, all resulted in further decreases in the diameter down to 152 nm; mainly due to increased charge density of the polymer solution. Moreover, in vitro degradation analysis of all types of electrospun nanofiber mats in a simulated body fluid revealed that increasing the immersion period increased their degradation rate in terms of “% weight loss”. It was also observed that, mats with fine diameter fibers had higher degradation rate.

Effects of different salt ions on the structure and rheological behavior of sulfated cellulose nanocrystal hydrogel

Cellulose nanocrystal (CNC) hydrogels are increasingly used in various applications. Here, CNC hydrogels were formed by adding four salt ions (NaCl, KCl, MgCl2, and CaCl2) to sulfated CNC suspensions. NaCl and KCl are monovalent salt ions and MgCl2 and CaCl2 are divalent salt ions; each pair has similar cation charges but different cation radii. This study compared the effects of four salt ions on the structure and rheological behavior of CNC hydrogels. At the same ion concentration, compared with NaCl and KCl, the addition of MgCl2 and CaCl2 significantly reduced the distance between the CNC particles, forming pronounced aggregates and denser network structures. Furthermore, the G′ and G″ of the CNC hydrogels with salt ions followed the order NaCl < KCl < MgCl2 < CaCl2 in the small-amplitude oscillatory shear (SAOS) test, and more viscoelastic hydrogels exhibited relatively lower deformability in the creep-recovery test. Under large-amplitude oscillatory shear (LAOS) conditions, the CNC hydrogels with salt ions exhibited LAOS type III behavior, and the change in yield stress followed the same order as the SAOS results. Among them, CNC hydrogel with CaCl2 exhibited stronger nonlinear response and enhanced strain-stiffening behavior (higher I3/I1 and e3/e1) to resist deformation before 20% strain, as well as an enhanced softening effect (higher |v3/v1|) as the structure was destroyed and rearranged at strains ranging from 20% to 100%. Such CNC hydrogels with different salt ions, which can regulate structural and rheological properties, provide basis for designing hydrogels and meet potential requirements in food and biomedicine fields.

Cellulose nanocrystals-gelatin composite hydrocolloids: Application to controllable responsive deformation during 3D printing

Three-dimensional (3D) food printing is an effective technology for creating food designs with complex appearances and customized nutritional profiles. However, controlling the deformation of 3D printed foods during processing remains a challenge. Here, a food hydrocolloid with customizable designs during heating and dehydration was designed using cellulose nanocrystals (CNC) and gelatin (G). The resultant cellulose nanocrystals-gelatin (CNC-G) hydrocolloid exhibited favorable rheological characteristics for three-dimensional (3D) printing. 3D printing allows the controlled oriented alignment of the CNC particles within the hydrocolloid along the printing direction, endowing the CNC-G hydrocolloid with highly anisotropic structures. This anisotropic property can cause a strain mismatch during dehydrated food processing, leading to a specific deformation of the hydrocolloid. By adjusting the 3D printing parameters and intentionally designing of the 3D printed structures, the alignment degree of CNCs within the hydrocolloid can be controlled, and thus, its deformation can be programmed. The customizable deformation of CNC-G hydrocolloid during food processing was deliberately designed through printing, and its adaptability and flexibility are demonstrated through the "flapping" of a butterfly and the "blooming" of a four-leaf clover. The flexibility and customizability of CNC-G hydrocolloid in 3D printing provide a new strategy to achieve deformation and precise control of 3D printed foods during processing.

Acetic acid as a protic solvent for reducing sulphuric acid concentrations in the production of cellulose nanocrystals alongside transition metal co-catalysts

Cellulose nanocrystals (CNC) conventionally involve highly concentrated sulphuric acid, which typically resulted in the formation of undesirable by-products. Although less corrosive mineral acids have been explored as alternatives, high concentrations are still required. In this study, CNC was successfully isolated from Leucaena leucocephala wood using mild sulphuric acid with acetic acid as protic solvent, and it was further studied with the addition of Lewis acids in the form of multivalent transition metal salts as co-catalyst. Selected divalent and trivalent transition metal salts including (Cr(NO3)3, Fe(NO3)3, Co(NO3)2, and Ni(NO3)2) were investigated. The morphology, chemical structure, particle size, and physicochemical properties of the CNCs were determined. Controlled depolymerization of cellulose was observed using transmission electron microscopy (TEM). Rod-like morphology for all CNCs was obtained during the hydrolysis process with the smallest CNC particles found at an average length of 278.1 ± 35.1 nm and a diameter of 13.4 ± 3.0 nm. The results showed that higher valence state metal ions resulted in better cellulose hydrolysis efficiency. In addition, the use of transition metal salt as a co-catalyst improved production efficiency and minimised carbonization of CNC while maintaining desired crystallinity and thermal properties.

Cellulose nanocrystal stabilized pickering nanoemulsions and their coalescence stability studied by fluorescence microscopy

Cellulose nanocrystals (CNCs) have been used as Pickering emulsifiers by forming rigid interfacial layer coated around oil droplets. Sulfated and desulfated CNCs were used to emulsify squalane oil to produce Pickering nanoemulsions. The formation of CNCs-Pickering nanoemulsions was investigated and their stability against mechanical stresses was studied using fluorescence microscopy with a lab-made image analysis program. The formation of Pickering nanoemulsions using CNC particles was tuned by screening their surface charges with cations. Sulfated and desulfated CNC nanoemulsions showed submicron droplet size of 619 and 555 nm, respectively. The mechanical stresses could induce droplet encounter leading to physical instability. The sulfated CNCs displayed superior stability than the desulfated CNCs in terms of droplet aggregation after treatment with mechanical stresses. Fluorescence microscopy image analysis revealed the physical instability of Pickering nanoemulsions at the microscopic level, which is a useful tool for studying the destabilization mechanisms.

Carboxylated cellulose nanocrystal cryogel monoliths: a multi-tool study of morphology and porosity of pure and magnetite nanoparticle-decorated CNC scaffolds

Tissue scaffolds are known to benefit from incorporation of nanoscale bio-additives like cellulose nanocrystals (CNC), which can affect porosity as an important tunable design parameter for bio-based scaffolds. In this paper, we probe how freeze-casting of carboxylated cellulose nanocrystals and CNC derivatized with magnetite nanoparticles yields macroscale cryogel scaffold monoliths. Cryogel topographical features and macropore morphologies depend on the conditions under which ice formation takes place, and on exposure to static magnetic fields. We examine porosity over several length scales with scanning electron microscopy (SEM) coupled with Local Thickness Euclidean distance image processing, small angle X-ray scattering (SAXS), and dynamic vapor sorption (DVS). SAXS data fitted with a mass fractal model and power law suggest that CNC particles aggregate to form well-defined compact walls in the range of 96.7–27.3 nm for all samples, while inclusion of Fe3O4 nanoparticles disrupts this compactness in the range of 27.3–4.8 nm. Analysis of DVS reveals that nanoparticles directly impact water uptake by the cryogel scaffolds and can reduce water sorption in mesopores with a radius of 5–6 nm.

In-situ formation of thermo-responsive petal-like cellulose nanocrystals hybridized particles towards optimizing mechanical, rheological and dielectric properties of polylactic acid blends

Enhancing the toughness of biodegradable polylactic acid (PLA) blends with minimal filler content meanwhile preserving their thermomechanical properties remains a highly desirable objective. Here, through a simple in situ mixing of PLA with cellulose nanocrystals (CNC) and cellulose nanocrystal nanofluids (CNCfs), the electrostatic interaction between CNCfs (+22.6 mv) and CNC (−9.07 mv) formed petal-like hybridized particles with CNCfs as the core and CNC particles as the outer layer. The rheological tests indicated a significant reduction in the zero-shear viscosity and storage modulus of PLA/CNCfs blends, while the viscosity of PLA/CNCfs@CNC slightly decreased but retained its storage modulus compared to pure PLA. The optimized PLA/CNCfs@CNC blends not only exhibited excellent melt processing performance, but also increased the elongation at break (increased by 184 % and 375 % at 8 °C and 45 °C, respectively) and enhanced toughness remarkably (increased by 3.5 and 3.3-fold at 8 °C and 45 °C, respectively) meantime retaining the modulus with 1 GPa. The addition of CNCfs@CNC hardly affects the glass transition temperature and thermo-mechanical properties of PLA. The dielectric properties of PLA/CNCfs1.0/CNC2.0 blends were maximized at 1000 Hz, reaching a value of 21, which can be attributed to the synergistic effect of multilayer interfacial polarization.

Surface modification of cellulose nanocrystals by physically adsorbing lactoferrin as pickering stabilizers: Emulsion stabilization and in vitro lipid digestion

Surface modification is a prerequisite procedure for using cellulose nanocrystals (CNCs) in food and other industries. This study reports a simple and safe procedure for CNCs surface modification using physically absorbing food protein (lactoferrin, LF) that could improve the emulsification performance and modulating emulsion lipid digestion in vitro. Modification of CNCs by LF was characterized by adsorption percentage (%), zeta-potential, atom force microscopy, and contact angle. The modification occurred electrostatically between negatively CNCs and positively LF. LF-modified CNCs are more hydrophobic and aggregation-prone depending on the ratio of protein to CNCs and pH. Emulsions stabilized by LF-modified CNCs which are characterized by visual appearance, microstructure, droplet size, and stability against lipid oxidation. Modification of CNCs by LF could improve the emulsification performance of CNCs and show high stability against lipid oxidation. In vitro gastrointestinal digestion of emulsions stabilized by LF-modified CNCs was also investigated by Free fatty acid released (FFA, %) and microstructure. Overall, emulsions stabilized by CNCs particles have lower lipid digestion extent than that of tween 20. The findings would have potential applications in fabrication of novel functional emulsions in food and other industries.

On the stabilization of emulsions by cellulose nanocrystals and nanofibrils: Interfacial behavior and synergism

Competitive adsorption of cellulose nanofibers at oil-water interface in Pickering emulsion is reported here. Dodecane-in-water emulsions stabilized by either of two types of nanocelluloses, cellulose nanocrystals (CNC) or cellulose nanofibrils (CNF), as well as by their binary mixtures with increasing fractions of CNC, were prepared using particle concentrations of 0.1–0.5 wt% and studied. Despite differences in shape and morphology, both forms of nanofibers produced stable emulsion droplets even at low particle concentrations (0.1 wt%), with CNC producing smaller droplets and emulsions with higher stability. When mixed, an increased fraction of CNC in the mixture reduced the average droplet size, which however applied only for higher contents of oil (30 and 50 wt%) and higher total contents of cellulose particles used under emulsification. The CNC particles controlled the size of emulsion droplets, while the role of CNF contributed to the further surface coverage. When the fraction of CNF in the mixture increased, the capability of CNC particles to readily adsorb at the oil-water interface was reduced by the CNF nanofibrils present in aqueous phase. The stability of emulsions with respect to changes in droplet size and creaming index was influenced more by oil content and total particle concentration than by the fraction of CNC present in the mixture.

Acetylation of Cellulose Nanocrystals Extracted from Cotton for Drilling Fluid Application: Structural and Thermal Characterization

In petroleum exploration, cellulose derivatives such as carboxymethylcellulose (CMC) are frequently used in drilling, cementing and fracturing fluids. However, under extreme drilling conditions, these additives have limited performance. In this regard, cellulose nanocrystals particles (CNCs) which are also derived from cellulose material are a suitable candidate due to their shear thinning rheology and thixotropy properties, even at low concentrations, among so many properties thanks to their crystalline structure and their nanometric dimensions.In this work, hydrolyzed fibers from industrial cotton are acetylated using acetic anhydride and sulfuric acid as catalysts, with the aim to modify surface properties of the obtained CNCs without changing their fiber structure and morphology. FTIR analysis pointed out the acetylation success of the obtained nanocrystals whose dimensions were found to be unaltered by the modification process. SEM images of cotton nanocrystal indicate that CNCcsurface modification preserves the nanoscale dimensions of the nanoparticles. Also, TGA analysis showed thermal stability for the acetylated CNCc.

Preparation and Characterization of Cellulose Nanocrystals from Bamboos and Their Application in Cassava Starch-Based Film.

Cellulose from different species of bamboo (Thyrsostachys siamesi Gamble, Dendrocalamus sericeus Munro (DSM), Bambusa logispatha, and Bambusa sp.) was converted to cellulose nanocrystals (CNCs) by a chemical-mechanical method. First, bamboo fibers were pre-treated (removal of lignin and hemicellulose) to obtain cellulose. Next, the cellulose was hydrolyzed with sulfuric acid using ultrasonication to obtain CNCs. The diameters of CNCs are in the range of 11-375 nm. The CNCs from DSM showed the highest yield and crystallinity, which was chosen in the film fabrication. The plasticized cassava starch-based films with various amounts (0-0.6 g) of CNCs (from DSM) were prepared and characterized. As the number of CNCs in cassava starch-based films increased, water solubility and the water vapor permeability of CNCs decreased. In addition, the atomic force microscope of the nanocomposite films showed that CNC particles were dispersed uniformly on the surface of cassava starch-based film at 0.2 and 0.4 g content. However, the number of CNCs at 0.6 g resulted in more CNC agglomeration in cassava starch-based films. The 0.4 g CNC in cassava starch-based film was found to have the highest tensile strength (4.2 MPa). Cassava starch-incorporated CNCs from bamboo film can be applied as a biodegradable packaging material.

Cellulose Nanocrystals (CNCs) and Cellulose Nanofibers (CNFs) as Adsorbents of Heavy Metal Ions

The isolation of nanocellulose has been extensively investigated due to the growing demand for sustainable green materials. Cellulose nanocrystals (CNCs) and cellulose nanofibers (CNFs), which have the same chemical composition but have different morphology, particle size, crystallinity, and other properties depending on the precursor and the synthesis method used. In comparison, CNC particles have a short rod-like shape and have smaller particle dimensions when compared to CNF particles in the form of fibers. CNC synthesis was carried out chemically (hydrolysis method), and CNF synthesis was carried out mechanically (homogenization, ball milling, and grinding), and both can be modified because they have a large surface area and are rich in hydroxyl groups. Modifications were made to increase the adsorption ability of heavy metal ions. The Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric (TG), and dynamic light scattering (DLS) can reveal the characteristics and morphology of CNCs and CNFs. The success and effectiveness of the heavy metal adsorption process are influenced by a few factors. These factors include adsorbent chemical structure changes, adsorbent surface area, the availability of active sites on the adsorbent’s surface, adsorption constants, heavy metal ionic size differences, pH, temperature, adsorbent dosage, and contact time during the adsorption process. In this review, we will discuss the characteristics of CNCs and CNFs synthesized from various precursors and methods, the modification methods, and the application of CNCs and CNFs as heavy metal ion adsorbents, which includes suitable isotherm and kinetics models and the effect of pH on the selectivity of various types of heavy metal ions.

Rheological studies of cellulose nanocrystal/dimethyl sulfoxide organogels

Cellulose nanocrystals (CNCs)/H2O gels have received significant interest in various applications for the past decades. And yet CNCs organogels, which are important to their wider application, are less explored. In this work, CNCs/Dimethyl sulfoxide (DMSO) organogels are carefully investigated by rheological methods. It is found that metal ions also can facilitate the organogel formation as in hydrogel. Charge screening and coordination effects play vital roles in the organogel formation and their mechanical strength. CNCs/DMSO gels with different cations display similar mechanical strength, while CNCs/H2O gels show increasing mechanical strength with the increasing valence of cations. It seems that the coordination between cations and DMSO alleviate the influence of valence on gel mechanical strength. Due to weak, fast and reversible electrostatic interactions among CNCs particles, both CNCs/DMSO and CNCs/H2O gels show instant thixotropic behavior, which may find some interesting applications in the field of drug delivery. The morphological changes observed in polarized optical microscope appear to be consistent with rheological results.

Regulatory Mechanism of Opposite Charges on Chiral Self-Assembly of Cellulose Nanocrystals.

The charge plays an important role in cellulose nanocrystal (CNC) self-assembly to form liquid crystal structures, which has rarely been systematically explored. In this work, a novel technique combining atomic force microscopy force and atomistic molecular dynamics simulations was addressed for the first time to systematically investigate the differences in the CNC self-assembly caused by external positive and negative charges at the microscopic level, wherein sodium polyacrylate (PAAS) and chitosan oligosaccharides (COS) were used as external positive and negative charge additives, respectively. The results show that although the two additives both make the color of CNC films shift blue and eventually disappear, their regulatory mechanisms are, respectively, related to the extrusion of CNC particles by PAAS and the reduction in CNC surface charge by COS. The two effects both decreased the spacing between CNC particles and further increased the cross angle of CNC stacking arrangement, which finally led to the color variations. Moreover, the disappearance of color was proved to be due to the kinetic arrest of CNC suspensions before forming chiral nematic structure with the addition of PAAS and COS. This work provides an updated theoretical basis for the detailed disclosure of the CNC self-assembly mechanism.

3D Printing-Assisted Self-Assembly to Bio-Inspired Bouligand Nanostructures.

Architected materials with nano/microscale orders can provide superior mechanical properties; however, reproducing such levels of ordering in complex structures has remained challenging. Inspired by Bouligand structures in nature, here, 3D printing of complex geometries with guided long-order radially twisted chiral hierarchy, using cellulose nanocrystals (CNC)-based inks is presented. Detailed rheological measurements, in situ flow analysis, polarized optical microscopy (POM), and director field analysis are employed to evaluate the chiral assembly over the printing process. It is demonstrated that shear flow forces inside the 3D printer's nozzle orient individual CNC particles forming a pseudo-nematic phase that relaxes to uniformly aligned concentric chiral nematic structures after the flow cessation. Acrylamide, a photo-curable monomer, is incorporated to arrest the concentric chiral arrangements within the printed filaments. The time series POM snapshots show that adding the photo-curable monomer at the optimized concentrations does not interfere with chiral self-assemblies and instead increases the chiral relaxation rate. Due to the liquid-like nature of the as-printed inks, optimized Carbopol microgels are used to support printed filaments before photo-polymerization. By paving the path towards developing bio-inspired materials with nanoscale hierarchies in larger-scale printed constructs, this biomimetic approach expands 3D printing materials beyond what has been realized so far.

Influences of modified fiber inclusion with varying particle size on corn starch-based extrudate expansion.

The inclusion of cellulose nanocrystals (CNC) and microcrystalline cellulose (MCC) during extrusion processing of corn starch (CS) is presented in this study. Blends were prepared by incorporating CNC and MCC at different concentrations, 1%, 3%, 5%, and 10% w/w in CS. The crystallinity index (CrI) of CNC and MCC was determined using X-ray diffraction, and the chemical functionality of CNC, MCC, and CS was studied using Fourier transform infrared spectroscopy. The pasting properties of the blends were studied using Micro Visco-Amylo-Graph before extrusion. The blends were preconditioned to 18±0.5% (w.b.) moisture and extruded using a twin-screw extruder at 200 and 250rpm at 140°C. CS-CNC's expansion ratio (ER) values were 2.95 to 3.35 and 2.72 to 3.22 for MCC. CNC's CrI and particle size were significantly lower than MCC, allowing CNC-based extrudates to have ER values similar to the control even at high CNC concentration (≤10% w/w). This study demonstrated that fiber with particle size<100µm can be added in direct-expanded product formulations at high concentrations without negatively influencing the extrudate texture while offering increased nutritional value. PRACTICAL APPLICATION: This study gives insight into the potential application of cellulose nanocrystals and microcrystalline cellulose in manufacturing direct-expanded extruded products, providing high fiber content without compromising the product quality. This knowledge could also be translated into manufacturing other food products such as breakfast cereals, pasta, and bread.

Enantioselective disruption of cellulose nanocrystal self-assembly into chiral nematic phases in D-alanine solutions.

The chiral environment of enantiomerically pure D-alanine solutions is observed to disrupt and modify the entropy-driven assembly of cellulose nanocrystals (CNCs) into a chiral nematic mesophase. The effect is specific to D-alanine and cannot be attributed to the adsorption of alanine molecules (neither D- nor L-alanine) onto the CNC particles.

All-Aqueous Bicontinuous Structured Liquid Crystal Emulsion through Intraphase Trapping of Cellulose Nanoparticles.

Here, we describe the all-aqueous bicontinuous emulsions with cholesteric liquid crystal domains through hierarchical colloidal self-assembly of nanoparticles. This is achieved by homogenization of a rod-like cellulose nanocrystal (CNC) with two immiscible, phase separating polyethylene glycol (PEG) and dextran polymer solutions. The dispersed CNCs exhibit unequal affinity for the binary polymer mixtures that depends on the balance of osmotic and chemical potential between the two phases. Once at the critical concentration, CNC particles are constrained within one component of the polymer phases and self-assemble into a cholesteric organization. The obtained liquid crystal emulsion demonstrates a confined three-dimensional percolating bicontinuous network with cholesteric self-assembly of CNC within the PEG phase; meanwhile, the nanoparticles in the dextran phase remain isotropic instead. Our results provide an alternative way to arrest bicontinuous structures through intraphase trapping and assembling of nanoparticles, which is a viable and flexible route to extend for a wide range of colloidal systems.