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.     

Nanofibrillated cellulose: surface modification and potential applications

Interest in nanofibrillated cellulose has been increasing exponentially because of its relatively ease of preparation in high yield, high specific surface area, high strength and stiffness, low weight and biodegradability etc. This bio-based nanomaterial has been used mainly in nanocomposites due to its outstanding reinforcing potential. Solvent casting, melt mixing, in situ polymerization and electrospinning are important techniques for the fabrication of nanofibrillated cellulose-based nanocomposites. Due to hydrophilic character along with inherent tendency to form strong network held through hydrogen-bonding, nanofibrillated cellulose cannot uniformly be dispersed in most non-polar polymer matrices. Therefore, surface modification based on polymer grafting, coupling agents, acetylation and cationic modification was used in order to improve compatibility and homogeneous dispersion within polymer matrices. Nanofibrillated cellulose opens the way towards intense and promising research with expanding area of potential applications, including nanocomposite materials, paper and paperboard additive, biomedical applications and as adsorbent.     

Nanofibrillated cellulose/carboxymethyl cellulose composite with improved wet strength

In this paper, nanofibrillated cellulose/carboxymethyl cellulose (CMC) composite films were prepared using tape casting. The obtained transparent films showed shear induced partial alignment of fibrils along the casting direction, resulting in birefringence in cross polarized light. The carboxyl groups of CMC could be further utilized to create ionic crosslinking by treatment with glycidyl trimethyl ammonium chloride (GTMA). The GTMA treated composite films had improved mechanical properties both in wet and dry state. The chemical composition and morphologies of composites were analyzed with X-ray photoelectron spectroscopy, elemental analysis, scanning electron microscopy and wide-angle X-ray scattering.     

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.     

Nanofibrillated cellulose originated from birch sawdust after sequential extractions: a promising polymeric material from waste to films

The residual cellulose of wood processing waste, sawdust, which was leftover after sequential hot-water extraction processes to isolate hemicelluloses and lignin in a novel forest biorefinery concept, was explored as the starting material for preparation of a highly value-added polymeric material, nanofibrillated cellulose (NFC) also widely termed as cellulose nanofiber, which has provided an alternative efficient way to upgrade sawdust waste. The residual cellulose in sawdust was converted to a transparent NFC suspension in water through the 2,2,6,6-tetramethylpiperidine-1-oxyl radical/NaClO/NaBr oxidization approach. The resultant NFC with a dimension of ca. 5 nm in width and hundreds of nanometers in length were further processed into NFC films. The morphological features of the NFC suspension and its films were assessed by transmission electron microscopy and scanning electron microscopy. Highly even dispersion of NFC fibrils in the films originated from sawdust feasibly contributes to the outstanding mechanical performance of the films. NFC suspension with higher carboxylate content and its resultant NFC films were found to show higher transmission of light.     

Ultra-lightweight cellulose foam material: preparation and properties

Ultra-lightweight cellulose foams were prepared by regeneration of sodium dodecyl sulfate (SDS)/cellulose/NaOH/urea blend solution via mechanical agitation and then freeze-drying. The morphology and properties of the blend solutions and foams were investigated via optical microscope, rheometer, BET and SEM. As a result, it was found that the inclusion complex structure between cellulose macromolecules and the solvent molecules was not destroyed. Moreover, the bubbles were about 20–50 μm in the solutions and larger (>100 μm) in the foams. Not only the micropores (bubbles) but also the nanopores could be observed in the wet and dried foams. The cellulose foams possessed ultra-low density of about 30 mg/cm³ and high specific surface area. The result of X-ray diffraction and Fourier transform infrared spectroscopy indicated that the cellulose foams were transited from cellulose I to cellulose II after dissolution and gelation. Bubbles inside the wet foams weakened the mechanical properties, but inversely increased the mechanical properties in the dried foams. Typical “J”-shaped curves were observed during the mechanical test, which revealed good compressive strength of dried foams. In this work, cellulose foams with ultra-lightweight and good mechanical properties were obtained, which exhibited great potentials for further development and comprehensive utilization of cellulose.     

Viability of 4,5-dihydro-1,2,3,4-oxatriazoles reinvestigated

The first procedures to prepare 4-bromo-4-methylpentanal and 4-azido-4-methylpentanal are reported. The latter compound and also the parent 4-azidobutanal do not lead to 4,5-dihydro-1,2,3,4-oxatriazoles by intramolecular 1,3-dipolar cycloaddition, although it was claimed to be so in the literature. The NMR spectroscopic data of such heterocycles reported previously do not agree with those of similar substances and are incompatible with (13)C NMR spectroscopic chemical shifts calculated by quantum chemical methods in the presented work. These calculations show furthermore that the intramolecular cycloaddition of 4-azidobutanals to give the title compounds is strongly endothermic and thus most probably not possible.     

Thermal properties of oxidized cellulose

Three series of oxidized celluloses – 2,3-dialdehyde celluloses (DACs), 2,3-dicarboxycelluloses (DCCs) and sodium 2,3-dicarboxycelluloses (NaDCCs) — were prepared, having incremental changes in their degrees of oxidation. Their thermogravimetric analysis (TG) and differential thermal analysis (DTA) were studied. It was found that oxidation generally destabilized cellulose at lower temperatures (below 250 °C), but at higher temperatures the oxidized products were found to be more stable. Cellulose, DACs, and DCCs all showed final weight losses in the region of 80–85%. However, 80% NaDCC and 98% NaDCC showed weight losses of only 30 and 37%, respectively.NCL Communication No. 6051.     

Rheological properties of sulfate cellulose

Rheological properties of concentrated aqueous solutions of sulfate cellulose prepared by various sulfation methods were studied. Information on the variation of structure of the concentrated solutions under action of external forces during viscous current depending on sulfate cellulose molecular parameters was obtained.     

Elastic properties of cellulose nanopaper

Nanopaper is a transparent film made of network-forming nanocellulose fibers. These fibers are several micrometers long with a diameter of 4–50 nm. The reported elastic modulus of nanopaper often falls short of even conservative theoretical predictions based on the modulus of crystalline cellulose, although such predictions usually perform well for other fiber composite materials. We investigate this inconsistency and suggest explanations by identifying the critical factors affecting the stiffness of nanopaper. A similar inconsistency is found when predicting the stiffness of conventional paper, and it is usually explained by the effects introduced during drying. We found that the effect of the drying cannot solely explain the relatively low elastic modulus of nanopaper. Among the factors that showed the most influence are the presence of non-crystalline regions along the length of the nanofibers, initial strains and the three-dimensional structure of individual bonds.     

Thermal properties of cellulose carbamate

The thermal properties of cellulose carbamate with various nitrogen content are discussed. Thermal analysis was performed in air and under nitrogen atmosphere. The increase in the nitrogen content in cellulose carbamate brings about only a shift of the maximum decomposition rate towards lower temperatures. It can be concluded that cellulose carbamate heated to 320 °C is readily dehydrated and cross-linked, which results in the formation of aromatic structure.     

Dielectric properties of moist cellulose

The dielectric constant ?′ and the dielectric loss ?″ for cellulose fiber were measured over a frequency band 0.2 to 10 Mc/sec and a temperature range from ?20 to 80°C. Also, the variation of the dielectric behavior with relative humidity was measured at 25°C. From these data, both the specific resistivity R_s and the dissociation energy U₀ were calculated. The results showed that the dielectric constant increased with frequency and temperature. This may be due to the increase in the rotation and the polarization of the flexible part in the fiber. The variation of the dielectric loss with temperature showed a maximum absorption corresponding to the β-relaxation. For the moist fiber, it is found that as the relative humidity increases, the dielectric constant and the dielectric loss increase. This increase may be due to the presence of polar water molecules, to the freeing of the polar groups, and to the freeing of the ions in the fiber molecule as well as to the increase in the number of OH^? and H⁺ ions resulting from the ionization of water. A relation between the dielectric constant and resistivity at different humidities is represented graphically. From this relation, it is found that the dissociation energy is equal to 0.318 × 10^?12 and 5.46 × 10^?12 erg below and above 52% RH, respectively.     

Single crystals of cellulose IVII: Preparation and properties

Lamellar single crystals of cellulose were obtained from dilute solutions of low-DP cellulose triacetate, by deacetylation followed by precipitation. At temperatures between 150 and 160°C, pure cellulose IV_II crystals were obtained whereas at temperatures between 90 and 150°C, hybrid crystals, having cellulose II and cellulose IV_II domains cocrystallized in syntaxy were obtained. In both cases, the crystals were identified and characterized by electron diffraction. When the solutions leading to cellulose IV_II were seeded with native cellulose microfibrils, a shish-kebab structure resulted with the microfibrils decorated by cellulose II lamellae.     

Synthesis and properties of cellulose phosphates

Conditions for modification of cellulose under laboratory and industrial conditions with A-1 and A-2 fire retardants as P,N-containing modifiers were examined with the aim to prepare difficultly inflammable materials. The degrees of crystallinity of the products, crystallite size, and features of their thermal decomposition in air in the range 20–500°C were examined. Original Russian Text N.K. Luneva, L.I. Petrovskaya, T.I. Ezovitova, 2007, published in Zhurnal Prikladnoi Khimii, 2007, Vol. 80, No. 11, pp. 1899–1903.     

Electrokinetic properties of processed cellulose fibers

Natural cellulose fibers (cotton) comprise several noncellulose compounds (hemicellulose, wax and pectin substances) and cationic impurities which cause problems during different adsorption processes such as dying, or final fiber finishing and coating. Therefore the chemical purification (NaOH boiling, enzymatic purification, demineralization, extraction or oxidative bleaching) is the most important step in cellulose textile finishing. Alternative ways to describe the success of different processes in fiber purification which result in distinct surface charge and hydrophilicity are the determination of electrokinetic properties and the water uptake of textile fibers. The zeta-potential (ζ) was determined by streaming potential measurement as a function of the pH. From the ζ–pH functions the adsorption potential for all ionic species Φ_i (i.e. ( , in the case of potassium chloride solutions), the charge densities σ^k and the pK values are calculated according to the Börner and Jacobasch model.

The degradation and removal of hydrophobic noncellulose compounds which cover the primary hydroxyl and carboxyl groups of the cellulose polymer is clearly shown by an increase of the negative ζ of the plateau, which is in good agreement with the electrokinetic parameters of cotton samples determined by the Börner and Jacobasch model. The electrokinetic parameters determined by the Börner and Jacobasch model can be used to describe the adsorption/dissociation ability of textile fibers. The progress of the fiber processing (cleaning) is reflected by the surface charge as well as the hydrophilicity of the fiber.     

Rheological properties of cellulose nanocrystal-embedded polymer composites: a review

Nanotechnology provides useful insights into the behavioural properties of materials from the nanoscale point of view, enabling researchers to develop new materials that were previously inconceivable. Cellulose is an ideal candidate for nanomaterial for nanotechnology because of its nanofibrillar structure, abundance, renewability, biodegradability and eco-friendly nature. Nanocrystalline cellulose materials have become the focus many studies related to these materials and their applications. This review summarises the current knowledge on the field of nanomaterials, focussing mainly on the rheological behaviour of polymer nanocomposites embedded with nanocrystalline cellulose. This review will enable better understanding of the use of nanocrystalline cellulose for the development and applications of cellulose nanocrystal-based nanocomposites.     

Dilute solution properties of sodium cellulose disulphate

Sodium cellulose sulphate (NaCaS), with degree of substitution (DS) of 1.90, was synthesized by reacting samples of cellulose, covering a wide range of average molecular weight, with S03/dimethyl formamide complex. A solution of NaCS in 0.5 M aq. NaCl was studied by solution viscometry, light scattering and membrane osmometry. The solution was dialysed against solvent. The following MarkHouwink-Sakurada equation and relation between the z-average radius of gyration and weightaverage molecular weight, Mw, were established for $\text{7.2 × 10}{}^4\text{?}\text{M}{}_{\mathrm{w}}\text{? 1.5 × 10}{}^6\text{at 25°}$.The NaCS with salt system was analysed according to the theory of linear non-ionic polymers. Flory's viscosity parameter φ is significantly molecular weight dependent. The partially free draining effect and the excluded volume effect were estimated and the former predominated. The unperturbed chain can be regarded as Gaussian and its dimension A was found to be 1.21 × 10^?8 cmand the conformation parameter a was 2.9.     

Surface properties of cellulose modified by imidazolidinone

The influence of the modification of cellulose fibres by the imidazolidinone derivative 1,3-dimethyl-4,5-dihydroxyethylene urea (DMeDHEU) on fibre surface free energy and electrochemical potential was studied. The presence of DMeDHEU in the cellulose structure was confirmed by infrared spectral analysis. The surface free energy of untreated and treated cellulose fibres was determined from the results of thin-layer wicking, where the rate of liquid penetration into the cellulose fabric was measured. Using the van Oss-Chaudhury-Good theoretical approach, apolar, γ _S ^LW , polar electron-acceptor, γ _S ⁺, and electron-donor, γ _S ⁻, components of the surface free energy were calculated. The electrokinetic potential was determined from the results of steaming potential measurements. The results revealed that the incorporation of DMeDHEU into the cellulose structure lead to a decrease in the value of γ _S ⁻, whereas the values of γ _S ^LW and γ _S ⁺ remained almost unchanged. Despite their decreased γ _S ⁻ value, the treated cellulose fibres still represent a monopolar solid with a strongly expressed electron-donor component. The values of ΔG _iw and ΔG _iwi suggested that both untreated and treated cellulose samples could be considered hydrophilic substrates. The results of the electrokinetic potential measurements showed that the consumption of cellulose hydroxyl groups in the crosslinking reaction with DMeDHEU did not decrease the electrokinetic properties of the cellulose surface.