Overview of Nanocellulose As Additives in Paper Processing and Paper Products Promising for Future Development
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Nanotechnology Reviews 2021; 10: 264–281 Review Article Ao Li, Dezhong Xu, Lu Luo, Yalan Zhou, Wen Yan, Xin Leng, Dasong Dai, Yonghui Zhou, Hassan Ahmad, Jiuping Rao*, and Mizi Fan* Overview of nanocellulose as additives in paper processing and paper products https://doi.org/10.1515/ntrev-2021-0023 promising for future development. This report shall pro- received March 9, 2021; accepted April 9, 2021 vide most useful database information for researchers Abstract: The rapid economic growth and environmental and industries for paper recycling and enhancement, - concerns have led to high demands on paper and paper- and paper based products innovation and application. based products in terms of variety, quantity, quality, Keywords: nanocellulose bio-additive, paper and paper- and specialty. Enhancement and functionalization with based product, specialty paper, recycle, functionalization additives are constantly required. Moving away from traditional petroleum-based additives, researchers have attempted to use “green” nanoadditives by introducing renewable environmentally friendly nanocellulose. This 1 Introduction article studies the functions of nanocellulose as bio-addi- ( ) tives (enhancer, retention and filtration reagent, and Nanocellulose NC is a nanoscale term used to refer coating aid) in paper and paper products, and overviews to cellulosic materials, which are the most abundant, the research development of nanocellulose-based addi- renewable, and biodegradable biopolymer on earth. Wood tives and their applications in the paper industry for is currently the most extensive source of the industrialized fi both efficient production and paper functionalization. cellulose, which is the orderly structure of the ber elements [ ] - The review shows that (1) a variety of nanocellulose- that make up cells 1,2 . The hierarchical nature and com based bioadditives have been reported for various appli- plexity of biomass cellulose allow its structure to be analyzed ff cations in paper and paper-based products, while com- at di erent levels, which is composed of growth ring, cell fi fi mercially viable developments are to be advanced; (2) structure, cell wall, ber matrix, micro bers, and cellulose - nanocellulose was mostly formulated with other polymer molecules, being analyzed from the macroscopic, micro [ – ] and particles as additives to achieve their synergistic scopic to nanoscale, as shown in Figure 1 3 5 . - effects; (3) major interests have concentrated on the Cellulose is a linear biopolymer, which occurs natu nanocellulose in the specialty papers as representing rally in all plants. In the early nineteenth century, the fi more value added products and in the efficient utilization chemical structure of cellulose was con rmed, followed - of recycled fibers, which remains most attractive and by in depth research activities. The linear polymer in cellulose is linked by D-glucopyranose with β-1,4-glyco- sidic bonds (Figure 2); two D-glucopyranoses compose cellobiose as the repeating unit of cellulose polymer. * Corresponding author: Jiuping Rao, College of Materials Each D-glucopyranose unit has six carbon atoms and Engineering, Fujian Agriculture and Forestry University, Fuzhou three hydroxyl groups (respectively C2, C3, and C6 atoms). - 350108, China, e mail: [email protected] The degree of polymerization ranges between 10,000 and * Corresponding author: Mizi Fan, College of Materials Engineering, 15,000. Cellulose is hydrophilic because of its molecular Fujian Agriculture and Forestry University, Fuzhou 350108, China; Nanocellulose and Biocomposites Research Centre, Brunel structure, insoluble in water and most organic solvents, University, London, UB8 3PH, United Kingdom, degradable, and chiral [6–10]. In addition, the cellulose is e-mail: [email protected] odorless and inexpensive, and has high crystallinity, excel- Ao Li, Dezhong Xu, Lu Luo, Yalan Zhou, Wen Yan, Xin Leng, Dasong lent biocompatibility, low density, and robust strength [11]. Dai: College of Materials Engineering, Fujian Agriculture and The content and characteristics of cellulose may vary with Forestry University, Fuzhou 350108, China [ ] Yonghui Zhou, Hassan Ahmad: Nanocellulose and Biocomposites the sources 12 . Research Centre, Brunel University, London, UB8 3PH, United NC refers to a fibrous biomass-based material with Kingdom a size less than 100 nm in at least one dimension, and Open Access. © 2021 Ao Li et al., published by De Gruyter. This work is licensed under the Creative Commons Attribution 4.0 International License. Nanocellulose bio-additives 265 Figure 1: Hierarchical structure of cellulose. Figure 2: Molecular structure of cellulose polymer. belongs to cellulose chain aggregates, including crystal- The application of nanoscale cellulose has attracted line and amorphous regions [13–15]. Around the 1940s, more and more attention, because of not only its bio- some scholars began to get involved in the exploration of degradability and richness, but also its unparalleled NC, and NC colloidal suspension by mixing acid hydrolyzed unique properties, such as barrier properties, mechanical wood and cotton wool was obtained for the first time [16]. and colloidal properties, low density, unique rheology, Ranby then used the concentrated sulfuric acid to degrade and many other excellent characteristics [31–43].Itsspecific the amorphous region of cellulose to prepare rod-shaped properties are summarized in Table 1. rigid cellulose nanocrystals (CNC) with sulfate groups on The rapid economic development has led to high the surface [17,18]. With the advances in theory and tech- demands on paper-based products recently, especially in nology for decades, Turbak, Herrick, and their colleagues packaging industry. One of the major developments is to reported for the firsttimethathigh-pressure homogenization use “green” nanoadditives to enhance paper performance of softwood cellulose fiber slurry could lead to a translucent and functionalize papers with specific characteristics, and highly consistent gel, which was called nanofibrillated by introducing renewable environmentally friendly NC to cellulose (NFC)[19,20]. Since then, many scholars have improve the properties, such as mechanical strength, gloss, opened the road of in-depth and promising research on writing and recyclability. This article overviews and presents NC-based materials [21–29], and gradually expanded its the working principle of NC in paper and NC-based additives potential application in many industrial sectors. Till today, for paper products, including the NC as a paper enhancer on a relatively mature theoretical basis has been established paper, a retention and filtration reagents to increase the reten- and a solid foundation identified for the relevant research tion rate of fine fibers and improve the filtration efficiency, on NC materials. There are a variety of NCs and their and a coating aid to improve the barrier properties of paper. derivatives in publications, which could nevertheless be The application of NC in specialty papers has also been grouped into two divisions: one is nanoparticles or cellulose discussed, including the waterproof paper, fresh paper, nanofibers, including the nanocrystalline cellulose (NCC), insulation paper, blotting paper, and wrapping paper. CNC, cellulose nanowhiskers/NFC, and cellulose nanofibrils (CNF); the other is the micron-sized particles or cellulose nanostructured materials, including the microcrystalline cel- lulose (MCC), cellulose microcrystalline, microfiber cellulose 2 Working mechanisms of NC in (MFC),andcellulosemicrofiber (CMF)[3].Inprinciple,CNC are extracted from the fibers after the amorphous part is paper matrix dissolved, while NFC is highly fibrillated because of the application of high shear force disintegration, resulting in It is well known that the strength of paper depends highly interconnected fibers [30]. mainly on the strength of the fibers themselves, fiber 266 Ao Li et al. Table 1: Properties of NC Nature Specific performance Application Ref. Mechanical Young’s modulus: 150 GPa; excellent network Reinforcement in polymer matrix [41,55,56] properties hydrogen bonding between celluloses Rheology Strong hydrogen bond and the ability to form a Green adhesive; paint; paper coating; [51–54] uniform layer on a hydrophilic substrate; rheology modifier for food, coatings, suspension viscosity decreasing with increasing cosmetics, and pharmaceutical products shear rate Optical properties Translucent, highly consistent gel Transparent material; nano-paper [49,50] Thermal performance Up to 350°C degradation temperature Insulation material [47,48] Biodegradability Hydrophilic surface; rapid degradation at ambient Films/membranes, beads/microspheres, [44] temperature hydrogels/aerogels, bioplastics Oxygen barrier Tight configuration between the fibers leads to Liquid and gas material barrier [45,46] reduced porosity length, fiber orientation distribution, contact area between As a natural polymer enhancer, NC is environmen- fibers, and the strength and number of hydrogen bonds tally friendly and renewable, but its adsorption capacity in the matrix [57]. CNF generally achieves its function for on the fiber surface and the effect of a single use are the strength enhancement of paper by increasing the limited, making it difficult to achieve high strength bonding area of the sheet. The reinforcement mechanism goals of modification. To address this insufficiency, some may be explained from two scenarios: (a) covering the researchers have considered using NCs together with some fiber