Industrial Application of Nanocelluloses in Papermaking: A Review of Challenges, Technical Solutions, and Market Perspectives.

Nanocelluloses (NC) increase mechanical and barrier paper properties allowing the use of paper in applications actually covered by other materials. Despite the exponential increase of information, NC have not been fully implemented in papermaking yet, due to the challenges of using NC. This paper provides a review of the main new findings and emerging possibilities in this field by focusing mainly on: (i) Decoupling the effects of NC on wet-end and paper properties by using synergies with retention aids, chemical modification, or filler preflocculation; (ii) challenges and solutions related to the incorporation of NC in the pulp suspension and its effects on barrier properties; and (iii) characterization needs of NC at an industrial scale. The paper also includes the market perspectives. It is concluded that to solve these challenges specific solutions are required for each paper product and process, being the wet-end optimization the key to decouple NC effects on drainage and paper properties. Furthermore, the effect of NC on recyclability must also be taken into account to reach a compromise solution. This review helps readers find upscale options for using NC in papermaking and identify further research needs within this field.

In Situ Production and Application of Cellulose Nanofibers to Improve Recycled Paper Production.

The recycled paper and board industry needs to improve the quality of their products to meet customer demands. The refining process and strength additives are commonly used to increase mechanical properties. Interfiber bonding can also be improved using cellulose nanofibers (CNF). A circular economy approach in the industrial implementation of CNF can be addressed through the in situ production of CNF using side cellulose streams of the process as raw material, avoiding transportation costs and reducing industrial wastes. Furthermore, CNF fit for use can be produced for specific industrial applications.This study evaluates the feasibility of using two types of recycled fibers, simulating the broke streams of two paper machines producing newsprint and liner for cartonboard, to produce in situ CNF for direct application on the original pulps, old newsprint (ONP), and old corrugated container (OCC), and to reinforce the final products. The CNF were obtained by 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO)-mediated oxidation and homogenization at 600 bar. Handsheets were prepared with disintegrated recycled pulp and different amounts of CNF using a conventional three-component retention system. Results show that 3 wt.% of CNF produced with 10 mmol of NaClO per gram of dry pulp improve tensile index of ONP ~30%. For OCC, the same treatment and CNF dose increase tensile index above 60%. In both cases, CNF cause a deterioration of drainage, but this effect is effectively counteracted by optimising the retention system.

Fit-for-Use Nanofibrillated Cellulose from Recovered Paper.

The cost-effective implementation of nanofibrillated cellulose (CNF) at industrial scale requires optimizing the quality of the nanofibers according to their final application. Therefore, a portfolio of CNFs with different qualities is necessary, as well as further knowledge about how to obtain each of the main qualities. This paper presents the influence of various production techniques on the morphological characteristics and properties of CNFs produced from a mixture of recycled fibers. Five different pretreatments have been investigated: a mechanical pretreatment (PFI refining), two enzymatic hydrolysis strategies, and TEMPO-mediated oxidation under two different NaClO concentrations. For each pretreatment, five high-pressure homogenization (HPH) conditions have been considered. Our results show that the pretreatment determines the yield and the potential of HPH to enhance fibrillation and, therefore, the final CNF properties. These results enable one to select the most effective production method with the highest yield of produced CNFs from recovered paper for the desired CNF quality in diverse applications.

Influence of dispersion of fibrillated cellulose on the reinforcement of coated papers.

The use of cellulose micro/nanofibrils (CMNFs) as reinforcement paper additive at industrial scale is delayed due to inconsistent results, suggesting a lack of proper consideration of some key parameters. The high influence of fibrillated nanocellulose dispersion has been recently identified as a key parameter for paper bulk reinforcement but it has not been studied for surface coating applications yet. This paper studies the effect of CMNF dispersion degree prior to their addition and during mixing with starch on the reinforcement of paper by coating. Results show that this effect depends on the type of CMNFs since it is related to the surface interactions. For a given formulation, a correlation is observed between the CMNF dispersion and the CMNF/starch mixing agitation with the rheology of the coating formulation which highly affects the paper properties. The optimal dispersion degree is different for each nanocellulose, but the best mechanical properties were always achieved at the lowest viscosity of the coating formulation. In general, the initial state of the nanocellulose 3D network, influences the mixing and smooth application of the coating and affects the reinforcement effect. Therefore, the CMNF industrial implementation in coating formulations will be facilitated by the on-line control of formulations prior to their surface application.

Recycled Fibers for Sustainable Hybrid Fiber Cement Based Material: A Review.

Reinforcing fibers have been widely used to improve physical and mechanical properties of cement-based materials. Most fiber reinforced composites (FRC) involve the use of a single type of fiber to improve cement properties, such as strength or ductility. To additionally improve other parameters, hybridization is required. Another key challenge, in the construction industry, is the implementation of green and sustainable strategies based on reducing raw materials consumption, designing novel structures with enhanced properties and low weight, and developing low environmental impact processes. Different recycled fibers have been used as raw materials to promote circular economy processes and new business opportunities in the cement-based sector. The valuable use of recycled fibers in hybrid FRC has already been proven and they improve both product quality and sustainability, but the generated knowledge is fragmented. This is the first review analyzing the use of recycled fibers in hybrid FRC and the hybridization effect on mechanical properties and workability of FRC. The paper compiles the best results and the optimal combinations of recycled fibers for hybrid FRC to identify key insights and gaps that may define future research to open new application fields for recycled hybrid FRC.

Chitosan grafted/cross-linked with biodegradable polymers: A review.

Public perception of polymers has been drastically changed with the improved plastic management at the end of their life. However, it is widely recognised the need of developing biodegradable polymers, as an alternative to traditional petrochemical polymers. Chitosan (CH), a biodegradable biopolymer with excellent physiological and structural properties, together with its immunostimulatory and antibacterial activity, is a good candidate to replace other polymers, mainly in biomedical applications. However, CH has also several drawbacks, which can be solved by chemical modifications to improve some of its characteristics such as solubility, biological activity, and mechanical properties. Many chemical modifications have been studied in the last decade to improve the properties of CH. This review focussed on a critical analysis of the state of the art of chemical modifications by cross-linking and graft polymerization, between CH or CH derivatives and other biodegradable polymers (polysaccharides or proteins, obtained from microorganisms, synthetized from biomonomers, or from petrochemical products). Both techniques offer the option of including a wide variety of functional groups into the CH chain. Thus, enhanced and new properties can be obtained in accordance with the requirements for different applications, such as the release of drugs, the improvement of antimicrobial properties of fabrics, the removal of dyes, or as scaffolds to develop bone tissues.

Enhanced Morphological Characterization of Cellulose Nano/Microfibers through Image Skeleton Analysis.

The present paper proposes a novel approach for the morphological characterization of cellulose nano and microfibers suspensions (CMF/CNFs) based on the analysis of eroded CMF/CNF microscopy images. This approach offers a detailed morphological characterization and quantification of the micro and nanofibers networks present in the product, which allows the mode of fibrillation associated to the different CMF/CNF extraction conditions to be discerned. This information is needed to control CMF/CNF quality during industrial production. Five cellulose raw materials, from wood and non-wood sources, were subjected to mechanical, enzymatic, and (2,2,6,6-Tetramethylpiperidin-1-yl)oxyl (TEMPO)-mediated oxidative pre-treatments followed by different homogenization sequences to obtain products of different morphologies. Skeleton analysis of microscopy images provided in-depth morphological information of CMF/CNFs that, complemented with aspect ratio information, estimated from gel point data, allowed the quantification of: (i) fibers peeling after mechanical pretreatment; (ii) fibers shortening induced by enzymes, and (iii) CMF/CNF entanglement from TEMPO-mediated oxidation. Being mostly based on optical microscopy and image analysis, the present method is easy to implement at industrial scale as a tool to monitor and control CMF/CNF quality and homogeneity.

Characterizing highly fibrillated nanocellulose by modifying the gel point methodology.

The characterization of nanocellulose fibres (NC) length is a difficult and indirect measurement which relies on aspect ratio calculation and fibre diameter analysis. The aspect ratio can be directly calculated from the gel point, a parameter obtained from sedimentation experiments. The gel point has been used with macroscopic fibres and microfibrillated cellulose, that easily sediment by gravity. However, this methodology has not yield consistent results with highly charged nanofibres nor with fibres with sediment layer difficult to observe. In this study, the gel point methodology is modified: 1) dying the fibres with Crystal Violet to enable the visualization of the fibrils sedimentation line without affecting the fibre network; and 2) by optimizing the sedimentation time to ensure complete settling. The two types of fibrils characterized -low and high fibrillated NC (LF-NC, HF-NC)- behave differently due to the slower sedimentation of HF-NC. The time to reach a stable sedimented layer increases with the level of fibre fibrillation, the charge and the decrease of fibre dimension. Reproducible gel point can be measured after 2 days for LF-NC; however, 8 days are required for HF-NC. The modified methodology was validated by quantifying the influence of pH and salt concentration. As expected, low pHs and the addition of CaCl2 coagulate HF-NC into flocs which increase the ratio: final over initial fibres height (Hs/Ho); this decreases significantly the gel point, as a lower amount of HF-NC are required to interconnect all fibres. This modified method is a valuable tool for the accurate dimensional characterisation of highly charged and low diameter cellulose nanofibres.

Comparison Of Mechanical And Chemical Nanocellulose As Additives To Reinforce Recycled Cardboard.

Recycling cycles cause a decrease in mechanical paper properties due to cellulose fiber degradation. The use of cellulose micro/nanofibers (CMF/CNF) to reinforce paper strength has been well studied, although it has been found to have negative effects on drainage. However, the application of CMF/CNF as paper reinforcement is affected by the nanocellulose type. Thus in this study mechanical and chemical treatments in CNF production were compared. Old corrugated container (OCC) pulp used to produce recycled cartonboard was reinforced with 1) CMF from never-dried northern bleached softwood kraft pulp (NBSK) highly refined in a 16-inch low consistency refiner at 1200 rpm and 25 kW of net power; and 2) CNF from NBSK pulp treated by TEMPO-mediated oxidation and homogenization at 600 bars. CMF/CNF and OCC were pulped at the same time and handsheets formed with cationic starch (CS) as retention system. Mechanical, drainage and flocculation properties were evaluated and compared. Data were also compared with other sources of TEMPO CNF. Results show an improvement in mechanical properties, drainage and flocculation when OCC is reinforced with CMF obtained with LCR. Therefore, high fibrillation was not necessary to improve mechanical paper or cardboard properties.

Study of The Reaction Mechanism to Produce Nanocellulose-Graft-Chitosan Polymer.

Cellulose and chitin are the most abundant polymeric materials in nature, capable of replacing conventional synthetic polymers. From them, cellulose nano/microfibers (CNFs/CMFs) and chitosan are obtained. Both polymers have been used separately in graft copolymerization but there are not many studies on the use of cellulose and chitosan together as copolymers and the reaction mechanism is unknown. In this work, the reaction mechanism to produce nano/microcellulose-graft-chitosan polymer has been studied. Recycled cellulose pulp was used, with and without a 2,2,6,6-tetramethylpiperidin-1-oxyl-radical (TEMPO)-mediated oxidation pretreatment, to produce CNFs and CMFs, respectively. For chitosan, a low-molecular weight product dissolved in an acetic acid solution was prepared. Grafted polymers were synthesized using a microwave digester. Results showed that TEMPO-mediated oxidation as the cellulose pretreatment is a key factor to obtain the grafted polymer CNF-g-CH. A reaction mechanism has been proposed where the amino group of chitosan attacks the carboxylic group of oxidized cellulose, since non-oxidized CMFs do not achieve the desired grafting. 13C NMR spectra, elemental analysis and SEM images validated the proposed mechanism. Finally, CNF-g-CH was used as a promising material to remove water-based inks and dyes from wastewater.

Application of cellulose nanofibers to remove water-based flexographic inks from wastewaters.

Water-based or flexographic inks in paper and plastic industries are more environmentally favourable than organic solvent-based inks. However, their use also creates new challenges because they remain dissolved in water and alter the recycling process. Conventional deinking technologies such as flotation processes do not effectively remove them. Adsorption, coagulation/flocculation, biological and membrane processes are either expensive or have negative health impacts, making the development of alternative methods necessary. Cellulose nanofibers (CNF) are biodegradable, and their structural and mechanical properties are useful for wastewater treatment. TEMPO-oxidised CNF have been evaluated for the decolourisation of wastewaters that contained copper phthalocyanine blue, carbon black and diarlyide yellow pigments. CNF in combination with a cationic polyacrylamide (cPAM) has also been tested. Jar-test methodology was used to evaluate the efficiency of the different treatments and cationic/anionic demand, turbidity and ink concentration in waters were measured. Results show that dual-component system for ink removal has a high potential as an alternative bio-based adsorbent for the removal of water-based inks. In addition, experiments varying CNF and cPAM concentrations were performed to optimise the ink-removal process. Ink concentration reductions of 100%, 87.5% and 83.3% were achieved for copper phthalocyanine blue, carbon black and diarlyide yellow pigments, respectively. Flocculation studies carried out show the decolourisation mechanism during the dual-component treatment of wastewaters containing water-based inks.