Multifunctional Polymeric Nanocomposites Based on Cellulosic Reinforcements

Spain

Preface

Nanocellulose in all its forms (whiskers, nanofibrils, nanofibers, etc.) has in the last few years become one of the most relevant materials in advanced technologies. The rapidly expanding field of biobased technologies is generating many exciting new materials with novel properties and promises to yield advanced applications in diverse industrial sectors in coming years. The availability of new extraction and production techniques, including biotechnological routes and the development of compatibilization procedures for the inclusion of nanocellulose in polymer matrices, has guided the development of new nanocomposites with multifunctional properties for advanced technological applications. Therefore, this book is intended to provide some necessary fundamentals on nanocellulose extraction methodologies, as well as specialized knowledge on processing, design, and applications of polymer matrix nanocomposites with cellulose nanofillers.

Readers are introduced to the study of new materials, collecting in a unified way the state of the art of this novel nanofiller, its polymer matrix nanocomposites, and how they are expanding into many different sectors to enhance classical materials and methods. With a focus on the application of nanocellulose-based nanocomposites with multifunctional activity, the book addresses the methodology of nanocellulose extraction and production, and demonstrates the potential and performance benefits of these particular nanostructured polymers for applications across a variety of sectors, including food active packaging, energy/photovoltaics, the biomedical field, and filtration systems. Furthermore, the book describes how different biomimetic self-assembling processes, functionalization, and organization at the nanoscale level might contribute to the design of required properties at the macro level.

It is our intent that this work be an indispensable resource for the growing number of scientists and engineers from both academia and industry who are interested in the preparation and applications of nanocellulose. It is designed to be useful for those interested in finding new ideas for potential applications, and for industrial scientists active in the formulation and fabrication of polymer products based on renewable resources. Finally, it is our hope that this book will be a valuable guide and resource for undergraduate and postgraduate students in materials science, polymer science, and nanotechnology programs.

We hope you enjoy and profit from the scientific and technical content of this book and the many possibilities offered by nanocelluloses and their polymer matrix nanocomposites.

Chapter 1

Extraction of Lignocellulosic Materials From Waste Products

E. Fortunati, F. Luzi, D. Puglia and L. Torre,    Civil and Environmental Engineering Department, UdR INSTM, University of Perugia, Terni, Italy

Abstract

The need to both avoid waste production and find new renewable resources has led to new and promising research based on the possibility of revalorizing the biomass producing sustainable chemicals and/or materials. This may play a major role in replacing systems traditionally obtained from non-renewable sources. Most of the low-value biomass is termed lignocellulosic, referring to its main constituent biopolymers: cellulose, hemicellulose, and lignin. Different extraction methods were optimized over the years for the extraction of these components from natural fibers and sources, and most of these techniques have been adapted for the extraction of lignocellulosic components from agricultural and forest wastes.

This chapter reviews the characteristics, applications, and especially, the extraction methods for lignocellulosic materials (cellulose, hemicellulose, and lignin), focusing on their advantages and drawbacks in terms of technical issues and environmental impact. Also reported and discussed are a number of recent advances developed in our laboratories.

Keywords

Agricultural wastes; forest wastes; raw materials; cellulose; lignin; extraction methods; green chemistry; sustainability

Contents

1.1 Introduction 1

1.2 Cellulosic-Based Material Structure and Properties 7

1.2.1 Methods for Cellulose-Based Material Extraction From Agro-waste Products 12

1.3 Hemicellulose Structure, Properties, and Applications 15

1.3.1 Hemicellulose Extraction From Agro-waste Products 18

1.4 Lignin Structure, Properties, and Applications 24

1.4.1 Methods for Lignin Extraction From Agro-waste Products 28

1.5 Conclusions 30

References 31

1.1 Introduction

Lignocellulosic materials are the most promising feedstock as they are natural and renewable resources essential to the function of modern industrial societies (Pérez, Muñoz-Dorado, de la Rubia, & Martínez, 2002). Lignocellulose is the term used to describe the three-dimensional polymeric composites formed by plants as structural material. It consists of variable amounts of cellulose, hemicellulose, and lignin, besides other minor compounds. The high heterogeneity of this feedstock mainly depends on its origin, but also on other less manageable factors related to growing, harvesting, and storage conditions. A considerable amount of such materials as waste by-products is being generated through agricultural practices, mainly from various agro-based industries (Pérez et al., 2002). Sadly, much of the lignocellulosic biomass is often disposed of by burning, a practice that is not restricted to only developing countries. Recently, lignocellulosic biomasses have garnered increased research interest and special importance because of their renewable nature (Asgher, Ahmad, & Iqbal, 2013). Therefore, the huge quantities of lignocellulosic biomass can potentially be converted into different high-value products, including biofuels, value-added fine chemicals, and cheap energy sources for microbial fermentation and enzyme production (Iqbal, Kyazze, & Keshavarz, 2013). In the last few years, the use and revalorization of lignocellulosic biomass have represented a strategic solution to reduce natural wastes. At the same time, the use of these materials has represented a significant reduction in the volume of wastes accumulated in soil after cultivation and the pruning of trees (Gencer, 2015), or accumulated on marine coastal regions by the presence of algae such as Zostera seagrass and Posidonia oceanica (Davies, Morvan, Sire, & Bale, 2007; Ferrero, Boronat, Moriana, Fenollar, & Balart, 2013; Fortunati et al., 2015; Khiari, Marrakchi, Belgacem, Mauret, & Mhenni, 2011; Puglia et al., 2014), thereby minimizing the creation of residues and the use of raw materials (Dos Santos et al., 2013). Every year more than 24 million tons of processed vegetable wastes are produced from the agro-food industry, generating an enormous amount of residues without any application or revalorization (Bayer et al., 2014). The biomass obtained from agro-food industries is composed of essentially cellulosic components. These materials are considered an important resource for the extraction of biofuels (Singh, Kuila, Adak, Bishai, & Banerjee, 2012), for other applications as a component to realize composites (Jamil, Ahmad, & Abdullah, 2006), or for the extraction of cellulosic nanostructures (Hsieh, 2013; Johar, Ahmad, & Dufresne, 2012) to use as the reinforcement phase in the production of biodegradable nanocomposites, as previously described in the literature (Battegazzore, Bocchini, Alongi, Frache, & Marino, 2014; Fortunati et al., 2012, 2015). Most of the agricultural lignocellulosic biomass is comprised of about 10–25% lignin, 20–30% hemicellulose, and 40–50% cellulose (Kumar, Barrett, Delwiche, & Stroeve, 2009). As just indicated, cellulose is the major structural component of plant cell walls, while hemicellulose macromolecules are often repeated polymers of pentoses and hexoses. Lignin contains three aromatic alcohols (coniferyl alcohol, sinapyl alcohol, and p-coumaryl alcohol) produced through a biosynthetic process, and it forms a protective seal around the other two components (ie, cellulose and hemicelluloses; Calvo-Flores & Dobado, 2010; Menon & Rao, 2012).

In general, the composition of lignocellulosic material highly depends on its source, whether it is derived from hardwood, softwood, or grasses. Agro-industrial wastes are generated during the industrial processing of agricultural or animal products. Those derived from agricultural activities include materials such as straw, stem, stalk, leaves, husk, shell, peel, lint, seed/stones, pulp or stubble from fruits, legumes or cereals (rice, wheat, corn, sorghum, barley, etc.), bagasses generated from sugarcane or sweet sorghum milling, spent coffee grounds, brewer spent grains, and many others. These wastes are generated in large amounts throughout the year, and are the most abundant renewable resources on earth. They are mainly composed of sugars, fibers, proteins, and minerals, which are compounds of industrial interest. Due to their high availability and composition rich in compounds that could be used in other processes, there is a great interest in the reuse of these wastes, both from an economic and environmental point of view (Table 1.1). The management of these wastes effectively and economically must be given major priority to ensure not only a reduction of the detrimental impact of wastes on the environment, but most importantly, transformation of these wastes into useful raw materials, or the production of value-added products with industrial and commercial potential. Due to the large variations of the chemical compositions of agro-residues, especially polysaccharides and lignin, it is important to choose an appropriate method of biomass fractionation for their effective biotechnological utilization (Howard, Abotsi, Van Rensburg, & Howard, 2003). The cell wall consists of three main components: cellulose microfibrils (with characteristic distributions and organization), hemicellulose, and lignin. There are also smaller amounts of pectin, protein, extractives, and ash. The structure of these materials is complex, and native biomass is generally resistant to chemical and enzymatic hydrolysis (Saha, 2003). During dilute acid hydrolysis of agro-residues, parameters such as temperature, time, acid concentration, and solid-to-liquid ratio play critical roles in obtaining optimum sugar recovery and minimum generation of inhibitors (Taherzadeh & Karimi, 2007). Establishment of these parameters is fundamental to defining optimal conditions for hydrolysis to ensure the success of the process.

Table 1.1

Chemical composition of common agricultural residues and wastes

Source: Reprinted from Lee, H. V., Hamid, S. B. A., Zain, S. K. (2014). Conversion of lignocellulosic biomass to nanocellulose: Structure and chemical processes. Scientific World Journal. Article ID 631013, http://dx.doi.org/10.1155/2014/631013.

Moreover, the need to both avoid waste and find new renewable resources has led to a new and promising avenue of research: the use of food supply chain waste (FSCW) as a renewable biorefinery feedstock. FSCW could be defined as the organic material produced for human consumption discarded, lost, or degraded, primarily at the manufacturing and retail stages. Our food supply chain (FSC) has recently been recognized as being inefficient, producing large and accumulative quantities of waste. The European Union (EU) each year produces just under 90 million tonnes of food waste (FW), 38% of which is directly produced by the food manufacturing sector (Pfaltzgraff, De bruyn, Cooper, Budarin, & Clark, 2013).

In this scenario, the revalorization of different wastes from the agro-food industries (Fig. 1.1A and 1.1B), and the reuse of cellulosic sea wastes (eg, algae) (Fig. 1.1C and 1.1D) or agro-forest (wood and soft wood sources) (Fig. 1.1E and 1.1F) cellulosic wastes, represent a valid strategy for reducing petroleum consumption and, consequently, its environmental impact. In the last several years, these areas have been investigated by different authors, and also in our laboratories.

Figure 1.1 Images of different natural sources: Agave tequilana bagasse (A), barley husks (B), Posidonia oceanica balls (C) and leaves (D), Phormium tenax leaves (E), and hemp fibers (F).

The fractionation of lignocellulosic feedstock is probably the single most crucial step in the biorefinery process because it has a large impact on the yield and efficiency of the subsequent treatments and the quality of the obtained components. It mainly consists of the disruption of the lignocellulosic structure, or biomatrix opening, by using chemical, physical, and/or mechanical treatments in order to enhance the separation of its constituent components, cellulose, hemicelluloses, and lignin. The current research concerning lignocellulose pretreatment processes has investigated several distinct technologies and reagents (see Table 1.2) with the aim of achieving yield and cost-efficient pathways for the comprehensive exploitation of lignocellulosic feedstocks.

Table 1.2

Advantages and disadvantages of several pretreatment methods

aDAH, diluted acid hydrolysis; OS, organosolv; MIC, microbial; SE, steam explosion; AFEX, ammonia fiber explosion; MIL, milling; IL, ionic liquids; COEX, CO2 explosion.

Source: Reprinted from Alvira, P., Tomás-Pejó, E., Ballesteros, M., Negro, M. J. (2010). Pretreatment technologies for an efficient bioethanol production process based on enzymatic hydrolysis: A review. Bioresource Technology, 101, 4851–4861; Pedersen, M., Meyer, A. S. (2010). Lignocellulose pretreatment severity – relating pH to biomatrix opening. New Biotechnology 27, 739–750.

In this context, the characteristics, applications, and especially, the extraction methods for lignocellulosic materials (cellulose, hemicellulose, and lignin) are discussed in this chapter. Also, a number of recent advances from the literature, and several developed in our laboratories, are here reported.

1.2 Cellulosic-Based Material Structure and Properties

Cellulose is one of the most abundant natural polymers on earth, and it represents an inexhaustible raw material (Khalil et al., 2014), with annual production estimated to be over 7.5×10¹⁰ tons (Habibi, 2014). It is the most important and abundant structural constituent of the all-wood plant (Bayer et al., 2014; Fig. 1.2A), and it determines the strength and the stability of cell walls (Moon, Martini, Nairn, Simonsen, & Youngblood, 2011); non-wood plants such as flax, hemp, cotton, and jute represent other cellulose sources. Cellulose is a crystalline, non-branched, renewable, natural polymer produced by photosynthesis (Missoum, Belgacem, & Bras, 2013). It consists of a linear homopolysaccaride composed of β-D-glucopyranose units linked by β-1-4-linkages. The repeat unit is composed of a dimer glucose known as cellobiose (Brinchi, Cotana, Fortunati, & Kenny, 2013). Each monomer presents three hydroxyl groups (Fig. 1.2B), van der Waals forces, and hydrogen bonding between oxygen atoms and hydroxyl groups of adjacent molecules, which promotes stacking of the multiple cellulose chains, forming fibrils as an elementary part of aggregate microfibrils (Moon et al., 2011). The fibrils are the basic structural component of cellulose created during biosynthesis (Jonoobi et al., 2015). The degree of polymerization (DP) or the number of glucose units of the cellulose chains is estimated to be up to 10,000 gluco-pyranose units in wood cellulose and 15,000 in native cotton, but the value depends on its origin (Habibi, 2014). Microfibrils are organized into lattices in the cell wall, with a highly crystalline structure that is resistant to reagents and insoluble in water solutions (Fleming, Derek, Gray, & Matthews, 2001).

Figure 1.2 Schematic representation of wood structure (A) and cellulose repeat unit (B).

Moreover, the ability to form hydrogen bonds plays a relevant role in the formation of fibrillar and semicrystalline packing, characteristics of the physical properties of cellulose. In nature, cellulose is assembled as fibers (Fig. 1.3) and does not occur isolated in individual molecules. Fig. 1.3 shows a schematic illustration of hierarchical cellulosic structures obtained from natural lignocellulosic materials (biomass), down to cellulose microfibrils and/or nanofibrils and cellulose nanocrystals, and the relative estimated elastic modulus for each. It is possible that the Young’s Modulus is related to the increased crystalline cellulose as a consequence of the absence of an amorphous phase such as in lignin, hemicellulose, and amorphous cellulose (Khalil et al., 2014).

Figure 1.3 Image of wood hierarchical structure from biomass tree. Reprinted from Khalil, H. P. S. A., Davoudpour, Y., Islam, M. N., Mustapha, A., Sudesh, K., Dungani, R., Jawaid, M. (2014). Production and modification of nanofibrillated cellulose using various mechanical processes: A review. Carbohydrate Polymers, 99, 649–665.

Cellulose structures are classified into three main categories on the basis of their dimensions, the preparation methods used for extraction, and their origin (native cellulose): (1) cellulose microfibers, also called microfibrillated cellulose (MFC); (2) cellulose nanofibers, also called nanofibrillated cellulose (NFC); and cellulose nanocrystals (CNCs), also called cellulose nanowhiskers (Fig. 1.4).

Figure 1.4 Transmission electron images of microfibrillated cellulose (MFC) from potato pulp (A), scanning electron image of nanofibrillated cellulose (NFC) (B), and transmission electron images of cellulose nanocrystals (CNCs) from Phormium tenax (C). Reprinted from Dufresne, A., Dupeyre, D., Vignon, M. R. (2000). Cellulose microfibrils from potato tuber cells: Processing and characterization of starch-cellulose microfibril composites. Journal of Applied Polymer Science, 76(14), 2080–2092; Fortunati, E., Luzi, F., Puglia, D., Dominici, F., Santulli, C., Kenny, J. M., Torre, L. (2014). Investigation of thermo-mechanical, chemical and degradative properties of PLA-limonene films reinforced with cellulose nanocrystals extracted from Phormium tenax leaves. European Polymer Journal, 56, 77–91; Ho, T. T. T., Zimmermann, T., Hauert, R., Caseri, W. (2010). Preparation and characterization of cationic nanofibrillated cellulose from etherification and high-shear disintegration processes. Cellulose, 18, 1391–1406.

Cellulose microfibrils are long and flexible nanostructures associated with the amorphous phase (Khalil et al., 2014), they have diameters ranging from 3 to 100 nm, and a length normally on the micrometer scale, depending on the natural source of cellulose, pretreatment, and defibrillation method (Andresen, Johansson, Tanem, & Stenius, 2006; Zimmermann, Pöhler, & Geiger, 2004). Microfibrils are considered a string of aggregated nanofibrils linked by an amorphous region (Lin & Dufresne, 2014); MFC is defined by the alternation of amorphous and crystalline domains. The properties and dimensions of MFC differ greatly from the properties of wood or non-wood fibers utilized, the cellulosic material present in high-volume cellulose, a large specific surface area, and high aspect ratio (Nakagaito & Yano, 2005). The delamination of cellulose materials is a procedure that requires intense mechanical treatments, and sometimes with wood material it is necessary to perform pretreatments (Antczak, 2012) to facilitate the mechanical one, expand the inner surface, and break cellulose hydrogen bonds (Khalil et al., 2014). The process also makes it possible to obtain uniform dimensions of the fibrils. The pretreatments reported in the literature are mechanical cutting, enzymatic pretreatment (Henriksson, Henriksson, Berglund, & Lindström, 2007; Pääkkö et al., 2007), and acid hydrolysis (Boldizar, Klason, Kubat, Näslund, & Saha, 1987). Different mechanical treatments are used to prepare MFC, principally microfluidization (Ferrer, Filpponen, Rodríguez, Laine, & Rojas, 2012), high-pressure homogenization (Dufresne et al., 2000; Herrick, Casebier, Hamilton, & Sandberg, 1983; Qua, Hornsby, Sharma, & Lyons, 2011; Turbak, Snyder & Sandberg, 1983), grinding (Siró & Plackett, 2010), and intense ultrasonication (Wang & Cheng, 2009). However, this production is associated with high energy consumption for fiber defibrillation (Zimmermann et al., 2004). After the defibrillation process, MFC is generally obtained in water suspension with a low concentration of around 2% wt. Moreover, if the increased viscosity during processing becomes too high to allow forward pumping of the suspension, the fibrils form a highly entangled network, which behaves as a pseudo plastic gel (Herrick et al., 1983; Saito, Kimura, Nishiyama, & Isogai, 2007). The increase in viscosity is also due to the strong increase of specific area and the higher number of hydrogen bonds for the same volume compared to native lignocellulosic fibers (Missoum, Martoïa, Belgacem, & Bras, 2013).

NFC was discovered by Turbak et al. (1983). NFC was also prepared from different cellulosic sources, including soft and hard woods, sugar beet pulp, banana, Opuntia ficus-indica (cactus), potato, wheat straw, bamboo, and seaweed (Habibi, 2014). NFC obtained from primary cell wall fibers is long and thin. Moreover, it was extracted from secondary cell wall fibers by enzymatic pretreatment followed by high-shear mechanical treatment. NFC consists of aggregates of cellulose microfibrils with a diameter in the range of 20–50 nm and a length of several micrometers (Fig. 1.4B). NFC exhibits both amorphous and crystalline parts, and presents a network structure (Missoum, Belgacem et al., 2013). NFC shows high specific area and a high ability to establish hydrogen bonding and high aspect ratio, which leads to possible entanglement. Its characteristics offer the possibility of preparing transparent nanoporous films once dried, and gel-like suspensions at low concentration in water (Missoum, Martoïa et al., 2013). NFC is used as nanofiller to prepare nanocomposites (Siqueira, Bras, & Dufresne, 2010; Srithep, Turng, Sabo, & Clemons, 2012).

Finally, CNCs are characterized by a typical acicular structure with monocrystalline domains of 1–100 nm in diameter and from tens to hundreds of nanometers in length (Brinchi et al., 2013; Habibi, Lucia, & Rojas, 2010). A colloidal suspension of CNCs was obtained for the first time by controlled sulfuric acid hydrolysis by Randy (Randy & Ribi, 1950). The particles were 100% cellulose and highly crystalline, between 54% and 88% (Habibi et al., 2010; Moon et al., 2011). The morphology and degree of crystallinity of CNCs depend on the natural sources utilized as raw materials and the preparation conditions, and also on the different parameters adopted during the extraction process (Habibi et al., 2010; Khalil et al., 2014; Luzi et al., 2014). The dimensions (width and length) of CNCs depend on the natural sources utilized (Habibi et al., 2010; Khalil et al., 2014; Luzi et al., 2014). In fact, as previously observed by other authors, the CNCs extracted from wood were 3–5 nm in width and 100–200 nm in length, and for a sea plant were reported to be 20 nm in width and 1000–2000 nm in length (Fortunati et al., 2015; Klemm et al., 2011). The CNCs extracted from tunicates and sea animals were larger in dimension with respect to the CNCs extracted from cotton; in fact, the first one gives c.10–20 nm in width and 500–2000 nm in length, while, the second one has smaller dimensions of 5–10 nm in width and 100–300 nm in length. The aspect ratio defined as the ratio length-to-width (L/w) can vary between 10 and 30 for cotton and c.70 for tunicates (Klemm et al., 2011). These different dimensions of CNCs extracted from wood and tunicates are due to the presence of higher quantities of crystalline domains with respect to the amorphous regions in the sea animal sources (Brinchi et al., 2013).

In the last few years, some reviewers have focused on the surface modifications of CNCs due to the presence and natural advantage for an abundance of hydroxyl groups on their surfaces. In particular, some functionalizations have been tried, including etherification, oxidation, esterification, polymer grafting, silylation, etc. Several chemical functionalizations have been investigated to obtain better dispersion of CNCs, introducing stable negative or positive electrostatic charges on the nanocellulose surface.

Concerning their final properties, CNCs have a high elastic modulus, around 150 GPa (Šturcová, Davies, & Eichhorn, 2005), high stiffness, a low thermal expansion coefficient of 10−7 K−1 (Nishino, Matsuda, & Hirao, 2004), and density of approximately 1.57 g cm−3. These characteristics permit the use of CNCs as the reinforcement phase in thermoplastic and/or thermosetting matrices in nanocomposites. Moreover, CNCs have other advantages, such as biodegradability, biocompatibility, and non-toxicity to cells. CNCs can be used in biomedicine to realize medical devices, including cardiovascular grafts (Lin & Dufresne, 2014), and in food packaging applications (Arrieta et al., 2014; Fortunati et al., 2015), both of which increase specific characteristics of fundamental importance in these two different sectors.

1.2.1 Methods for Cellulose-Based Material Extraction From Agro-waste Products

Several kinds of methods for extracting cellulose-based materials from plant fibers and then from agro-waste products have been proposed. These methods can be classified into three groups on the basis of the extraction mechanisms: physical, chemical, and enzymatic procedures. Several physical extractions, such as mechanical homogenization and mechanical grinding, typically used to produce cellulose nanofibrils, are time-consuming methods and require a lot of energy. The principle behind these methods is based on the modification of dilute cellulosic wood pulp-water suspensions through a mechanical homogenizer in which a large pressure drop facilitates microfibrillation (Siró & Plackett, 2010). High pressure, high velocity, and other forces on the fluid stream generate shear rates within the product stream, reducing particles at nanoscale (Lee, Chun, Kang, & Park, 2009). Crushing represents another mechanical procedure for disintegration of cellulose fibers in nanosized structures (Chakraborty, Sain, & Kortschot, 2005). The crushing process is influenced by a series of factors such as the origin of the fibers, technological factors, and equipment-dependent factors, and through this process, the crystallinity of cellulose material decreases due to the conformation and configuration adjustment, as well as the increase of polymer solubility. A subclass of the prior method is cryocrushing. This approach requires the immersion of the water-swollen cellulosic system in liquid nitrogen, followed by crushing.

A major obstacle which needs to be overcome for successful commercialization of cellulosic-based structures, especially nanocellulose, is the high energy usage from mechanical disintegration of the fibers into nanofibers, which often involves several passes through the disintegration device. For this reason, scientists have combined mechanical pretreatments with chemical procedures to increase the efficiency of size reduction before homogenization (Wang & Sain, 2007). One method for this purpose might be ultrasonication (Wang & Cheng, 2009), which could be used alone or in combination with other methods (eg, acid hydrolysis) in order to obtain cellulose fibers. Achieving a high dispersion requires the variation of parameters such as amplitude and intensity at the tip of the probe, temperature, and concentration of the disperser, pressure, volume, and shape of the vessel used.

Among the cellulose depolymerization treatments, oxidation pretreatment is one of the common techniques used to disintegrate cellulose into nanocellulose. It is achieved by applying 2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPO) radicals able to generate sinter-fibrillar repulsive forces between fibrils and, in such a way, to modify the surface of native cellulose (Saito, Nishiyama, Putaux, Vignon, & Isogai, 2006).

Steam explosion is another efficient pretreatment method for converting lignocellulosic biomass to cellulose nanofibers (Cherian et al., 2010). The steam explosion process entails saturating the dry material with steam at elevated pressure and temperature followed by a sudden release of pressure, during which the flash evaporation of water exerts a thermo-mechanical force that causes the material to rupture. By this method, the nanofibrils are liberated from the bundles as individual entities to increase their reinforcement ability in composites. Steam explosion causes the hemicelluloses and lignin from the wood to be decomposed and converted into a low-molecular-weight fraction that can be recovered by extraction. Therefore, most of the water-soluble fraction of hemicelluloses can be removed by water extraction. At the same time, a part of the low-molecular-weight fraction of lignin is also extracted. All these steps allow elimination of lignin and hemicelluloses, while leaving cellulose moieties intact if optimal conditions are respected.

The chemical-based approaches, represented mainly by strong acid hydrolysis, can remove the amorphous regions of cellulose fibers, producing cellulose nanostructures as nanocrystals. The isolation of nanocellulose typically occurs in two stages. The first is a pretreatment of the source material that involves the complete or partial removal of matrix materials and isolation of the cellulosic fibers, and the second one is a controlled chemical treatment—generally hydrolysis—that is able to remove the amorphous regions of the cellulose polymer (Bondeson, Mathew, & Oksman, 2006; Tang, Yang, Zhang, & Zhang, 2014). During hydrolysis, amorphous domains are preferentially hydrolyzed, whereas crystalline regions have higher resistance to acid attack. During the process, the hydronium ions penetrate the cellulose chains in the amorphous regions, thus promoting the hydrolytic cleavage of the glycosidic bonds and releasing individual crystallites. A variety strong acids have been shown to successfully degrade cellulose fibers, but hydrochloric and sulfuric acids have been used extensively. One of the main reasons for using sulfuric acid as the hydrolyzing agent is its reaction with the surface hydroxyl groups via an esterification process allowing the grafting of anionic sulfate ester groups. In addition, alkaline hydrolysis is able to enhance the partial separation of the cellulose fibers from the cell wall and improve the physical and chemical characteristics of cellulose, particularly its reactivity to other chemical agents (Taherdanak & Zilouei, 2014). These treatments are usually made using diluted solutions of NaOH (1–10%) at low or high temperatures, and concentrated NaOH solutions over 10% only at low temperatures. However, these conventional, strong, chemical-based treatments for nanocellulose synthesis are considered environmentally incompatible and economically unfriendly. Thus, researchers have claimed that the use of enzymatic hydrolysis may benefit from an environmental point of view in comparison with acid treatment (Satyamurthy & Vigneshwaran, 2013).

Biological-based hydrolyzing agents (composed of a multi-component enzyme system) allow restrictive and selective hydrolysis of specified components in the cellulosic fibers. For the production of nanocellulose, enzymes can also be used which, in combination with refining methods, is called biorefining. For this purpose, multi-enzyme preparations are usually applied which contain enzymes degrading both cellulose and other accompanying polymers, such as pectin, hemicellulose, and lignin. Enzymes can be used in two ways. First, the treatment of biomass with enzymes such as pectinase, hemicellulase, and ligninase may lead to the removal of non-cellulose materials. Second, in order to obtain nanofibers, industrial cellulases can be used, which are enzymes with various activities that can hydrolyze cellulose into smaller structural elements, as well as into oligosaccharides, cellobiose, and ultimately, into glucose. Enzymatic processes are widely considered to be clean, however, although the enzymatic route for nanocellulose synthesis offers the potential for higher yields, lower energy costs, higher selectivity, and milder operating conditions than chemical approaches, this technology is still hindered by economic (costly cellulase enzyme) and technical (rate-limiting step of cellulose degradation with long processing period)