Novel aqueous spongy foams made of three-dimensionally dispersed wood-fiber: entrapment and stabilization with NFC/MFC within capillary foams

This article describes the preparation of novel aqueous spongy foams that are composed of three-dimensionally distributed wood-fiber networks stabilized with nanofibrillate cellulose (NFC) and/or microfibrillated cellulose (MFC). The free standing aqueous spongy foams were prepared with the entrapment of NFC and/or MFC—stabilized air-in-water (A/W) capillary foams using “gel trapping technique”. The stability of spongy foams could be controlled by manipulating the volume fraction of NFC and/or MFC and a secondary liquid immiscible with the continuous phase of the NFC and/or MFC suspension. Possible morphology and mechanical distribution of NFC and/or MFC within spongy foams were verified with optical microscope, SEM, and functional load-bearing method. Owing to three-dimensionally dispersed wood-fiber structure, ultra-lightweight (0.01–0.06 g/cm³), high porosity (>90%), and microporous (10–80 μm), the NFC and/or MFC reinforced spongy foams, improved compressional strength-vertical direction obviously, from 0.0 to more than 13.78 kPa.     

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/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.     

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.     

Influence of drying restraint on physical and mechanical properties of nanofibrillated cellulose films

Nanofibrillated cellulose (NFC) is a renewable and biodegradable fibril that possesses high strength and stiffness resulting from high level hydrogen bonding. Films made from NFC shrink and distort as they transition from a wet state (20 wt% solids) to a state of moisture equilibrium (90 wt% solids at 50 % RH, 23 °C). Material distortions are driven by development of moisture gradients within the fibril network and effectively reduce mechanical performance. For this study, NFC was extracted from softwood holocellulose by first employing a chemical pretreatment [(2,2,6,6-tetramethylpiperidin-1-yl)oxyl catalyzed oxidation] followed by mechanical fibrillation using ultrasound energy. To assess the problem of film distortion, neat NFC films were dried at 50 % RH, 23 °C under one of the following three restraint conditions: fully restrained, partially restrained, and uniaxially drawn. The influence of restraint condition on the resulting physical and mechanical properties was evaluated. Raman and X-ray results showed that fibrils in the uniaxially drawn specimens tended to align with the drawing axis, whereas no in-plane orientation effects were observed for the fully or partially restrained specimens. Fully restrained specimens had a respective strength and stiffness of 222 MPa and 14 GPa in every (in-plane) direction. However, samples that were wet-drawn to a 30 % strain level had a respective strength and stiffness of 474 MPa and 46 GPa in the direction of draw. Mechanical properties for axially drawn specimens had both fibril alignment and fibril straightening contributions.     

Cationic gel crystals of lightly cross-linked poly(2-vinylpyridine) spheres (170∼180 nm in diameter) in the deionized aqueous suspension

Colloidal crystallization of deionized suspensions of the cationic gel spheres of lightly cross-linked poly(2-vinylpyridine), AIBA-P2VP (170～180 nm in diameter) has been studied from the microscopic observation, morphology, phase diagram, and elastic property. Critical concentrations of melting that coexisted with ion-exchange resins were low compared with those without resins and decreased as the degree of cross-linking decreased. The density of a gel sphere in suspension state (ρ), i.e., weight percent of the gel spheres divided by the corresponding volume percent, was between 0.5 and 0.8, and decreased as the degree of cross-linking of the spheres decreased. The ρ values also decreased with decreasing size of gel spheres, which supports the small P2VP gel spheres being softer than the large ones. The closest intersphere distances of the crystals were much longer than the hydrodynamic diameters of the gel spheres especially at low sphere concentrations. Fluctuation parameters evaluated from the rigidities of the crystals of AIBA-P2VP (0.05～0.09) were similar to those of gel crystals of cationic gel spheres of lightly cross-linked poly(2-vinylpyridine) spheres coated with poly(ethylene glycol), 400 nm in diameter, and thermo-sensitive gel spheres of pNIPAm, poly(N-isopropylacrylamide), but larger than those of typical colloidal hard spheres. The stable crystal phase formed beyond the adsorbed monolayer of cationic gel spheres on the surface of the substrate. These experimental findings support important role of the extended electrical double layers around the cationic gel spheres in addition to the excluded volume effect of the sphere themselves on the crystallization.     

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.     

From paper to nanopaper: evolution of mechanical and physical properties

In the present work the evolution of physical and mechanical properties of papers and nanopapers is studied. Handsheets made of eucalyptus fibres reinforced with 0, 25, 50, 75 and 100 wt% of nanofibrillated cellulose (NFC) content were fabricated using a Rapid Köthen-like equipment. The obtained papers and nanopapers were physical- and mechanically-characterized. The results showed a significant increase in density and a reduction of porosity in the samples during their transition from paper to nanopaper; besides, nanopapers were more transparent and smoother than normal papers. These physical changes where more evident with increasing amounts of NFC. Regarding mechanical properties, nanopapers with a 100 wt% content of NFC improved their strength and rigidity in 228 and 317 %, respectively, in comparison with normal papers. The evolution of strength and rigidity from paper to nanopaper was linear in relation to the amount of NFC, which means that the ultimate tensile strength was mainly dependant on nanofibril failure.     

Study of quasi-solid electrolyte in dye-sensitized solar cells using surfactant as pore-forming materials in TiO<Subscript>2</Subscript> photoelectrodes

A novel polymer gel electrolyte was used to improve the performance and long-term stability in dye-sensitized solar cells (DSSCs). The polymer gel electrolyte (PGE) was prepared by mixing 5 wt% poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) and 2 % TiO₂ nanoparticles. The conductivity of PGE with P25 reached 9.98 × 10^?3 S/cm, which increased by 34.9 % compared with 7.40 × 10^?3 S/cm of PGE without P25, and the diffusion coefficient was also increased by 19.0 %. Different photoelectrodes were obtained by using three kinds of surfactants (cetylamine, octadecylamine, and P123) as pore-forming materials, and their morphologies were contrasted through scanning electron microscopy (SEM). The results showed that gel electrolyte can increase the short-circuit current density (J _sc) from 11.01 to 12.99 mA/cm² in DSSCs. Moreover, unlike the liquid electrolyte, the gel electrolyte is more conducive to the TiO₂ photoelectrodes with larger pores. In conclusion, the efficiency of DSSC with gel electrolyte and P123 as pore-forming material was 6.73 %, which was 12 % higher than the liquid electrolyte in the same test condition. In addition, the sealed gel electrolyte DSSCs showed better stability than did liquid electrolyte DSSCs during nearly 600 h.     

Soy protein–nanocellulose composite aerogels

Organic aerogels based on two important and widely abundant renewable resources, soy proteins (SP) and nanofibrillar cellulose (NFC) are developed from precursor aqueous dispersions and a facile method conducive of channel- and defect-free systems after cooling and freeze-drying cycles that yielded apparent densities on the order of 0.1 g/cm³. NFC loading drives the internal morphology of the composite aerogels to transition from network- to fibrillar-like, with high density of interconnected cells. Composite aerogels with SP loadings as high as ca. 70 % display a compression modulus of 4.4 MPa very close to that obtained from reference, pure NFC aerogels. Thus, the high compression modulus of the composite system is not compromised as long as a relatively low amount of reinforcing NFC is present. The composite materials gain moisture (up to 5 %) in equilibrium with 50 % RH air, independent of SP content. Furthermore, their physical integrity is unchanged upon immersion in polar and non-polar solvents. Fast liquid sorption rates are observed in the case of composite aerogels in contact with hexane. In contrast, water sorption is modulated by the chemical composition of the aerogel, with an important contribution from swelling. The potential functionalities of the newly developed SP–NFC composite green materials can benefit from the reduced material cost and the chemical features brought about the amino acids present in SPs.     

Synthesis of high-performance superabsorbent glycerol acrylate-cross-linked poly (acrylic acid)

Glycerol acrylate (GA) is synthesised by an acryloylation reaction with acryloyl chloride. An ester was used as a cross-linking agent at varying proportions in the synthesis of poly acrylic acid (PAA). The amount of cross-linking density in the product (GA-PAA) and degree of neutralisation determine the absorbency of the polymer samples. A sample of GA-PAA containing 0.8 % GA was discovered to absorb 395 and 66 g/g of water and saline solution, respectively. Different solvent uptakes were tested with the sample showing varying capacity for different solvents. The temperature of the reaction was maintained at 60 °C and a reaction time of 2½ h. FTIR, TGA, SEM and XRD analyses were used to characterise the products.     

Development of nanofibrillated cellulose coated with gold nanoparticles for measurement of melamine by SERS

The objective of this study was to develop nanofibrillated cellulose (NFC)-based substrate for rapid detection of melamine in milk by surface-enhanced Raman spectroscopy (SERS). NFC were served as a highly porous platform to load with gold nanoparticles (AuNPs), which can be used as a flexible SERS substrate with nanoscale roughness to generate strong electromagnetic field in SERS measurement. The NFC/AuNP substrate was characterized by UV–Vis spectroscopy and electron microscopy. Milk samples contaminated by different concentrations of melamine were measured by SERS coupled with NFC/AuNP substrate. The spectral data analysis was conducted by multivariate statistical analysis [i.e. partial least squares (PLS)]. Satisfactory PLS result for quantification of melamine in milk was obtained (R = 0.9464). The detection limit for melamine extracted from liquid milk by SERS is 1 ppm, which meets the World Health Organization’s requirement of melamine in liquid milk. These results demonstrate that NFC/AuNP substrate has improved homogeneity and can be used in SERS analysis for food safety applications.     

Rigidity of the crystals of thermo-sensitive gel spheres of poly (N-isopropyl acrylamide) in the deionized aqueous media as studied by the reflection spectroscopy in the sedimentation equilibrium

Reflection spectroscopy of deionized suspensions of the thermo-sensitive gels of poly (N-isopropylacrylamide) with various degrees of cross-linking were made in the sedimentation equilibrium at 20 °C. Rigidity of the crystals increased as sphere concentration increased and increased slightly as the degree of the cross-linking of the gel spheres increased. The fluctuation parameters of the gel crystals were between 0.05 and 0.07 and slightly larger than those of typical hard-sphere systems. These experimental results emphasize that the gel crystals are soft compared with those of typical hard-sphere systems and role of the extended electrical double layers for the crystallization of gel spheres is important but weak compared with that of hard colloidal spheres.     

The state of carboxymethylated nanofibrils after homogenization-aided dilution from concentrated suspensions: a rheological perspective

The rheological properties of a carboxymethylated (D.S. ≈ 0.1) nanofibrillated cellulose (NFC) were investigated at different solid contents. The critical overlap concentration was determined to be in the range between 0.04 and 0.07 % (w/w) using shear stress versus shear rate measurements. From the critical overlap concentration using the simple Mason excluded volume formalism, the apparent aspect ratio was estimated to be 75 [at a critical overlap concentration of 0.04 % (w/w)]. The aspect ratio of the NFC system was also estimated by using the Einstein–Simha equation together with the intrinsic viscosity value of the system (corrected for the electroviscous effects). The obtained value was found to be around 80, which is in good agreement with the value obtained from the excluded volume calculation. Further, by combining oscillatory measurements and the equation of Shankar et al. the apparent fibril length was determined to be 4 µm. As the production of NFC through homogenization occurs at concentrations far above the critical overlap concentration an NFC-gel is constituted by a severely entangled structure. The disentanglement of the fibrils is therefore difficult and the employed dilution method was found not to lead to fully liberated nanofibrils, which was also indicated by atomic force microscopy-imaging.     

The influence of shear on the dewatering of high consistency nanofibrillated cellulose furnishes

This paper demonstrates a way to utilize the rheological properties of high consistency microfibrillated and nanofibrillated cellulose (MFC and NFC) based furnishes for improved dewatering. This is relevant to a new manufacturing platform that is being developed to form composite webs from suitable mixtures of MFC or NFC, traditional pulp fibres and pigments. The studied furnishes were evaluated in the consistencies range of 5–15 % with an MCR 300 rheometer and an immobilization cell. This setup enables us to characterize the rheology of the samples before and during the dewatering process. Classical rheological methods are used to characterise MFC and NFC furnishes. Yield stress as an indicator of the flocculated network strength was found to increase with the consistencies, following the increase in elastic moduli, which indicated a gel-like strongly flocculated matrix. The shear thinning properties of furnishes are observed to follow the Oswald’s rheological model on a wide range of shear rates. It was found that when the MFC and NFC furnishes were dewatered under vacuum conditions, the final solids content was increased with application of shear. This behaviour is more pronounced for furnishes which contained the more swollen NFC (higher WRV, i.e. higher zeta potential). This effect is further exemplified by the change of the complex and dynamic viscosities during the dewatering. The shear rate, the fibre content, and the furnish consistencies were also found to influence the dewatering rate.     

Colloidal crystallization of thermo-sensitive gel spheres of poly (N-isopropyl acrylamide). Influence of degree of cross-linking of the gels

Morphology, phase diagram, and reflection spectroscopy of the colloidal crystals of thermo-sensitive gel spheres, poly (N-isopropylacrylamide) having degrees of cross-linking 10 and 2?mol.% (pNIPAm(200?C10) and pNIPAm(200?C2)) were studied. Giant colloidal single crystals formed at very low gel concentrations. Critical concentrations of melting increased as the degree of cross-linking decreased in the range from 10 to 0.5?mol.% and/or suspension temperature increased from 20 to 45?°C. The critical concentration decreased sharply as the suspensions were deionized with coexistence of the mixtures of cation- and anion-exchange resins. Density of a gel sphere (gel concentration in weight percent divided by that in volume percent) increased sharply as the degree of cross-linking and/or temperature increased. These results demonstrated that the colloidal crystallization takes place by the extended electrical double layers formed around the gel spheres in addition of the excluded-volume effect of the gels. Most of the researchers including the authors have believed that the crystallization of the gel spheres takes place by the excluded-volume effect. However, the present work clarified that the colloidal interfaces, which are inevitable for the formation of the electrical double layers, are formed firmly between the water phase and gel spheres, though the gel spheres contain a lot of water molecules in the sphere region.     

Lateral sol–gel cross-linking of polyurethane using the a grafted triethoxysilyl group

3-Triethoxysilylpropyl isocyanate was used to graft a triethoxysilyl group to polyurethane (PU), and the grafted triethoxysilyl groups were used to cross-link PU chains through a sol–gel process. The soft segment melting temperature and enthalpy change were not significantly altered by the sol–gel cross-linking. The sol–gel cross-linked PUs exhibited significantly increased tensile strength and better tensile strain compared to the plain linear PU: the maximum stress and strain increased to 41 MPa and 1,972 %, respectively. Control series containing tetraethyl orthosilicate, a series without cross-linking, was also prepared for comparison with the sol–gel cross-linked PU series. The control series did not exhibit the increased tensile strength shown by the sol–gel cross-linked PU series. The cyclic shape memory tests demonstrated that the shape recovery was as high as 97 %, and both shape recovery and shape retention remained high after the four repeated tests. The sol–gel cross-linked PU series exhibited enhanced low-temperature flexibility compared to the plain linear PU due to the flexible silyl cross-linking group.     

Topochemical acetylation of cellulose nanopaper structures for biocomposites: mechanisms for reduced water vapour sorption

Moisture sorption decreases dimensional stability and mechanical properties of polymer matrix biocomposites based on plant fibers. Cellulose nanofiber reinforcement may offer advantages in this respect. Here, wood-based nanofibrillated cellulose (NFC) and bacterial cellulose (BC) nanopaper structures, with different specific surface area (SSA), ranging from 0.03 to 173.3 m²/g, were topochemically acetylated and characterized by ATR-FTIR, XRD, solid-state CP/MAS ¹³C-NMR and moisture sorption studies. Polymer matrix nanocomposites based on NFC were also prepared as demonstrators. The surface degree of substitution (surface-DS) of the acetylated cellulose nanofibers is a key parameter, which increased with increasing SSA. Successful topochemical acetylation was confirmed and significantly reduced the moisture sorption in nanopaper structures, especially at RH = 53 %. BC nanopaper sorbed less moisture than the NFC counterpart, and mechanisms are discussed. Topochemical NFC nanopaper acetylation can be used to prepare moisture-stable nanocellulose biocomposites.     

Gelation behavior of cellulose in NaOH/urea aqueous system via cross-linking

Sol–gel transition of cellulose solution in NaOH/urea aqueous solution with the addition of epichlorohydrin (ECH) was investigated by rheological means. The gelation was controlled by a synergy of chemical and physical cross-linking processes, namely, the etherification reaction between cellulose and ECH as well as the self-association and entanglement of cellulose chains via hydrogen bonding re-construction in NaOH/urea. The results revealed that the cross-linker concentration, cellulose concentration and temperature played important roles in the gelation behavior. The gel time decreased with increasing either ECH or cellulose concentration, and the gel temperature dropped from 38 to 28 °C with an increase of cellulose concentration from 4 to 6 wt%, i. e. easier gelation was reached with higher cross-linker concentration, cellulose concentration or temperature, since higher cross-linker or cellulose concentration led to more network junctions via chemical or physical cross-linking, while higher temperature was favorable to both the etherification reaction and re-construction of cellulose hydrogen bonds. The compressive modulus of cellulose/ECH hydrogels was improved a lot by increasing either cellulose or ECH concentration, indicating the chemical cross-linking obviously improved the mechanical property, on the other hand, the swelling property could be tunable by changing the gelation parameter. This work supplied useful information to the control and optimization of the structure and properties of cellulose based hydrogels.     

Concentration effects on the isolation and dynamic rheological behavior of cellulose nanofibers via ultrasonic processing

Chemical pretreatment combined with high-intensity ultrasonication was performed to disintegrate cellulose nanofibers from poplar wood powders. The cellulose content in each suspension was treated as the control variable because the suspension concentration significantly influences the properties of the resultant cellulose nanofibers via ultrasonic processing. The as-obtained cellulose nanofibers were characterized by fiber diameter distribution, crystal structure, and rheological analysis. An increase of not more than 1.2 % of the cellulose content resulted in finer nanofibers. Both storage modulus and loss modulus of cellulose nanofiber suspensions rapidly increased with increasing concentration because of the gradual formation of a stronger network structure. In addition, the dynamic mechanical behavior of suspensions with fiber contents lower than 0.8 % was affected by the frequency and temperature alteration in contrast with the suspension with higher fiber contents. The sol–gel transformation and the visco-elastic transition depend on the hydroxyl bonding and the cross-linking extent of cellulose nanofibers in various concentration environments.