Nanocrystalline Cellulose Suspensions Research Articles

Synthesis and Physicochemical Properties of Poly(vinyl) Alcohol Nanocomposites Reinforced with Nanocrystalline Cellulose from Tea (Camellia sinensis) Waste.

The purpose of this study was to utilize cellulose from tea waste as nanocrystalline cellulose (NCC), which is used as a filler in poly(vinyl) alcohol (PVA) nanocomposites. To obtain the NCC, a chemical process was conducted in the form of alkali treatment, followed by bleaching and hydrolysis. Nanocomposites were formed by mixing PVA with various NCC suspensions. With chemical treatment, lignin and hemicellulose can be removed from the tea waste to obtain NCC. This can be seen in the functional groups of cellulose and the increase in crystallinity. The NCC had a mean diameter of 6.99 ± 0.50 nm. Furthermore, the addition of NCC to the PVA nanocomposite influenced the properties of the nanocomposites. This can be seen in the general increase in opacity value, thermal and mechanical properties, and crystallinity, as well as the decrease in the value of the swelling ratio after adding NCC. This study has revealed that NCC from tea waste can be used to improve the physicochemical properties of PVA film.

Synthesis of nanocrystalline cellulose via ammonium persulfate-assisted swelling followed by oxidation and their chiral self-assembly

A single-step ammonium persulfate (APS)-assisted swelling, followed by oxidation, can prepare nanocrystalline cellulose (NCC) from cotton linters. The APS-swelling is the critical step in the process, and the effects of swelling time, temperature and solid–liquid ratios were thoroughly investigated. The optimal conditions for NCC preparation were a swelling time of 3.0 h, a swelling temperature of 25 °C, and a solid–liquid ratio of 1:50. Upon heating at 60 °C, the persulfate enters the amorphous region of the cellulose and produces active SO4·− and H2O2, which effectively attack the two-phase structure of cellulose and oxidize the –OH group at the C-6 position. The swelling temperature of 25 °C plays a crucial role in breaking the hydrogen bonds between the molecular chains of cellulose. It permits the preparation of NCC with a high yield and crystallinity index. The crystalline structure of cellulose Iβ did not change after APS swelling and oxidation. The atomic force microscopic analysis confirmed the formation of spindle-shaped particles with a helical structure. Upon natural evaporation of the NCC suspension, brittle films were obtained, which exhibited a left-hand layered structure and high iridescence with a fingerprint-texture. These materials can be applied as strength additives and chiral templates.

Structure and rheology of liquid crystal hydroglass formed in aqueous nanocrystalline cellulose suspensions

HypothesisLiquid crystal hydroglass (LCH) is a biphasic soft material with flow programmable anisotropy that forms via phase separation in suspensions of charged colloidal rods upon increases in ionic strength. The unique structure and rheology of the LCH gel formed using nanocrystalline cellulose (NCC) is hypothesised to be dependent on colloidal stability that is modulated using specific ion effects arising from Hofmeister phenomena. ExperimentsLCHs are prepared in NCC suspensions in aqueous media containing varying levels of sodium chloride (NaCl) or sodium thiocyanate (NaSCN). The NCC suspensions are characterised using rheology and structural analysis techniques that includes polarised optical microscopy, zeta potential, dynamic light scattering and small-angle X-ray scattering. FindingsThe two salts have a profound effect on the formation process and structure of the LCH. Differences in network density and size of the liquid crystal domains are observed within the LCH for each of the salts, which is associated with the strength of interaction between NCC particles during LCH formation. In comparison to Cl− at the same salinity, the chaotropic nature of the weakly hydrated SCN− enhances colloidal stability by rendering NCC particles more hydrated and repulsive, but this also leads to weaker gel strength of the LCH. The results suggest that salts are a means in which to control the formation, structure and rheology of these anisotropic soft materials.

Enhancement of Biodegradable Poly(Ethylene Oxide) Ionic–Polymer Metallic Composite Actuators with Nanocrystalline Cellulose Fillers

Biodegradable ionic polymer metallic composite (IPMC) electroactive polymers (EAPs) were fabricated using poly(ethylene oxide) (PEO) with various concentrations of lithium perchlorate. Nanocrystalline cellulose (NCC) rods created from a sulfuric acid hydrolysis process were added at various concentrations to increase the EAPs’ elastic modulus and improve their electromechanical properties. The electromechanical actuation was studied. PEONCC composites were created from combining a 35-mg/mL aqueous NCC suspension with an aqueous, PEO solution at varying vol.%. Due to an imparted space charge from the hydrolysis process, composites with an added 1.5 vol.% of NCC suspension exhibited an electromechanical tip displacement, strain, and elastic modulus that was 40.7%, 33.4% and 20.1% higher, respectively, than those for PEO IPMCs without NCC. This performance represented an increase of 300% in the energy density of these samples. However, the electromechanical response decreased when the NCC content was high. NCC without the space charge were also tested to verify the analysis. Additionally, the development of new relationships for modeling and evaluating the time-dependent instantaneous tip angular velocity and acceleration was discussed and applied to these IPMCs.

The resilience of nanocrystalline cellulose viscosity to simulated digestive processes and its influence on glucose diffusion

Intake of dietary fibre may modulate digesta viscosity and suppress the rise of postprandial plasma glucose by attenuating glucose diffusion in the lumen of the gastrointestinal tract. In this study, nanocrystalline cellulose (NCC), extracted by sulfuric acid was morphologically characterised by atomic force microscopy. To investigate the influence of digestive processes on NCC viscosity, NCC-protein-starch systems, and NCC suspensions were subjected to two-step static in vitro digestions using Infodigest protocol. Changes in viscosity and subsequent release and diffusion of glucose were monitored. The results demonstrated that the crystalline rod-like NCC particles were sensitive to dilution and constituents in the simulated digestive fluids, and could modulate viscosity of the digesta. Consequently, glucose release and diffusion rates were significantly (p < 0.05) reduced in NCC-food system compared with control. NCC may be used as a dietary fibre in food systems to modulate viscosity and delay the digestion and diffusion of starch and glucose respectively.

Homogenous and transparent nanocellulosic films from carrot

Nano fibrillated cellulose (NFC) and nanocrystalline cellulose (NCC) have been extracted from carrot pulp by using non-conventional ball milling and acid hydrolysis process respectively. Initially, hot water washed carrot raw fibers treated with hydrogen peroxide, yielded the cellulose rich fibers in the absence of β-carotene and lignin. The scanning electron microscopy (SEM) of raw and bleached fibers showed that carrot consisting of both classical and unusual spring shaped fibers. The ensued purified fibers were fibrillated by ball milling process at three different grinding time to obtain NFC. The consequence of grinding time on fibrillation and morphology of the resulted NFC was investigated by SEM. In parallel, alkali treated pure carrot fibers were used to extract the NCC by acid hydrolysis process. The structural, functional, crystalline and thermal properties of resulted NFC and NCC was characterized by means of transmission electron microscopy (TEM), atomic force microscopy (AFM), Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD) and thermogravimetric analysis (TGA). The length and the diameter of the NCC prepared from carrot was in the range of 54–610 nm. Significant improvement in crystallinity was observed for 5NFC (69%) and NCC (78%) compared to that of raw fibers (36%). The obtained NFC and NCC suspensions were separately cast into nanocellulosic films (NCF). The optical and morphological properties of the resulted films were analysed systematically by ultraviolet–visible spectrophotometry (UV–vis) and SEM respectively. NCF exhibited the significant improvement in the transparency and homogeneity with increase in the grinding time. Furthermore, the mechanical properties of the carrot NCF were studied by using the tensile test.

Effect of Cationic Surface Modification on the Rheological Behavior and Microstructure of Nanocrystalline Cellulose

In the present work, the microstructure and rheological behavior of nanocrystalline cellulose (NCC) and cationically modified NCC (CNCC) were comparatively studied. The resultant CNCC generally showed improved dispersion and higher thermal stability in comparison to the un-modified NCC. The rheological behavior demonstrated that the viscosity of the NCC suspension substantially decreased with the increasing shear rate (0.01–100 s−1), showing the typical characteristics of a pseudoplastic fluid. In contrast, the CNCC suspensions displayed a typical three-region behavior, regardless of changes in pH, temperature, and concentration. Moreover, the CNCC suspensions exhibited higher shear stress and viscosity at a given shear rate (0.01–100 s−1) than the NCC suspension. Meanwhile, the dynamic viscoelasticity measurements revealed that the CNCC suspensions possessed a higher elastic (G′) and loss modulus (G″) than NCC suspensions over the whole frequency range (0.1–500 rad·s−1), providing evidence that the surface cationization of NCC makes it prone to behave as a gel-like structure.

"Liquid, gel and soft glass" phase transitions and rheology of nanocrystalline cellulose suspensions as a function of concentration and salinity.

The colloidal size and rod morphology of nanocrystalline cellulose (NCC) lead to suspensions with useful phase and gelation behaviours as well as complex rheologies. However, these have not been comprehensively evaluated previously. Here we report the detailed phase behaviour of sulphonated NCC aqueous suspensions as a function of concentration and salinity. Four phases - liquid, viscoelastic, repulsive glass and attractive glass/gel - are identified in terms of their distinct rheological behaviours. The liquid-solid transitions (LSTs) are determined rheologically, and these are supported by a simplified model based on the DLVO theory that indicates the importance of charge in determining the phase behaviour. Rheology is also used to investigate the solid-solid transition from a repulsive glass to an attractive gel with increasing salt at high NCC concentrations. A time-dependent aging phenomenon is observed in suspensions with a composition just below the LSTs, and the implications of this on the dynamics occurring during gelation processes are discussed. This work can be directly applied to the development of structure-function relationships and the expanding utilisation of NCC suspensions, whilst also providing a basis for the study of charged colloidal rods more generally and evaluation of theoretical models.

Ion-Induced Hydrogel Formation and Nematic Ordering of Nanocrystalline Cellulose Suspensions.

Nanocrystalline cellulose (NCC) is a promising material for formation of hydrogels and nematic liquid crystals. While salt addition is known to facilitate hydrogel formation, it remains unclear whether this originates from cationic bridging or charge screening effects. Herein, we demonstrate the effect of mono- and divalent salts on NCC gelation and nematic ordering. A strong correlation of NCC suspension zeta-potential and rheological behavior was found. Lower concentrations of divalent cations were needed to decrease NCC zeta-potential and form hydrogels. The same zeta-potentials and gel strengths were achieved at higher concentrations of monovalent salts. Salt-induced NCC aggregation is thus caused by intermolecular attractive forces rather than cationic bridging. Against excluded volume argumentation, salt addition was found to promote NCC nematic phase formation. Increased nematic ordering was observed in a transition regime of moderate salt addition before complete aggregation occurs. This regime is governed by an equilibrium of repulsive and attractive forces. Small angle neutron scattering suggests lateral orientation of NCC. Hence, NCC gelation and nematic ordering can be modulated via its zeta-potential by targeted salt addition.

Potential aspect of rice husk biomass in Australia for nanocrystalline cellulose production

Abstract Nanocrystalline cellulose (NCC) was produced from rice husk biomass (Oryza sativa) by a chemical extraction process to explore the potential aspect of agro-waste biomass in Australia. In this work, the delignified rice husk pulp (D-RHP) was produced by alkaline delignification of raw rice husk biomass (R-RHB) using 4 mol·L− 1 alkali solutions (NaOH) in a jacketed glass reactor under specific experimental conditions. D-RHP was bleached using 15% sodium hypochlorite, and the bleached rice husk pulp was coded as B-RHP. Finally, raw suspension of NCC was produced by the acid hydrolysis of B-RHP using 4 mol·L− 1 sulphuric acid. The raw suspension of NCC was neutralized by a buffer solution and analyzed by TAPPI, FT-IR, XRD, SEM, AFM, and TEM. FT-IR spectra of NCC are different to R-RHB but similar with B-RHP and D-RHP. From XRD results, the crystallinity of NCC was found to be approximately 65%. In AFM analysis particle thicknesses have been confirmed to be in the range of (25 ± 15.14) nm or (27 ± 15.14) nm which is almost the same. From TEM analysis particle dimensions have been confirmed to be in the range of (50 ± 29.38) nm width and (550 ± 302.75) nm length with the aspect ratio ~ 11:1 (length/diameter) at a 500 nm scale bar. On the other hand, at a 200 nm scale bar the particle dimensions have been confirmed to be in the range of (35 ± 17) nm width and (275 ± 151.38) nm length with the aspect ratio ~ 8:1. The aspect ratio of individual crystalline domain was determined in TEM analysis which is 10:1 (100/10). Therefore the aspect ratios and dimensions of nanoparticles in NCC suspension are almost the same and in nano-meter scale, as confirmed from both AFM and TEM results. The yield of NCC from B-RHP was found to be approximately 95%, and the recovery of cellulose from R-RHB is about 90%.

Cationic surface modification of nanocrystalline cellulose as reinforcements for preparation of the chitosan-based nanocomposite films

Nanocrystalline cellulose (NCC) is a promising nanofiller for reinforcing chitosan (CTS) film. The flocculation of the NCC suspension in acidic CTS solution is the key problem that makes many properties such as the tensile strength bad. A derivative of nanocellulose, namely cationic dialdehyde cellulose (CDAC), is synthesized in the current study to avoid the flocculation. A CDAC suspension is prepared in a successive oxidation-reductive amination process of NCC. The oxidation of NCC led to smaller rod-like nanocrystals with a reduced crystallinity. The suspension with 1.0% CDAC is well mixed with 1.0% CTS solution. Besides, the tensile strength and anti-swelling properties of CDAC-filled CTS nanocomposite films are improved because of the uniform distribution of CDAC in the CTS matrix plus the intermolecular chemical cross-linking between CDAC and CTS. The tensile strength of CTS-based nanocomposite film with 12% CDAC is about 58.4% higher than that of the pure CTS film.

Nanocrystalline cellulose extracted from pine wood and corncob

The extraction of nanocrystalline cellulose from agro-residues is an interesting alternative to recover these materials. In the present study, nanocrystalline cellulose was extracted from pine wood and corncob. In addition, microcrystalline cellulose was used as a reference to compare results. Initially, the lignocellulosic residues were submitted to delignification pre-treatments. At the end of the process, the bleached fibre was submitted to acid hydrolysis. Additionally, microparticles were obtained from the spray-drying of the nanocrystalline cellulose suspensions. The nanocrystalline cellulose yield for the pine wood was 9.0-% of the value attained for the microcrystalline cellulose. For the corncob, the value was 23.5-%. Therefore, complementary studies are necessary to improve the yield. The spray-dried microparticles showed a crystallinity index of 67.8-% for the pine wood, 70.9-% for the corncob and 79.3-% for the microcrystalline cellulose. These microparticles have great potential for use in the production of polymer composites processed by extrusion.

Polymer blend of PLA/PHBV based bionanocomposites reinforced with nanocrystalline cellulose for potential application as packaging material

The current research discusses the development of poly (lactic acid) (PLA) and poly-(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) reinforced nanocrystalline cellulose bionanocomposites. The nanocrystalline cellulose was derived from waste oil palm empty fruit bunch fiber by acid hydrolysis process. The resulting nanocrystalline cellulose suspension was then surface functionalized by TEMPO-mediated oxidation and solvent exchange process. Furthermore, the PLA/PHBV/nanocrystalline cellulose bionanocomposites were produced by solvent casting method. The effect of the addition of nanocrystalline cellulose on structural, morphology, mechanical and barrier properties of bionanocomposites was investigated. The results revealed that the developed bionanocomposites showed improved mechanical properties and decrease in oxygen permeability rate. Therefore, the developed bio-based composite incorporated with an optimal composition of nanocrystalline cellulose exhibits properties as compared to the polymer blend.

Preparation of Colloidal Properties and Water Dispersible Conductive Polypyrrole Nanocomposite of Nanocrystalline Cellulose

The development of conductive polypyrrole (PPY) processability was successfully achieved by a synthesis of colloidal form with high dispersion stability in aqueous medium. In-situ polymerization method of pyrrole monomers (PY) assisted by aqueous suspension nanocrystalline cellulose (NCC) and the oxidizing agent ammonium persulfate (APS). Facial and fast technique consisted of deposition of PY monomers on the NCC surface via electrostatic attractions between the sulfate groups in NCC surface and the amine group of the PY. Steric hindrance feature of NCC suspension significantly influences the colloid production. The nanocomposite of PPY and NCC (PPY-NCC), purified by centrifuge repeatedly and desiccated by freeze-dry technique. The observations of scanning electron microscopy (SEM) and transmission electron microscopy (TEM), clearly shows the nanostructure modification for nanocomposite and the NCC particles after the composition. The PPY-NCC nanocomposite have very good dispersion stability in aqueous media. The variation between PPY and PPY-NCC in the crystallinity and thermal stability was studied by thermogravimetric analysis (TGA) and x-ray diffraction (XRD) respectively.

Rheological properties of nanocrystalline cellulose suspensions

Rheological behavior, including linear and nonlinear, as well as transient rheology of nanocrystalline cellulose (NCC) suspensions was studied in this work. Two kinds of polymer solutions, aqueous poly(vinyl alcohol) (PVA) with flexible chain structure and aqueous carboxymethyl cellulose (CMC) with semi-rigid chain structure, were used as the suspension media to further explore the role that the interactions among NCC and polymers played during shear flow. The results reveal that NCC has lower values of percolation threshold in the PVA solution than in the CMC one during small amplitude oscillatory shear (SAOS) flow because the flexible PVA chain has higher adsorbed level onto NCC particles than the negatively charged semi-rigid CMC chain, which is further confirmed by the Fourier transformed infrared (FT-IR) spectroscopy tests. As a result, the NCC suspension shows a weak strain overshoot in PVA solution during large amplitude oscillatory shear (LAOS) flow, which cannot be seen on the one in CMC solution. During startup shear flow, both of these two suspensions show evident stress overshoot behavior with the strain-scaling characteristics, indicating the formation of ordered long-term structure of rod-like NCC particles with self-similarity during flow. However, NCC suspension have far stronger stress overshoot response in CMC solution relative to the one in PVA solution. A possible synergy mechanism between NCC and CMC chain is hence proposed.

The fast and effective isolation of nanocellulose from selected cellulosic feedstocks

A new process for the production of nanocellulose from selected cellulose-containing natural materials has been developed. The liquefaction reaction, using glycols and mild acid catalysis (methane sulphonic acid), was applied to four model materials, namely cotton linters, spruce wood, eucalyptus wood and Chinese silver grass. The process contains only four steps, the milling, the glycolysis reaction, centrifugation and final rinsing with an organic solvent. The nanocrystalline cellulose recovery was between 56% and 75%. The crystallinity index was greater than that of the starting materials due to the liquefaction of lignin, hemicelluloses and amorphous cellulose. The final product was a stable, highly concentrated nanocrystalline cellulose suspension in the organic medium. The liquid residue, after the liquefaction of the cotton linters contained significant quantities of levulinic acid. Different sugars were identified in the liquid residues that were derived from cellulose and hemicelluloses during the liquefaction reaction.

The effect of low frequency ultrasound on the production and properties of nanocrystalline cellulose suspensions and films

Suspension of nanocrystalline cellulose (NCC) produced from bleached cotton by controlled sulphuric acid hydrolysis was treated with low frequency ultrasound at 20kHz and 60% amplitude for 0, 1, 2, 5 and 10min and the effects of sonication on the properties of both the cellulose nanocrystals and their aqueous suspensions were investigated. Furthermore, a series of nanocellulose films were manufactured from the suspensions that were sonicated for different periods of time and tested. Laser diffraction analysis and transmission electron microscopy proved that sonication not only disintegrated the large NCC aggregates (Dv50 14.7μm) to individual nanowhiskers with an average length and width of 171±57 and 17±4nm, respectively, but also degraded the nanocrystals and yielded shorter and thinner particles (118±45 and 13±3nm, respectively) at 10-min sonication. The ultrasound-assisted disintegration to nano-sized cellulose whiskers decreased the optical haze of suspensions from 98.4% to 52.8% with increasing time from 0 to 10min, respectively. Sonication of the suspensions significantly contributed to the preparation of films with low haze (high transparency) and excellent tensile properties. With the increasing duration of sonication, the haze decreased and the tensile strength rose gradually. Irrespectively of sonication, however, all films had an outstanding oxygen transmission rate in a range of 5.5–6.9cm3/m2day, and a poor thermal stability.

Morphology and Structural Characteristic of Nanocrystalline Cellulose (NCC) Hydrolyzed from Filter Paper

The aim of this study was to study the morphology and structural characteristic of NCC hydrolyzed from filter paper. The NCCs were extracted by acid hydrolysis at 50°C for 1 hour, using 55% conc. H2SO4 under vigorous mechanical stirring, centrifugation at 12000 rpm in distillate water and followed by homogenizing at 7000 rpm. The morphology and surface profiles of the NCC suspension was characterized using field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and atomic force microscopy (AFM). The crystalline structure of the NCC was evaluated by using X-ray diffraction (XRD) technique. As a result, hydrolysed NCC was found to have a rod liked shape with diameter in the range of 100-300nm length and 10-50nm width, with the aspect ratio value of 10.3 nm. According to XRD investigations, the semi-crystalline cellulose was observed with the presence of an amorphous broad hump and crystalline peaks at 2θ of 15o and 22.7o, respectively. The crystalinity index of the raw filter paper was calculated as 86.7 % and increased to 94.4 % as it was extracted to NCC. Crystallite size of raw filter paper and NCC was calculated as 20.6 nm and 11.4 nm, respectively

Unique viscoelastic behaviors of colloidal nanocrystalline cellulose aqueous suspensions

Unique rheological and phase behaviors of rod-like nanocrystalline cellulose (NCC) suspensions in aqueous media are revealed in the present article. Specifically, the NCC aqueous suspension remained isotropic in a wide NCC concentration range in which the suspension underwent transition from dilute solution to gel, and the relative viscosity of the NCC suspension could be well fitted by the Sato-Teramoto theory in the full concentration range tested. Correspondingly, both zero-shear viscosity and complex viscosity increased monotonically with NCC concentration, and no maximum value was observed along the curves of zero-shear viscosity or complex viscosity versus NCC concentration, indicating a deviation from the lyotropic system. However, a shear-induced birefringence phenomenon was observed, indicating the NCC suspension formed a temporary ordered structure in the external force field but was unable to form an anisotropic (liquid crystalline) phase. The Cox-Merz rule was not applicable for the NCC suspension as a result of oriented domains, i.e., rod-like NCC particles. Moreover, time-concentration superposition was successfully applied to both the storage and loss modulus, attributed to the isotropic feature of the NCC suspension in the tested concentration range. The reason why this NCC suspension remained isotropic could be because of the strong electrostatic repulsions between NCC particles and the weak tendency or driving force of anisotropy formation as a result of the small aspect ratio of NCC particles, Na+ counterions and large amounts of negative charges along the NCC particles. The results suggested that not all the rod-like particles were able to form an anisotropic phase in aqueous suspension, but dominated by various factors.

Preparation and characterization of nanocrystalline cellulose via low-intensity ultrasonic-assisted sulfuric acid hydrolysis

Nanocrystalline cellulose (NCC) was extracted from microcrystalline cellulose via low-intensity ultrasonic-assisted sulfuric acid hydrolysis process. NCC samples were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), particle size distribution (PSD) analysis, Fourier-transformed infrared spectra (FT-IR), X-ray diffraction (XRD), thermogravimetric analysis (TGA) and rheological measurement. It was found that NCC yield reached 40.4 % under the optimum process of low-intensity ultrasonic-assisted sulfuric acid hydrolysis, while it was only 33.0 % in the absence of ultrasonic treatment. Furthermore, the results showed that the two NCC samples obtained from ultrasonic-assisted hydrolysis and conventional hydrolysis were very similar in morphology, both exhibiting rod-like structures with widths and lengths of 10–20 and 50–150 nm, respectively. XRD result revealed that the NCC sample from ultrasonic-assisted hydrolysis contained a small amount of cellulose II and possessed a Segal Crystallinity Index of 90.38 % and a crystallite size of 58.99 A, higher than those of the NCC sample from conventional hydrolysis. Moreover, PSD analysis demonstrated that the former exhibited a smaller value in average particle size than the latter. In addition, rheological measurements showed that the NCC suspensions from the ultrasonic-assisted process exhibited a lower viscosity over the range of shear rate from 0.1 to 100 s−1 in comparison with that prepared in the absence of ultrasonic treatment.