Nanofibrillated cellulose (NFC) reinforced polyvinyl alcohol (PVOH) nanocomposites: properties, solubility of carbon dioxide, and foaming

Polyvinyl alcohol (PVOH) and its nanofibrillated cellulose (NFC) reinforced nanocomposites were produced and foamed and its properties—such as the dynamic mechanical properties, crystallization behavior, and solubility of carbon dioxide (CO₂)—were evaluated. PVOH was mixed with an NFC fiber suspension in water followed by casting. Transmission electron microscopy (TEM) images, as well as the optical transparency of the films, revealed that the NFC fibers dispersed well in the resulting PVOH/NFC nanocomposites. Adding NFC increased the tensile modulus of the PVOH/NFC nanocomposites nearly threefold. Differential scanning calorimetry (DSC) analysis showed that the NFC served as a nucleating agent, promoting the early onset of crystallization. However, high NFC content also led to greater thermal degradation of the PVOH matrix. PVOH/NFC nanocomposites were sensitive to moisture content and dynamic mechanical analysis (DMA) tests showed that, at room temperature, the storage modulus increased with decreasing moisture content. The solubility of CO₂ in the PVOH/NFC nanocomposites depended on their moisture content and decreased with the addition of NFC. Moreover, the desorption diffusivity increased as more NFC was added. Finally, the foaming behavior of the PVOH/NFC nanocomposites was studied using CO₂ and/or water as the physical foaming agent(s) in a batch foaming process. Only samples with a high moisture content were able to foam with CO₂. Furthermore, the PVOH/NFC nanocomposites exhibited finer and more anisotropic cell morphologies than the neat PVOH films. In the absence of moisture, no foaming was observed in the CO₂-saturated neat PVOH or PVOH/NFC nanocomposite samples.     

Comparing microcrystalline with spherical nanocrystalline cellulose from waste cotton fabrics

Microcrystalline cellulose (MCC) and spherical nanocrystalline cellulose (SNCC) were successfully prepared from waste cotton fabrics through acid hydrolysis. The comparative analysis of the morphology and structure between the obtained MCC and SNCC was carried out. The SNCC suspension exhibited higher stability than the MCC suspension. Transmission electron microscopy in combination with atomic force microscopy showed that the cellulose nanospheres with average size of 35?nm were achieved, while the average particle size of MCC was 49?μm. The MCC and SNCC had similar functional groups and crystalline structure as confirmed by Fourier transform infrared spectroscopy and X-ray diffraction analysis, respectively. Viscometric average molecular weight measurement and thermo gravimetric analysis indicated that the degree of polymerization and thermal stability of SNCC was lower than that of MCC. These results should improve understanding of the characteristics of MCC and SNCC derived from waste cotton fabrics and lead to many new applications.     

The behaviour of cationic NanoFibrillar Cellulose in aqueous media

This paper deals, with cationically modified NanoFibrillar Cellulose (cat NFC), obtained by reacting a dissolving pulp with 2,3-epoxypropyl trimethylammonium chloride (EPTMAC). The cat NFC was thoroughly characterized in terms of morphology and physical properties. The dimensions of individual cellulose nanofibrils were determined by atomic force microscopy (AFM) imaging in water and in air. Fibrils as thin as 0.8–1.2 nm were observed in water. The fibril diameter changed upon drying and the average size was further quantified by image analysis. The experiments showed the importance of characterizing nanocellulosic materials in situ before drying. The fibril size in air was confirmed by cryogenic transmission electron microscopy (cryo-TEM), and it was found to be 2.6–3.0 nm. Smooth ultrathin films of cationic NFC were prepared by spincoating on silica substrates. The effect of electrolyte concentration and pH on swelling of the cationic NFC film was studied using a quartz crystal microbalance with dissipation. The results showed that at pH = 8 the cat NFC film was insensitive to electrolyte changes while at pH = 4.5, the water content of the film decreased with increasing ionic strength. The electrophoretic mobility measurements showed a cationic zeta potential for the cat NFC that decreased at increasing pH, verifying the swelling behaviour.     

Comparison of nano- and microfibrillated cellulose films

Nanocellulose is an interesting building block for functional materials and has gained considerable interest due to its mechanical robustness, large surface area and biodegradability. It can be formed into various structures such as solids, films and gels such as hydrogels and aerogels and combined with polymers or other materials to form composites. Mechanical, optical and barrier properties of nanofibrillated cellulose (NFC) and microfibrillated cellulose (MFC) films were studied in order to understand their potential for packaging and functional printing applications. Impact of raw material choice and nanocellulose production process on these properties was evaluated. MFC and NFC were produced following two different routes. NFC was produced using a chemical pretreatment followed by a high pressure homogenization, whereas MFC was produced using a mechanical treatment only. TEMPO-mediated oxidation followed by one step of high pressure (2,000 bar) homogenization seems to produce a similar type of NFC from both hardwood and softwood. NFC films showed superior mechanical and optical properties compared with MFC films; however, MFC films demonstrated better barrier properties against oxygen and water vapor. Both the MFC and NFC films were excellent barriers against mineral oil used in ordinary printing inks and dichlorobenzene, a common solvent used in functional printing inks. Barrier properties against vegetable oil were also found to be exceptionally good for both the NFC and MFC films.     

Nanofibrillated cellulose/nanographite composite films

Though research into nanofibrillated cellulose (NFC) has recently increased, few studies have considered co-utilising NFC and nanographite (NG) in composite films, and, it has, however been a challenge to use high-yield pulp fibres (mechanical pulps) to produce this nanofibrillar material. It is worth noting that there is a significant difference between chemical pulp fibres and high-yield pulp fibres, as the former is composed mainly of cellulose and has a yield of approximately 50 % while the latter is consist of cellulose, hemicellulose and lignin, and has a yield of approximately 90 %. NFC was produced by combining TEMPO (2,2,6,6-tetramethypiperidine-1-oxyl)-mediated oxidation with the mechanical shearing of chemi-thermomechanical pulp (CTMP) and sulphite pulp (SP); the NG was produced by mechanically exfoliating graphite. The different NaClO dosages in the TEMPO system differently oxidised the fibres, altering their fibrillation efficiency. NFC–NG films were produced by casting in a Petri dish. We examine the effect of NG on the sheet-resistance and mechanical properties of NFC films. Addition of 10 wt% NG to 90 wt% NFC of sample CC2 (5 mmol NaClO CTMP-NFC homogenised for 60 min) improved the sheet resistance, i.e. from that of an insulating pure NFC film to 180 Ω/sq. Further addition of 20 (CC3) and 25 wt% (CC4) of NG to 80 and 75 wt% respectively, lowered the sheet resistance to 17 and 9 Ω/sq, respectively. For the mechanical properties, we found that adding 10 wt% NG to 90 wt% NFC of sample HH2 (5 mmol NaClO SP-NFC homogenised for 60 min) improved the tensile index by 28 %, tensile stiffness index by 20 %, and peak load by 28 %. The film’s surface morphology was visualised using scanning electron microscopy, revealing the fibrillated structure of NFC and NG. This methodology yields NFC–NG films that are mechanically stable, bendable, and flexible.     

Aerosol-assisted self-assembly of hybrid Layered Double Hydroxide particles into spherical architectures

Over the last decade, the use of nanocellulose in advanced technological applications has been promoted both due the excellent properties of this material in combination with its renewability. In this study, multilayered thin films composed of nanofibrillated cellulose (NFC), polyvinyl amine (PVAm) and silica nanoparticles were fabricated on polydimethylsiloxane (PDMS) using a layer-by-layer adsorption technique. The multilayer build-up was followed in situ by quartz crystal microbalance with dissipation, which indicated that the PVAm-SiO(2)-PVAm-NFC system adsorbs twice as much wet mass material compared to the PVAm-NFC system for the same number of bilayers. This is accompanied with a higher viscoelasticity for the PVAm-SiO(2)-PVAm-NFC system. Ellipsometry indicated a dry-state thickness of 2.2 and 3.4 nm per bilayer for the PVAm-NFC system and the PVAm-SiO(2)-PVAm-NFC system, respectively. Atomic force microscopy height images indicate that in both systems, a porous network structure is achieved. Young's modulus of these thin films was determined by the Strain-Induced Elastic Buckling Instability for Mechanical Measurements (SIEBIMM) technique. The Young's modulus of the PVAm/NFC films was doubled, from 1 to 2 GPa, upon incorporation of silica nanoparticles in the films. The introduction of the silica nanoparticles lowered the refractive index of the films, most probably due to an increased porosity of the films.     

All-cellulose multilayers: long nanofibrils assembled with short nanocrystals

Self-organized multilayer films were formed by sequential addition of oppositely charged cellulose I nanoparticles. The all-cellulosic multilayers were prepared via adsorption of cationicially modified cellulose nanofibrils (cat NFC) and anionic short crystalline cellulose (CNC) at pH 4.5 and pH 8.3. The properties and build-up behavior of layer-by-layer-constructed films were studied with microgravimetry (QCM-D) and the direct surface forces in these systems were explored with colloidal probe microscopy to gain information about the fundamental interplay between cat NFC and anionic CNC. The importance of the first layer on the adsorption of the consecutive layers was demonstrated by comparing pure in situ adsorption in the QCM-D with multilayer films made by spin coating the first cationic NFC layer and then subsequently adsorbing the following layers in situ in the QCM-D chamber. Differences in adsorbed amount and viscoelastic behavior were observed between those two systems. In addition, a significant pH dependence of cat NFC charge was found for both direct surface interactions and layer properties. Moreover the underlying cellulose layer in multilayer film was established to influence the surface forces especially at lower pH, where the cat NFC chains extensions were facilitated and overall charge was affected by the cationic counterpart within the layers. This enhanced understanding the effect of charge and structure on the interaction between these renewable nanoparticles is valuable when designing novel materials based on nanocellulose.     

Investigation of cross-linked PVA/starch biocomposites reinforced by cellulose nanofibrils isolated from aspen wood sawdust

In this study, a bio-based composite prepared from cross-linked polyvinyl alcohol/starch/cellulose nanofibril (CNF) was developed for film packaging applications. For this purpose, CNF, as reinforcing phase, was initially isolated from aspen wood sawdust (AWS) using chemo-mechanical treatments, and during these treatments, hydrolysis conditions were optimized by experimental design. Morphological and chemical characterizations of AWS fibers were studied by transmission electron microscopy, scanning electron microscopy, Kappa number, and attenuated total reflectance-Fourier transform infrared spectroscopy, as well as National Renewable Energy Laboratory and ASTM procedures. Morphological images showed that the diameter of the AWS fibers was dramatically decreased during the chemo-mechanical treatments, proving the successful isolation of CNF. Moreover, chemical composition results indicated the successful isolation of cellulose, and Kappa number analysis demonstrated a dramatic reduction in lignin content. Mechanical, morphological, biodegradability, and barrier properties of biocomposites were also investigated to find out the influence of CNF on the prepared biocomposite properties. The mechanical results obtained from tensile analysis revealed that Young’s modulus and ultimate tensile strength of biocomposite films were enhanced with increasing CNF concentration, while a significant decrease was observed in elongation at break at the same concentration of CNF. Furthermore, with adding CNF, barrier properties and resistance to biodegradability were increased in films, whereas film transparency gradually declined.     

Preparation and characterization of cationic nanofibrillated cellulose from etherification and high-shear disintegration processes

Oat straw cellulose pulp was cationized in an etherification reaction with chlorocholine chloride. The cationized cellulose pulp was then mechanically disintegrated in two process steps to obtain trimethylammonium-modified nanofibrillated cellulose (TMA-NFC). The materials thus obtained were analyzed by elemental analysis, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), scanning electron microscopy (SEM) and other techniques. A higher nitrogen content of TMA-NFC samples was found by XPS analysis than by elemental analysis, which indicates that the modification occurred mainly on the surface of cellulose fibrils. XPS also confirmed the existence of ammonium groups in the samples. SEM provided images of very fine network structures of TMA-NFC, which affirmed the positive effect of ionic charge on mechanical disintegration process. According to XRD and SEM results, no severe degradation of the cellulose occurred, even at high reaction temperatures. Because of the different properties of the cationic NFC compared to negatively charged native cellulose fibers, TMA-NFC may find broad applications in technical areas, for instance in combination with anionic species, such as fillers or dyes. Indeed, TMA-NFC seems to improve the distribution of clay fillers in NFC matrix.     

Effect of xylan in hardwood pulp on the reaction rate of TEMPO-mediated oxidation and the rheology of the final nanofibrillated cellulose gel

alkali-washed nanofibrillated cellulose (NFC) samples, obtained from hardwood kraft pulp, with different amounts of retained xylan were prepared to study the influence of xylan on the water-retention properties of NFC suspensions. In this study, NFC was produced using an oxoammonium-catalyzed oxidation reaction that converts the cellulosic substrate to a more highly oxidized material via the action of the nitroxide radical species 2,2,6,6-tetramethylpiperidine-1-oxyl. Reduction of the xylan content in NFC was achieved by cold alkali extraction of kraft pulp. The pulps were then oxidized to a set charge under constant chemical conditions, and the reaction time was determined. The xylan content of the feed pulp was found to have a large negative influence on the oxidation rate of the pulp, as the oxidation time shortened when xylan was removed, from 220 min (for 25.2 % xylan content) to 28 min (for 7.3 % xylan content). Following fibrillation by homogenization, the swelling of the NFC was determined by a two-point solute exclusion method. The distribution of hemicellulose over the fibril surface was observed by atomic force microscopy. Xylan was found to be distributed unevenly over the surface, and its presence increased the water immobilized within flocs of NFC, i.e., so-called network swelling. The swelling of the NFC had a large impact on its rheology and dewatering. Comparison of the morphological and swelling properties of the suspensions with their rheological and dynamic dewatering behavior showed that reducing the xylan content in NFC results in a weaker gel structure of the nanocellulose suspension. The results indicate that most of the water is held by the swollen structure by means of xylan particles trapped within the hemicellulose layer covering the fibril surface. Samples with high xylan content had high shear modulus and viscosity and were difficult to dewater.     

Nanofibrillated cellulose: properties reinvestigated

The scientific publications on nanofibrillated cellulose (NFC) were reviewed in the light of recent developments in the field of characterization of NFC, and the evolving understanding of the material. This led to several insights, which challenged few of the established assumptions with regard to e.g. rheological properties of NFC suspensions, and factors affecting tensile strength and barrier properties of NFC films. The realizations may promote the wider application of nanofibrillated celluloses.     

Effect of residual lignin and heteropolysaccharides in nanofibrillar cellulose and nanopaper from wood fibers

Unbleached (UN), oxygen-delignified and fully-bleached (FB) birch fibers with a residual lignin content of ca. 3, 2 and <1 %, respectively, were used to produce nanofibrillated cellulose (NFC) and nanopaper by using an overpressure device. The tensile index, elongation and elastic modulus of nanopaper were compared and the effect of residual cell wall components accessed. Under similar manufacturing conditions, UN NFC produced nanopaper with a density of 0.99 g/cm³, higher than that from FB NFC (0.7 g/cm³). This translated in much lower air permeability in the case of UN nanopaper (1 and 11 mL/min for UN and FB samples, respectively). Fundamentally, these observations are ascribed to the finer fibrils produced during microfluidization of UN fibers compared to those from lower yield counterparts (AFM roughness of 8 and 17 nm and surface areas of 124 and 98 m²/g for NFC from UN and FB fibers, respectively). As a result, values of stress at break and energy absorption of nanopaper from high yield fibers are distinctively higher than those from fully bleached NFC. Interactions of water with the surface and bulk material were affected by the chemical composition and structure of the nanofibrils. While UN nanopaper presented higher water contact angles their sorption capacity (and rate of water absorption) was much higher than those measured for nanopaper from FB NFC. These and other observations provided in this contribution are proposed to be related to the mechanoradical scavenging capacity of lignin in high shear microfluidization and the presence of residual heteropolysaccharides.     

Prediction of elastic properties of nanofibrillated cellulose from micromechanical modeling and nano-structure characterization by transmission electron microscopy

Cellulose-based materials have a great potential in terms of mechanical performance, since crystalline cellulose is known to have excellent stiffness along the main axis. This potential is not completely fulfilled in structural wood materials and in composite materials, due to structural inhomogeneities, misalignment, voids etc. on several length scales. This study investigates the difference in stiffness of nanofibrillated cellulose (NFC) compared to that of cellulose crystallites, based on nanostructural characterization, image analysis and micromechanical modeling. Nanofibrillated cellulose is believed to be composed of a distribution of crystallites in an amorphous matrix, and it is assumed to represent the distribution of the crystalline allomorph I_β. To predict the elastic properties of NFC, a micromechanical model based on a Mori–Tanaka approach and self-consistent scheme was used. The input data, i.e. orientation distribution, aspect ratio and volume fraction of these crystalline regions, were estimated from image analysis of transmission electron micrographs. The model predicts a ca. 56 % loss of stiffness of NFC compared to that of cellulose crystals along the main axis.     

Optimization of the isolation of nanocrystals from microcrystalline cellulose by acid hydrolysis

The objective of this work was to find a rapid, high-yield process to obtain an aqueous stable colloid suspension of cellulose nanocrystals/whiskers. Large quantities are required since these whiskers are designed to be extruded into polymers in the production of nano-biocomposites. Microcrystalline cellulose (MCC), derived from Norway spruce (Picea abies), was used as the starting material. The processing parameters have been optimized by using response surface methodology. The factors that varied during the process were the concentration of MCC and sulfuric acid, the hydrolysis time and temperature, and the ultrasonic treatment time. Responses measured were the median size of the cellulose particles/whiskers and yield. The surface charge as calculated from conductometric titration, microscopic examinations (optical and transmission electron microscopy), and observation of birefringence were also investigated in order to determine the outcome (efficiency) of the process. With a sulfuric acid concentration of 63.5% (w/w), it was possible to obtain cellulose nanocrystals/whiskers with a length between 200 and 400 nm and a width less than 10 nm in approximately 2 h with a yield of 30% (of initial weight).     

Rheology of nanofibrillated cellulose/acrylate systems for coating applications

In this work, the suitability of nanofibrillated cellulose (NFC) as a novel component for wood coatings has been evaluated. NFC was prepared from two different wood pulps with a high pressure homogeniser and a grinder, depending on the initial fibre size of the two pulps. The fibrillation process was monitored using viscosity measurements and scanning electron microscopy. Viscosity measurements were found to be a suitable, reliable and especially fast and easy method for process monitoring, optimization and quality assessment of the NFC fibrillation process. NFC was mixed with four different waterborne acrylic polymer emulsions and analysed regarding its rheological behaviour. The viscosity of the acrylate–NFC suspensions was dominated by the NFC, whereas the polymer type was of minor importance at the tested concentrations. The viscosity increased exponentially after NFC addition and consequently the viscosity of such suspensions would be precisely adjustable in the considered shear range. During accelerated storage at elevated temperatures, the general flow behaviour did not change; only a slight viscosity increase was observed. The study shows that rheology is an important issue that has to be taken into account when applying NFC as additive in water based coating systems and that NFC is suitable as component for coating applications.     

Preparation and properties of cellulose/silver nanoparticle composites with in situ-generated silver nanoparticles using Ocimum sanctum leaf extract

In the present work, silver nanoparticles were in situ-generated in cellulose matrix using Ocimum sanctum leaf extract as a reducing agent. Regenerated wet cellulose films were first immersed in O. sanctum leaf extract and then it was allowed to diffuse into the films. The leaf extract–diffused wet films were dipped in different concentrated aq.AgNO₃ solutions. The leaf extract inside the wet films reduced AgNO₃ into nanosilver. The dry composite films were black in color. Some of the nanoparticles were also formed outside the film in the solution. The nanoparticles were viewed by transmission electron microscopy and scanning electronic microscopy techniques. The composite films showed good antibacterial activity. The cellulose, matrix, and the composite films were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, and thermogravimetric analysis techniques. The tensile properties of the composite films were higher than those of the matrix. These biodegradable films can be used for packaging and medical purposes.     

Stability enhancement of nanofibrillated cellulose in electrolytes through grafting of 2-acrylamido-2-methylpropane sulfonic acid

This study aimed to improve the stability of nanofibrillated cellulose (NFC) in an electrolyte containing system, which was achieved by the grafting of 2-acrylamido-2-methylpropane sulfonic acid (AMPS) via the ceric ammonium nitrate-induced polymerization process. The results indicated that upon grafting the salt resistance and thermal stability of NFC were significantly improved. Moreover, the stability of the modified NFC increased with the AMPS loading. Compared to the control (the original NFC), the poly-AMPS/NFC (357.5 mg/g AMPS) exhibited much improved stability in a 400 mmol/L NaCl solution, and its viscosity was 350 mPa s. The thermogravimetric analysis results showed that the initial decomposition temperature of the modified NFC increased from 265 to 330 °C. Transmission electron microscopy (TEM) observations showed that the main morphologic features of NFC were not altered, suggesting that the grafting reaction occurred on the fiber surface. The modified NFC can have promising industrial applications, such as oil recovery.     

Nanocomposite films based on cellulose reinforced with nano-SiO2: microstructure, hydrophilicity, thermal stability, and mechanical properties

Microcrystalline cellulose/nano-SiO₂ composite films have been successfully prepared from solutions in ionic liquid 1-allyl-3-methylimidazolium chloride by a facile and economic method. The microstructure and properties were investigated by Fourier transform infrared spectroscopy, wide-angle X-ray diffraction, scanning electron microscopy, transmission electron microscopy, water contact angle, thermal gravimetric analyses, and tensile testing. The results revealed that the well-dispersed nanoparticles exhibit strong interfacial interactions with cellulose matrix. The thermal stability and tensile strength of the cellulose nanocomposite films were significantly improved over those of pure regenerated cellulose film. Furthermore, the cellulose nanocomposite films exhibited better hydrophobicity and a lower degree of swelling than pure cellulose. This method is believed to have potential application in the field of fabricating cellulose-based nanocomposite film with high performance, thus enlarging the scope of commercial application of cellulose-based materials.     

High strength cellulose composite films reinforced with clay for applications as antibacterial materials

High strength cellulose composite films with antibacterial activities were prepared by dispersing montmorillonites (MMT) into cellulose solution in LiOH/urea aqueous solvent followed by regeneration in ethanol coagulation bath, and then by soaking in 5 wt% hexadecylpyridine bromide ethanol solutions to induce the antibacterial action. The cellulose/MMT composite films were characterized by field emission scanning electron microscopy, transmission electron microscopy, thermogravimetric analysis, FTIR, UV-spectra, wide angle X-ray diffraction and mechanical test. The results revealed that MMT was dispersed well in the cellulose matrix to form layer structure with a thickness of approximately 3 nm. The mechanical properties of the cellulose/MMT composite films were significantly improved to achieve 132 MP for tensile strength as a result of the MMT delamination. The hexadecylpyridine bromide was fixed well in the cellulose/MMT matrix through cation exchange, leading to the excellent antibacterial activities against Staphylococcus aureus and Escherichia coli, which is important in their practical applications.     

Biobased films prepared from NaOH/thiourea aqueous solution of chitosan and linter cellulose

In the present study, films based on linter cellulose and chitosan were prepared using an aqueous solution of sodium hydroxide (NaOH)/thiourea as the solvent system. The dissolution process of cellulose and chitosan in NaOH/thiourea aqueous solution was followed by the partial chain depolymerization of both biopolymers, which facilitates their solubilization. Biobased films with different chitosan/cellulose ratios were then elaborated by a casting method and subsequent solvent evaporation. They were characterized by X-ray analysis, scanning electron microscopy (SEM), atomic force microscopy (AFM), thermal analysis, and tests related to tensile strength and biodegradation properties. The SEM images of the biofilms with 50/50 and 60/40 ratio of chitosan/cellulose showed surfaces more wrinkled than the others. The AFM images indicated that higher the content of chitosan in the biobased composite film, higher is the average roughness value. It was inferred through thermal analysis that the thermal stability was affected by the presence of chitosan in the films; the initial temperature of decomposition was shifted to lower levels in the presence of chitosan. Results from the tests for tensile strength indicated that the blending of cellulose and chitosan improved the mechanical properties of the films and that an increase in chitosan content led to production of films with higher tensile strength and percentage of elongation. The degradation study in a simulated soil showed that the higher the crystallinity, the lower is the biodegradation rate.