The present invention provides a method for the manufacturing of nanocellulose. The method includes a first modification of the cellulose material, where the cellulose fibres are treated with an aqueous electrolyte-containing solution of an amphoteric cellulose derivative. The modification is followed by a mechanical treatment. By using this method for manufacturing nanocellulose, clogging of the mechanical apparatus is avoided. Also disclosed is nanocellulose manufactured in accordance with said method and uses of said cellulose.
In this work the strength enhancing capabilities of microfibrillated cellulose (MFC) in highly filled papers was studied. Both the MFC production and the paper making were done in pilot scale under realistic industrial conditions. The results clearly show that MFC (2.5 - 5.0wt-%) could improve the mechanical properties of highly filled papers (20 - 35 wt-% filler contents). All studied dry mechanical properties were improved and the improvements were most pronounced for Z-strength and fracture toughness. By combining the MFC with a C-starch dosage further improvements in mechanical properties could be achieved. The improvements in mechanical properties enabled increased filler content with retained properties. The filler increase could be achieved at the same time as the sheet formation and the dry content after pressing were improved.
The layer-by-layer (LbL) deposition method was used for the build-up of alternating layers of nanofibrillated cellulose (NFC) or carboxymethyl cellulose (CMC) with a branched, cationic polyelectrolyte, polyethyleneimine (PEI) on flexible poly (lactic acid) (PLA) substrates. With this procedure, optically transparent nanocellulosic films with tunable gas barrier properties were formed. 50 layer pairs of PEI/NFC and PEI/CMC deposited on PLA have oxygen permeabilities of 0.34 and 0.71 cm(3).mu m/m(2).day.kPa at 23 degrees C and 50% relative humidity, respectively, which is in the same range as polyvinyl alcohol and ethylene vinyl alcohol. The oxygen permeability of these multilayer nanocomposites outperforms those of pure NFC films prepared by solvent-casting. The nanocellulosic LbL assemblies on PLA substrates was in detailed characterized using a quartz crystal microbalance with dissipation (QCM-D). Atomic force microscopy (AFM) reveals large structural differences between the PEI/NFC and the PEI/CMC assemblies, with the PEI/NFC assembly showing a highly entangled network of nanofibrils, whereas the PEI/CMC surfaces lacked structural features. Scanning electron microscopy images showed a nearly perfect uniformity of the nanocellulosic coatings on PLA, and light transmittance results revealed remarkable transparency of the LbL-coated PLA films. The present work demonstrates the first ever LbL films based on high aspect ratio, water-dispersible nanofibrillated cellulose, and water-soluble carboxymethyl cellulose polymers that can be used as multifunctional films and coatings with tailorable properties, such as gas barriers and transparency. Owing to its flexibility, transparency and high-performance gas barrier properties, these thin film assemblies are promising candidates for several large-scale applications, including flexible electronics and renewable packaging.
A novel, technically and economically benign procedure to combine vermiculite nanoplatelets with nanocellulose fibre dispersions into functional biohybrid films is presented. Nanocellulose fibres of 20 nm diameters and several micrometers in length are mixed with high aspect ratio exfoliated vermiculite nanoplatelets through high-pressure homogenization. The resulting hybrid films obtained after solvent evaporation are stiff (tensile modulus of 17.3 GPa), strong (strength up to 257 MPa), and transparent. Scanning electron microscopy (SEM) shows that the hybrid films consist of stratified nacre-like layers with a homogenous distribution of nanoplatelets within the nanocellulose matrix. The oxygen barrier properties of the biohybrid films outperform commercial packaging materials and pure nanocellulose films showing an oxygen permeability of 0.07 cm(3) mu m m(-2) d(-1) kPa(-1) at 50% relative humidity. The oxygen permeability of the hybrid films can be tuned by adjusting the composition of the films. Furthermore, the water vapor barrier properties of the biohybrid films were also significantly improved by the addition of nanoclay. The unique combination of excellent oxygen barrier behavior and optical transparency suggests the potential of these biohybrid materials as an alternative in flexible packaging of oxygen sensitive devices such as thin-film transistors or organic light-emitting diode displays, gas storage applications and as barrier coatings/laminations in large volume packaging applications.
A shear-lag approach to the prediction of the tensile strength of paper is outlined and examined. It is demonstrated that transition of fiber strength to paper strength requires long fibers for sheets with weak fiber-fiber bonds, or low relative bonded area. Fiber pull-out is encountered even for highly bonded sheets. Predictions of tensile strength for papers of the same fiber length, but with different beating degrees, and for papers with different fiber lengths and beating degrees, are in quantitative agreement with previously published data.
This work investigated the effect of using Kenaf bast fibre kraft pulps compared to Scotch Pine kraft pulps for producing microfibrillated cellulose (MFC) and its employment for improving mechanical and physical properties of handsheets made from unbleached kraft hardwood pulp. It was shown that MFC based on Kenaf fibres can be produced at higher consistencies [> 5 % (w/w)] compared to when Scotch Pine is employed [a parts per thousand 2 % (w/w)] as raw material. The possibility of using a higher consistency when processing Kenaf is beneficial for the processing in microfluidizers. The rheological properties of the products were shown to be consistent with what is known for MFC-based systems. The studies indicate that the mechanical properties of handsheets from unbleached kraft hardwood pulp can be improved by replacing part of the unbleached kraft hardwood pulp fibres with either unbleached kraft Kenaf pulp or unbleached Scotch Pine kraft pulp. However, the same levels of improvements were obtained when using only a small amount [a parts per thousand 6 % (w/w)] of MFC based on Kenaf or Scotch Pine, when introduced into the system either as a dry strength additive or by coating pre-made handsheets. Finally, it was shown that the incorporation of MFC in handsheets decreases the air-permeability; this effect became amplified when the MFC was applied as a coating onto the handsheets.
Low-cost production of nanocellulose from diverse lignocellulosic feedstocks has become an important topic for developing sustainable nanomaterials. The available feedstocks include both woody and non-woody plants, where the latter are relatively underutilized. Interestingly, the porous structure and low lignin content in most non-woody plants, such as agricultural residues and natural fibers, also makes them ideal sources for lower energy nanocellulose production using simpler methods than those required to process woody plants. To enhance the goal of circularity, this review first provides an overview of the nanocellulose conversion from cellulose and then comprehensively discusses the use of non-woody feedstocks for nanocellulose production. Specifically, the availability of suitable non-woody feedstocks and the use of low-cost processes for pulping and cellulose oxidation treatments, including alkaline, solvent pulping, and nitrogen-oxidation treatments, are discussed. The information in this review can lead to new opportunities to achieve greater sustainability in biobased economies. Additionally, demonstrations of nanocellulose-based water purification technologies using agricultural residues derived remediation materials are highlighted at the end of this review.
Nanocelluloses (NC) are nature-based sustainable biomaterials, which not only possess cellulosic properties but also have the important hallmarks of nanomaterials, such as large surface area, versatile reactive sites or functionalities, and scaffolding stability to host inorganic nanoparticles. This class of nanomaterials offers new opportunities for a broad spectrum of applications for clean water production that were once thought impractical. This Review covers substantial discussions based on evaluative judgments of the recent literature and technical advancements in the fields of coagulation/flocculation, adsorption, photocatalysis, and membrane filtration for water decontamination through proper understanding of fundamental knowledge of NC, such as purity, crystallinity, surface chemistry and charge, suspension rheology, morphology, mechanical properties, and film stability. To supplement these, discussions on low-cost and scalable NC extraction, new characterizations including solution small-angle X-ray scattering evaluation, and structure-property relationships of NC are also reviewed. Identifying knowledge gaps and drawing perspectives could generate guidance to overcome uncertainties associated with the adaptation of NC-enabled water purification technologies. Furthermore, the topics of simultaneous removal of multipollutants disposal and proper handling of post/spent NC are discussed. We believe NC-enabled remediation nanomaterials can be integrated into a broad range of water treatments, greatly improving the cost-effectiveness and sustainability of water purification.
The physical attachment of carboxymethylcellulose (CMC) onto kraft pulps during cooking and the effects of subsequent bleaching in an OD(EOP)DD sequence were investigated. Two CMC grades with different molecular weights and different degrees of substitution (D.S.) were used, CMC Finnfix WRH and CMC Cekol DVG. The effect of the CMC was studied by measuring the increase in the total charge density as well as in the surface charge density. In this way, both the total amount of attached CMC and the amount of the CMC attached onto the surface of the fibres Could be determined. Hand-sheets were made to study the effects of CMC addition on the physical properties of the paper. Different amounts of CMC were added to find the optimum, which was determined to be 1% CMC on wood. The proportion of CMC attached at a level addition of 1% (on wood) was about 40%. It was, however, found that a large part of the CMC was degraded during the cook. Whereas high molecular weight CMC is attached onto the surface of fibres, the degraded CMC is attached to the interior of the cell wall, decreasing the efficiency of the CIVIC to enhance the joint strength between fibres. The tensile index increased significantly, approximately 10% after beating to 2000 PFI revolutions, when 1% CMC Finnfix WRH on wood was added. The CMC Cekol DVG grade showed the greatest increase in tensile index, approximately 12% at 2000 PFI revolutions. The results of the bleaching of a sample treated with CMC Finnfix WRH showed that a part of the effect of CMC remains after bleaching. Most of the reduction in the positive effect was due to a loss of CMC molecules from the fibre surface.
The adsorption behavior of highly charged cationic polyelectrolytes onto porous substrates is electrostatic in nature and has been shown to be highly dependent on the polyelectrolyte properties. Copolymers of acrylamide (AM) and diallyldimethylammonium chloride (DADMAC) were synthesized to have a range of macromolecular properties (i.e., charge density and molecular mass). Traditional titration methods have been complemented by fluorescence labeling techniques that were developed to directly observe the extent that fluorescently labeled poly(AM-co-DADMAC) adsorbs into the pore structure of a cellulosic Substrate. Although contributing to the electrostatic driving force, the charge density acts to limit adsorption to the outermost surface under electrolyte-free conditions. However, adsorption into the pores call occur if both the molecular mass and charge density of poly(AM-co-DADMAC) are Sufficiently low. Adsorption initially increases as the electrolyte concentration is increased. However, the electrostatic persistence length of poly(AM-co-DADMAC) restricts the polyelectrolyte from entering the pores. Therefore, changes ill the adsorption behavior at moderate electrolyte concentrations have been attributed to swelling of the polyelectrolyte layer at the fiber exterior. The adsorption behavior changes again at high electrolyte concentrations Such that poly(AM-co-DADMAC) could adsorb into the pore Structure. This occurred when the electrolyte concentration was sufficient to screen the electrostatic persistence length of poly(AM-co-DADMAC), provided that the entropic driving force for adsorption still existed. It is suggested that adsorption into the pore structure is a kinetic process that is governed by localized electrostatic interactions between poly(AM-co-DADMAC) and the charges located within the pores.
The adsorption behavior of a low charge density cationic polyelectrolyte to cellulosic fibers has been studied. Cationic dextran served as a model polyelectrolyte, as it can be prepared over a range in molecular mass and charge density. The adsorption behavior of the cationic dextran was measured in electrolyte-free conditions using polyelectrolyte titration techniques. By fluorescent labeling the cationic dextran, the extent to which adsorption occurs inside the porous structure was further determined by fluorescent confocal laser scanning microscopy. Cationic dextran having a sufficiently low charge density adsorbed into the pores, although the extent the cationic dextran adsorbed was governed by the molecular mass. The adsorption behavior of the cationic dextran was also studied in various electrolyte concentrations. The adsorbed mass monotonically decreased with increasing electrolyte, as the electrostatic interaction with the substrate was more effectively screened. This behavior also suggests that the interactions between adsorbed polyelectrolyte chains, i.e. lateral correlation effects, are negligible for low charge density polyelectrolytes. Finally, the effect of having a preadsorbed layer of cationic dextran on the adsorption behavior was determined in electrolyte-free conditions using fluorescent double staining techniques. The preadsorbed cationic dextran had almost no effect on the adsorption of low molecular mass fractions. Low molecular mass fractions directly adsorbed into the pore structure, as opposed to adsorbing to a free surface and diffusing into the pores. It was also shown that cationic dextran can be selectively adsorbed to different locations, such that the surface of a porous substrate can be treated uniquely from the bulk.
The penetration of cationic polyelectrolytes into anionic cellulosic fibers was evaluated with fluorescent imaging techniques in order to clarify the mechanism and time scales for the diffusion process. The bulk charge of the cellulosic fibers indirectly creates a driving force for diffusion into the porous fiber wall, which is entropic in nature due to a release of counterions as the polyelectrolyte adsorbs. The individual bulk charges in the fiber cell wall also interact with the diffusing polyelectrolyte, Such that the polyelectrolyte diffuses to the first available charge and consequently adsorbs and remains fixed. Thus, Subsequent polyelectrolyte chains must first diffuse through the adsorbed polyelectrolyte layer before adsorbing to the next available bulk charges. This behavior differs from earlier suggested diffusion mechanisms, by which polyelectrolytes were assumed to first adsorb to the outermost surface and then reptate into the pore structure. The time scales for polyelectrolyte diffusion were highly dependent on the flexibility of the chain, which was estimated from calculations of the persistence length. The persistence length ultimately depended on the charge density and electrolyte concentration. The charge density of the polyelectrolyte had a greater influence on the time scales for diffusion. High charge density polyelectrolytes were observed to diffuse on a time scale of months, whereas the diffusion of low charge density polyelectrolytes was measured on the order of hours. An influence of the chain length, that is, steric interactions due the persistence length of the polyelectrolyte and to the tortuosity of the porous structure of the fiber wall, could only be noted for low charge density polyelectrolytes. Increasing the electrolyte concentration increased the chain flexibility by screening the electrostatic contribution to the persistence length, in turn inducing a faster diffusion process. However, a significant change in the diffusion behavior was observed at high electrolyte concentrations, at which the interaction between the polyelectrolyte charges and the fiber charges was almost completely screened.
The polyelectrolyte titration technique was used to investigate the relationship between bulk and surface charges for various pulps and treatments. The total and surface charge content is different for hardwood and softwood pulps; however, the charge ratio is the same. Mechanical pulping gives a higher charge ratio than chemical pulping. Even though the amount of charges are changed during different bleaching sequences for chemical pulp, the charge ratio is not affected because the bleaching process is non-surface selective. fn order to change the charge ratio for chemical pulp, beating or surface carboxymethylation can be performed.
Various forces govern the fiber–fiber interaction in a flowing suspension, causing fibers to create flocs. The aim with this investigation was to examine the influence of colloidal interactions on the fiber network strength by varying surface charge density, electrolyte concentration, and type of counterion. This was accomplished by comparing surface force measurements, utilizing colloidal probe microscopy (CPM), with the apparent yield stress, using a parallel plate rheometer. Results show that by increasing the charge density by grafting carboxymethyl cellulose (CMC) to the surface, a large electrosteric repulsion is created, which gives weaker network strength. Increasing the electrolyte concentration decreases the repulsion. The network strength was, however, not affected by electrolyte concentration for untreated fibers whereas a high electrolyte concentration increased the yield stress for CMC-treated fibers. The change of counterions affect the repulsion, causing a change in network strength due to differences in the surface swelling of cellulose.
The influence of mechanical surface linking and elastic fiber bending on the fiber network strength and elasticity (i.e. storage modulus and critical strain) was investigated for pulps with different lengths and stiffness, using a parallel plate rheometer. Results show that the storage modulus increases and critical strain decreases with increasing fiber length due to increased number of fiber contacts. Laboratory-cooked pulp has a higher storage modulus and a lower critical strain than commercial pulp because of straighter and stiffer fibers, which are more influenced by both mechanical surface linking and elastic fiber bending.
The effect of electrolyte (NaHCO3) concentration on the adsorption of poly-DADMAC (poly-diallyldimethylammonium chloride) onto cellulosic fibers with different charge profiles was investigated. Surface carboxymethylated fibers were obtained by grafting carboxymethyl cellulose (CMC) onto the fiber surface and bulk carboxymethylated fibers were obtained by reacting the fibers with monochloroacetic acid. It was shown that nonionic interactions do not exist between cellulose and poly-DADMAC, rather electrostatic interactions govern the adsorption. Charge stoichiometry prevails under electrolyte-free conditions, whereas surface charge overcompensation occurs at higher electrolyte concentrations. It was shown that charge stoichiometry prevails if the thickness of the electric double layer kappa(-1) was larger than the mean distance between the charges on the fiber surface, as predicted by polyelectrolyte adsorption theories, taking lateral correlation effects into account. In a second set of experiments the ESCA technique served to independently calibrate the polyelectrolyte titrations for determining the surface charge of cellulosic fibers. Various molecular masses of poly-DADMAC were adsorbed to carboxymethylated fibers having different charge profiles. The adsorption of low M-w poly-DADMAC (7.0 x 10(3)), analyzed by polyelectrolyte titration, was about 10 times higher than that of the high M-w poly-DADMAC (9.2 x 10(5)). Despite the difference in accessibility of these two polyelectrolytes to the fiber cell wall, ESCA surface analysis showed, as expected, only slight differences between the two polyelectrolytes, This gives strong credibility to the idea that surface charge content of cellulosic fibers can be analyzed by means of adsorption of a high-molecular-mass cationic polymer, i.e., by polyelectrolyte titration.
Ultrafiltration (UF) is a common technique used in wastewater treatments. However, the issue of membrane fouling in UF can greatly hinder the effectiveness of the treatments. This study demonstrated a low-fouling composite cellulose membrane system based on microfibrillated cellulose (MFC) and silica nanoparticle additives. The incorporation of 'non-spherical' silica nanoparticles was found to exhibit better structural integration in the membrane (i.e., minimal aggregation of silica nanoparticles in the membrane scaffold) as compared to spherical silica. The resulting composite membranes were tested for UF using local wastewater, where the best-performing membrane exhibited higher permeation flux than commercial polyvinylidene difluoride (PVDF) and polyether sulfone (PES) membranes while maintaining a high separation efficiency (similar to 99.6%) and good flux recovery ratio (>90%). The analysis of the fouling behavior using different models suggested that the processes of cake layer formation and pore-constriction were probably two dominant fouling mechanisms, likely due to the presence of humic substances in wastewater. The demonstrated cellulose composite membrane system showed low-fouling and high restoration capability by a simple hydraulic cleaning method due to the super hydrophilic nature of the cellulose scaffold containing silica nanoparticles.
Cellulose fibrils with widths in the nanometer range are nature-based materials with unique and potentially useful features. Most importantly, these novel nanocelluloses open up the strongly expanding fields of sustainable materials and nanocomposites, as well as medical and life-science devices, to the natural polymer cellulose. The nanodimensions of the structural elements result in a high surface area and hence the powerful interaction of these celluloses with surrounding species, such as water, organic and polymeric compounds, nanoparticles, and living cells. This Review assembles the current knowledge on the isolation of microfibrillated cellulose from wood and its application in nanocomposites; the preparation of nanocrystalline cellulose and its use as a reinforcing agent; and the biofabrication of bacterial nanocellulose, as well as its evaluation as a biomaterial for medical implants.
This short investigation deals with a review of the tensile strength properties of six different types of nanocellulose films (carboxymethylated, carboxymethylcellulose-grafted, enzymatically pretreated, phosphorylated, sulfoethylated, and alkoxylated nanocellulose films) manufactured using identical protocols and the determination of the apparent nanocellulose yield of the same nanocelluloses and their tensile strength properties at different extents of delamination (microfluidization). The purpose was to test a previously suggested procedure to estimate the maximum tensile strength on these different procedures. A second goal was to investigate the impact of the nanocellulose yield on the tensile strength properties. The investigations were limited to the nanocellulose research activities at RISE in Stockholm, because these investigations were made with identical experimental laboratory protocols. The importance of such protocols is also stressed. This review shows that the suggested procedure to estimate the maximum tensile strength is a viable proposition, albeit not scientifically proven. Secondly, there is a relationship between the nanocellulose yield and tensile strength properties, although there may not be a linear relationship between the two measures.
INTRODUCTION: This short review deals with some applications and research needs for nanocellulosic (NC) materials; primarily cellulose nanocrystals (CNC), cellulose nanofibers (CNF), and bacterial cellulose (BC). Whereas CNC and BC materials are fairly homogenous, CNF materials represent a wide sector of different materials, often with a high heterogeneity. This is due to different pretreatment methods (mechanical, chemical, enzymatic), woodbased or agricultural-based materials, delignification and bleaching procedures, etc. The purpose of this comprehensive review is not to discuss the various production methods, for which the reader may consult with a selected number of reviews [1-6]; thus, the focus is on practical applications. Practical applications and potential markets were also discussed some years ago by other investigators [7-8]. Upscaling and choice of pretreatment methods, as well as economic considerations and different business models, have also been discussed, along with: Toxicity and environmental issues [9-10] The complex characterization of cellulose nanomaterials [4] The reader should also be aware of new contenders to the three classic groups of cellulosic nanomaterials, which are already in a commercial phase. These include cellulose filaments [11-12] and materials from mechanical grinding processes [13], and these materials may be nanostructures or not, depending on our classification. Finally, as indicated by the editorial on p. 275, scientists are currently taking a deep dive into the fundamental features of nanocellulosic materials [14-15].
The revitalized paradigm shift in pulp and paper research in the papermaking industry, is discussed. The papermaking processes changed a lot and the old-fashioned beating operation disappeared. Slowly the recyclable 'Paper Solar' cells have become one of the epitomes of intelligent paper. Dramatic changes are also observed in the R&D structure which has started to evolve into new structure. Engineers realize that they had to do things in a different way, otherwise there could be no future for the industry.
The area of paper chemistry is by many knowledgeable suppliers conceived as pretty mature as most classical concepts in wet-end chemistry are reasonably well understood, although not always efficiently practised by papermakers. Hence, this evolution calls for more radical changes and among these changes fibre modification by different means has called for attention during recent years. Such modifications invoke biochemical modification of carrier polymers, new types of grafting methods and polyelectrolyte multilayering, which have been investigated particularly in the Nordic countries and also brought to commercial practice. Surface charge grafting constitutes a powerful means of fibre modification and the potential in this field will be reviewed and upcoming nanotechnology issues will also be discussed.
This communication is a review over the major market and technical challenges and opportunities for nanocellulosic materials on a large scale but in low-to-medium-end markets. Basically, the potential use of nanocellulose as a wet-end strength additive in papermaking has been known for decades, but not come into operation because of the high-energy costs of producing these materials. Cost performance compared to starch derivatives is one challenge, and the other is to design suitable dewatering/retention aid systems. Other paper applications are as a surface-sizing agent and as a barrier coating material. Major challenges are associated with the high viscosity of nanocellulosic materials and how to apply the nanocellulose in order to obtain good surface coverage. There are several opportunities in the nanocomposite markets. The packaging sector together with the automotive sector and the building sector constitute large potential markets. Challenges are related to the mixing of hydrophobic and hydrophilic materials so that a good dispersion of nanocellulose is obtained. Scaling up of nanocellulose production processes and procedures for nanocomposite manufacturing in order to obtain price-performance in the various applications remains, as expected, the largest challenge.
There has been extensive research and development activities in the field of nanofibrillated cellulose (NFC) materials during recent years, although microfibrillated cellulose was developed already during the late 1970s at ITT-Rayonier in USA. A major impediment for the large-scale use of NFC has been the high-energy use (excess of 30000 kWh/ton NFC in energy consumption). This problem has now been alleviated by a series of different pre-treatment procedures of the fibres prior to the subsequent mechanical cell wall delamination. The focus in practical papermaking applications of NFC is in the reinforcement of paper/board materials (dry strength wet-end additive) and in barrier coating applications. The driving forces in these applications are resource and energy efficiency in papermaking and the vision of substituting fossil-based films with nanocellulose barriers. Nanocellulose has excellent oil, fat and oxygen barrier properties in the dry state, but the oxygen barrier properties deteriorate at high relative humidities and the approaches to alleviate the moisture sensitivity will be discussed. Today, there are many companies in the process of commercializing NFC and several of them have pilot plants/pre-commercial operations and are planning for up scaling. A pilot plant for the nominal production of 100 kg/day (dry based NFC) was also taken into operation at Innventia AB in 2010. The current contribution will highlight critical issues in the production of NFC and discuss various applications and hurdles to be overcome in order to make NFC production for paper/board based end-use applications viable.
This paper deals with the details of preparation of three principal routes for bulking of cellulose fibres. One route is dry cross-linking/hornification using aluminium ions and other salts followed by drying/curing. The mechanisms of these reactions still remain unknown. A second route is physical grafting of fibres using carboxymethylcellulose and bringing the acidic groups into their aluminium form before forming a sheet of paper/board. Hence, curing is not necessary, and this constitutes a unique wet bulking methodology. The mechanism behind this method is believed to be an increase in the surface friction of fibres, when the electrostatic double layer is shielded together with electrostatic cross-linking with aluminium ions. The higher friction between fibres partly prevents the sheet consolidation during drying. A third route is physical grafting of fibres using carboxymethyl cellulose and ion-exchanging the acidic groups with aluminium salts before drying and curing of the fibres. A most interesting factor is that all the thermal treatment methods do not form fibre nodules due to interfibre crosslinking during the heat treatment, a commonly observed phenomena when dealing with chemical crosslinking of fibres. All routes investigated are water-based and should be fairly simple to implement in commercial operations. An inherent advantage is that the bulking is associated with lower water retention values, which should be advantageous for a higher solids content after pressing and, hence, beneficial for paper machine productivity. Bulking is, however, also associated with a loss in bond strength, which in most cases must be alleviated using various additives such as starches and microfibrillated cellulose and it has also been demonstrated in the project how the strength properties (such as z-strength) could be restored at a higher bulk.
This paper summarizes chemical technologies aimed at making bulking fibres, a technology mainly practiced in the area of tissue and hygiene products but also highly relevant for board products made by sheet stratification containing bulking layers in the middle of the board in order to improve the bending stiffness of the board. There is a long history of different ways to make bulking fibres albeit the fact that such technologies have scarcely been used for commercial stratified board (apart from a variety of different pulp types), but more in tissue and hygiene products. The objective is to review the very different approaches that may be used for the purpose of making bulking fibres.
This review deals with the evolution of bio-based packaging and the emergence of various nanotechnologies for primary food packaging. The end-of life issues of packaging is discussed and particularly the environmental problems associated with microplastics in the marine environment, which serve as a vector for the assimilation of persistent organic pollutants in the oceans and are transported into the food chain via marine and wild life. The use of biodegradable polymers has been a primary route to alleviate these environmental problems, but for various reasons the market has not developed at a sufficient pace that would cope with the mentioned environmental issues. Currently, the biodegradable plastics only constitute a small fraction of the fossil-based plastic market. Fossil-based plastics are, however, indispensable for food safety and minimization of food waste, and are not only cheap, but has generally more suitable mechanical and barrier properties compared to biodegradable polymers. More recently, various nanotechnologies such as the use of nanoclays, nanocellulose, layer-by-layer technologies and polyelectrolyte complexes have emerged as viable technologies to make oxygen and water vapor barriers suitable for food packaging. These technological developments are highlighted as well as issues like biodegradation, recycling, legislation issues and safety and toxicity of these nanotechnologies.
The rheological properties of carboxymethylated nanofibrillated cellulose (NFC), investigated with controlled shear rate- and oscillatory measurements, are reported for the first time. It was shown that the rheological properties of the studied system are similar to those reported for other NFC systems. The carboxymethylated NFC systems showed among other things high elasticity and a shear thinning behaviour when subjected to increasing shear rates. Further, the shear viscosity and storage modulus of the system displayed power-law relations with respect to the dry content of the NFC suspension. The exponential values, 2 and 2.4 respectively, were found to be in good agreement with both theoretical predictions and published experimental work. Furthermore, it was found that the pulp consistency at which NFC is produced affects the properties of the system. The rheological studies imply that there exists a critical pulp concentration below which the efficiency of the delamination process diminishes; the same adverse effect is also observed when the critical concentration is significantly exceeded due to a lower energy input during delamination.
Toward exploiting the attractive mechanical properties of cellulose I nanoelements, a novel route is demonstrated, which combines enzymatic hydrolysis and mechanical shearing. Previously, an aggressive acid hydrolysis and sonication of cellulose I containing fibers was shown to lead to a network of weakly hydrogen-bonded rodlike cellulose elements typically with a low aspect ratio. On the other hand, high mechanical shearing resulted in longer and entangled nanoscale cellulose elements leading to stronger networks and gels. Nevertheless, a widespread use of the latter concept has been hindered because of lack of feasible methods of preparation, suggesting a combination of mild hydrolysis and shearing to disintegrate cellulose I containing fibers into high aspect ratio cellulose I nanoscale elements. In this work, mild enzymatic hydrolysis has been introduced and combined with mechanical shearing and a high-pressure homogenization, leading to a controlled fibrillation down to nanoscale and a network of long and highly entangled cellulose I elements. The resulting strong aqueous gels exhibit more than 5 orders of magnitude tunable storage modulus G' upon changing the concentration. Cryotransmission electron microscopy, atomic force microscopy, and cross-polarization/magic-angle spinning (CP/MAS) C-13 NMR suggest that the cellulose I structural elements obtained are dominated by two fractions, one with lateral dimension of 5-6 nm and one with lateral dimensions of about 10-20 nm. The thicker diameter regions may act as the junction zones for the networks. The resulting material will herein be referred to as MFC (microfibrillated cellulose). Dynamical rheology showed that the aqueous suspensions behaved as gels in the whole investigated concentration range 0.125-5.9% w/w, G' ranging from 1.5 Pa to 10(5) Pa. The maximum G' was high, about 2 orders of magnitude larger than typically observed for the corresponding nonentangled low aspect ratio cellulose I gels, and G' scales with concentration with the power of approximately three. The described preparation method of MFC allows control over the final properties that opens novel applications in materials science, for example, as reinforcement in composites and as templates for surface modification.
Membrane technology remains the most energy-efficient process for removing contaminants (micrometer-size particles to angstrom-size hydrated ions) from water. However, the current membrane technology, involving relatively expensive synthetic materials, is often nonsustainable for the poorest communities in the society. In this article, perspectives are provided on the emerging nanocellulose-enabled membrane technology based on nanoscale cellulose fibers that can be extracted from almost any biomass. It is conceivable that nanocellulose membranes developed from inexpensive, abundant, and sustainable resources (such as agriculture residues and underutilized biomass waste) can lower the cost of membrane separation, as these membranes offer the ability to remove a range of pollutants in one step, via size exclusion and/or adsorption. The nanocellulose-enabled membrane technology not only may be suitable for tackling global drinking water challenges, but it can also provide a new low-cost platform for various pressure-driven filtration techniques, such as microfiltration, ultrafiltration, nanofiltration, and reverse osmosis. Some relevant parameters that can control the filtration performance of nanocellulose-enabled membranes are comprehensively discussed. A short review of the current state of development for nanocellulose membranes is also provided.
It is well known that a high linting and dusting tendency of newsprint will almost certainly cause a higher frequency of production stops in offset printing. Such stops are connected with production losses, health hazards and high costs for blanket cleaning. This report deals with the area of surface and internal treatments of thermomechanical pulp (TMP) containing paper grades such as newsprint. The objective of such treatments was to reinforce the surface strength of the paper in order to decrease the linting and dusting of the paper during printing. Surface treatments are usually employed in commercial practice by applying modified starches to the paper surface using film-press technology. Internal treatments of modified starches may also reduce the delamination resistance. In this investigation, laboratory TMP-sheets and commercial newsprint sheets were coated with microfibrillated cellulose (MFC) and anionic starch (A-starch). The surface treatments were also compared with internally treated TMP-sheets using cationic starch. The linting propensity of the sheets was evaluated using the Innventia linting propensity tester (Innventia-LPT). Both MFC and A-starch treatments greatly improved the linting propensity of the coated sheets. It was also found that there is a strong synergistic effect of using a mixture of microfibrillated cellulose and anionic starch. A mixture of these two additives gave a lower linting propensity than if either additive was used alone. When using MFC alone, sheet delamination may occur, due to the strong water retention and hold-out properties of MFC, but if anionic starch was used together with MFC a film anchoring of the coating to the base sheet was achieved, improving the linting propensity without risk for delamination.
Super-hydrophobic surfaces may arise due to an interplay between the intrinsic, relatively high, contact angle of the more or less hydrophobic solid surface employed and the geometric features of the solid surface. In the present work, this relationship was investigated for a range of different surface geometries, making use of surface free energy minimization. As a rule, the free energy minima (and maxima) occur when the Laplace and Young conditions are simultaneously fulfilled. Special effort has been devoted to investigating the free energy barriers present between the Cassie-Baxter (heterogeneous wetting) and Wenzel (homogeneous wetting) modes. The predictions made on the basis of the model calculations compare favorably with experimental results presented in the literature.