Subscriber access provided by READING UNIV Perspective IMPORTANCE OF AGRICULTURE AND INDUSTRIAL WASTE IN THE FIELD OF NANO CELLULOSE AND ITS RECENT INDUSTRIAL DEVELOPMENTS: A REVIEW Rajinipriya Malladi, Malladi Nagalakshmaiah, Mathieu Robert, and Said Elkoun ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.7b03437 • Publication Date (Web): 03 Feb 2018 Downloaded from http://pubs.acs.org on February 4, 2018
Just Accepted
“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.
ACS Sustainable Chemistry & Engineering is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties. Page 1 of 70 ACS Sustainable Chemistry & Engineering
1 2 3 1 IMPORTANCE OF AGRICULTURAL AND INDUSTRIAL WASTE IN THE FIELD OF 4 5 6 2 NANOCELLULOSE AND RECENT INDUSTRIAL DEVELOPMENTS OF WOOD 7 8 3 BASED NANOCELLULOSE: A REVIEW 9 10 11 4 Rajinipriya Malladi, Malladi Nagalakshmaiah*, Mathieu Robert and Saïd Elkoun* 12 13 5 Center for Innovation in Technological Eco design (CITE), University of Sherbrooke, Quebec, 14 6 Canada. 15 16 7 Abstract: 17 18 19 8 The nano sized cellulose materials is topical in the sphere of sustainable materials lately. The two 20 21 9 key groups of nanocellulose (NC) are 1) Nanofibrillated cellulose (NFC) and 2) Cellulose 22 23 24 10 nanocrystals (CNC). They are often considered as a second generation renewable resource, 25 26 11 which also serves as a better replacement for the petroleum based products. The major attention 27 28 12 on these materials are increasing because of their low density, high mechanical, renewable and 29 30 31 13 biodegradable properties. There are many literatures on the isolation of NFC and CNC from 32 33 14 different sources like hard/soft wood and agriculture biomass. However, this is a comprehensive 34 35 15 review dedicated to the extraction and properties of NFC and CNC only from the agriculture and 36 37 16 industrial waste using mechanical, chemical and enzymatic methods. This article explores in 38 39 40 17 detail about the importance of agriculture waste and the pre treatments, methods involved in the 41 42 18 production of nanocellulose, the properties of NC prepared from crop and industrial wastes. The 43 44 19 potential applications of nanocellulose from different sources are discussed. The current 45 46 47 20 extensive industrial activities in the production of nanocellulose had been presented. This review 48 49 21 will likely draw attention of researchers towards crop and industrial wastes as a new source in 50 51 22 the realm of nanocellulose. 52 53 54 55 56 57 58 59 60 ACS Paragon Plus Environment ACS Sustainable Chemistry & Engineering Page 2 of 70
1 2 3 23 Keywords: Nanocellulose (NC), Nanofibrillated cellulose (NFC), Cellulose nanocrystals (CNC), 4 5 6 24 Agriculture biomass and Industrial developments. 7 8 9 25 INTRODUCTION: 10 11 12 26 The production of cellulosic material increases tremendously to fulfil the need for renewable and 13 14 27 eco friendly sustainable materials.1 Cellulose is often considered as one of the most important 15 16 17 28 natural resource. With the advent of nanoscience, the researchers and industries focus in the 18 19 29 production of NC in huge quantities and it is evident from increasing number of publications and 20 21 30 patents in this field.2The trailing purpose behind the growth of research in NC lies in their 22 23 3 24 31 promising properties such as low density and high mechanical strength. Cellulose can be found 25 26 32 in different sources like wood, natural fibers (agriculture biomass), marine animal (tunicate), 27 28 33 algae and fungi.4 The composition of cellulose is highly dependent on the source.5 This review 29 30 31 34 deals with the crop waste as a core source for the extraction of NC. 32 33 35 34 With the ever increasing demand for renewable resource, the crop waste is meant to be an 35 36 36 appropriate material. The recovery of waste makes it possible to protect the environment and to 37 38 37 benefit from low cost reinforcements. Agriculture waste biomass is significant resource for the 39 40 38 reason it is environmental friendly, low cost, readily available, renewable and exhibit somehow 41 42 6 7 43 39 acceptable mechanical properties. The crop waste constitutes abundant natural fibers. The 44 45 40 agriculture waste fibers can be obtained from cotton stalk, pineapple leaf, rice straw, flax, hemp, 46 47 41 soy pods, rice husk, garlic straw, potato peel, grape skin etc. Agri biomass can be used in 48 49 50 42 multitude applications like paper, textile industry, composites, building, furniture and medical 51 52 43 fields. 53 54 55 56 57 58 59 60 ACS Paragon Plus Environment Page 3 of 70 ACS Sustainable Chemistry & Engineering
1 2 3 44 The NC market is currently emphasized because of the augmented focus of the governments, 4 5 6 45 industries, funding agencies and Universities. The bio based economy is rapidly increasing 7 8 46 resulting in the higher investments. The NC production includes high value added applications 9 10 47 like composites, paper industry, packaging, paints, oil &gas, personal care, medical care etc.8 11 12 48 The NC is first commercialised by celluforce Inc. in Quebec; a joint venture between FP 13 14 9 15 49 innovations and Domtar. The NC industries are prominent in the areas of Asia Pacific, North 16 17 50 America, Europe, Latin America and Middle East and Africa including leading names like 18 19 51 Paperlogic, University of Maine, Borregaard Norway, American Process, Nippon Paper Japan, 20 21 22 52 Innventia Sweden, CTP/FCBA France, Oji Paper, Japan. 23 24 25 53 This article aims to deliver the consolidate details on structure and multiple sources of cellulose, 26 27 54 NC, their extraction from agri based sources and the current industrial developments on NC 28 29 55 production and applications. There are numerous literature which deal with various aspects of 30 31 10,11 12–14 32 56 NC like source, production of nanofibrillated cellulose, production of nanocrystals, 33 11 15 16 17 34 57 extraction methods, pre treatments, properties and applications. However, there is only 35 36 58 limited review on the agriculture biomass for the extraction of NC.6,18 Since the urge of 37 38 59 converting agriculture waste into wealth is increasing for the reasons of waste management, 39 40 41 60 improve ecofriendly resource and creating new source of economy, this review paper 42 43 61 concentrates on the inside story of the agriculture biomass, extraction of NC from crop waste, 44 45 62 different treatments, pre treatments involved. It also deals with the properties of isolated NC. To 46 47 48 63 conclude, the applications and industrial evolution in the production of NC are also addressed. 49 50 51 64 SOURCE OF CELLULOSE: 52 53 54 65 Cellulose is the amplest resource of natural fibers. Annually, the extraction of cellulose is 55 10 12 56 66 assessed to be over 7.5 x 10 tons. Cellulose is extracted from various sources including wood 57 58 59 60 ACS Paragon Plus Environment ACS Sustainable Chemistry & Engineering Page 4 of 70
1 2 3 67 (Hard or soft wood), seed (cotton), bast (Flax, hemp), cane (bamboo, bagasse), leaf (Sisal), straw 4 5 19 6 68 (rice, wheat), fruit (Coir), tunicate, algae, fungi, bacteria and minerals. Figure 1 shows the 7 8 69 hierarchical representation of the chief sources from which cellulose can be extracted. 9 10 11 70 12 13 14 71 15 16 72 17 18 19 73 20 21 74 22 23 24 75 25 26 27 76 28 29 77 30 31 32 78 Figure 1. Hierarchical representation various sources of cellulose. 33 34 35 79 The source is placed in the order of conventional source like wood and cotton, which is 36 37 80 considered as the primary origin. Wood can be classified as soft/hard wood based on their 38 39 81 structural aspect.20 Then comes the agriculture waste which are the unprocessed wastes that are 40 41 42 82 coming directly from the field residues like rice straw, banana rachis, corncob etc. The crop 43 44 83 waste is becoming the second highest source of cellulose. The industrial waste is the processed 45 46 84 waste produced by the industries like sugarcane bagasse, tomato and garlic peels etc. which is 47 48 49 85 another source of cellulose emerging lately. Cellulose can be obtained from some other small 50 51 86 class of sources like marine animal (tunicate), algae, fungi and bacteria. The interest of this 52 53 87 review lies on the second and third grid of the pyramid representation i.e. Crop and industrial 54 55 56 88 waste for the fact that this source needs to be explored more. The basic constitution of the 57 58 59 60 ACS Paragon Plus Environment Page 5 of 70 ACS Sustainable Chemistry & Engineering
1 2 3 89 foretold fibers is cellulose, lignin and hemicelluloses. However, the chemical composition differs 4 5 6 90 for each some of which are tabulated in table 1 on dry basis. Besides cellulose lignin and 7 8 91 hemicelluloses, some sources contain pectin, waxes and other water soluble components. 9 10 11 12 13 14 15 Table 1. Chemical composition of different sources on dry basis. 16 17 18 Source Cellulose Hemicellulose Lignin Reference 19 20 (wt.%) (wt.%) (wt.%) 21 22 23 24 Pine (softwood) 44.0 27.0 28.0 25 26 27 28 Yellow birch 47.0 31.0 21.0 29 30 (hardwood) 31 32 21 33 34 Jute 73.2 13.6 13.4 35 36 37 Wheat straw 48.8 35.4 17.1 38 39 40 41 Rice husk 45.0 19.0 19.5 42 43 44 22 45 Bagasse 55.2 16.8 25.3 46 47 48 Banana 63–64 10 5 49 50 51 23 52 Flax 71 18.6 20.6 2.2 53 54 55 56 57 58 59 60 ACS Paragon Plus Environment ACS Sustainable Chemistry & Engineering Page 6 of 70
1 2 3 4 Hemp 70 74 17.9 22.4 3.7 5.7 5 6 7 Mulberry barks 37.38 ± 2.31 25.32 ± 2.45 9.99 ± 0.82 24 8 9 10 25 11 Garlic straw 41 18 6.3 12 13 14 26 15 Carrot residue 81 9 2.5 16 17 18 Ground nut shells 38.31 27.62 21.10 27 19 20 21 28 22 Onion skin 41.1 ± 1.1 16.2 ± 0.6 38.9 ± 1.3 23 24 25 92 26 27 28 93 CELLULOSE: 29 30 31 94 Cellulose is the natural polysaccharide first isolated by Anselme Payen in 1838 from wood when 32 33 95 treated with nitric acid.12 They exist as microfibrils in the plant cell wall of multiple sources. The 34 35 29 36 96 diameter of the fibrils varies from 3 35 nm depending on the source. Cellulose contains linear 37 38 97 polymer chain comprised of glucose monomer named β 1,4 linked anhydro D glucose units as 39 40 98 shown in figure 2. The degree of polymerization of cellulose is up to 20000 units. For wood and 41 42 30 43 99 cotton it is approximately 10000 and 15000 glucose units respectively. 44 45 100 Anhydroglucose is the monomer and cellobiase is the dimer of cellulose. Each glucopyranose 46 47 101 unit contains 3 highly reactive hydroxyl groups which are responsible for the hydrophilicity, 48 49 50 102 chirality, biodegradability etc. of cellulose. The individual cellulose chain contains reducing end 51 52 103 because of the hemiacetal unit with both aliphatic and carbonyl group and the non reducing end 53 54 55 56 57 58 59 60 ACS Paragon Plus Environment Page 7 of 70 ACS Sustainable Chemistry & Engineering
1 2 3 104 with closed end group.31 The higher mechanical properties of each microfibrils result from the 4 5 6 105 strong hydrogen bonds. 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 Figure 2. a) 3D structure of cellulose.b) structure formula of cellulose. Adopted from Cave 26 and Walker (1994).31 27
28 29 30 106 The β 1,4 glycosidic bonds builds an ordered crystalline structure by Vander Waals forces and 31 32 107 inter & intra molecular hydrogen bonding.32 In these regions, the cellulose chains are strongly 33 34 108 arranged into crystallites. The hydrogen bond existing between cellulose chains make it highly 35 36 37 109 stable but poorly soluble in water and other solvents. These hydrogen bonding network and the 38 39 110 molecular arrangement results in polymorphs or allomorphs of cellulose. There are six 40 41 111 interconvertible polymorphs of cellulose had been identified id Est cellulose I, II,IIII,IIIII,IVI and 42 43 33 44 112 IV II. In 1984 Atalla and Vander Hart proved that the native cellulose I can be subdivided into 45 34 35 36 46 113 Iα and Iβ. Cellulose II can be obtained from the chemical regeneration or by mercerization. 47 48 114 Cellulose III is formed when cellulose I or II is treated with ammonia or various amines37 and the 49 50 115 polymorphs IV and IV are produced by heating cellulose III or III respectively at 260ºC in 51 I II I II 52 38 53 116 glycerol. 54 55 56 57 58 59 60 ACS Paragon Plus Environment ACS Sustainable Chemistry & Engineering Page 8 of 70
1 2 3 117 The amorphous region results from the breakage and disordered hydrogen bonds.39 Figure 3 4 5 6 118 shows the crystalline and amorphous regions of cellulose. The hydrogen bonding and orientation 7 8 119 of cellulose differs extensively for the different source. 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 Figure 3. Crystalline and amorphous regions of cellulose. 25 26 27 120 28 29 30 121 HEMICELLULOSE: 31 32 33 122 Plant cell wall is mainly made up of cellulose, hemicellulose and lignin as stated before. 34 35 123 Hemicellulose is the second major component accounting 15 30% of the cell wall.40 They are 36 37 124 entrenched around the microfibrils bundles as shown in figure 4. 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 Figure 4. Cellulose bundles embedded by hemicelluloses and lignin. 55 56 57 58 59 60 ACS Paragon Plus Environment Page 9 of 70 ACS Sustainable Chemistry & Engineering
1 2 3 125 Hemicellulose can be divided into four different classes based on their structure as 1) Xylans, 2) 4 5 6 126 Mannans, 3) β glucans and 4) Xyloglucans. Hemicelluloses are branched polysaccharides 7 8 127 containing β 1→4 linked backbones of glucose, mannose or xylose in equatorial configuration at 9 10 128 C1 and C4 and the structure varies with the side chain type and the distribution of these 11 12 129 backbones. 41 The figure 5 shows the structure of some backbones of hemicellulose like β 1,4 13 14 42 15 130 glucan (figure 5a) β 1,4 xylan (figure 5b) and β 1,4 Mannan (figure 5b). 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 Figure 5. Structural backbone of hemicellulose a) β 1,4 glucan b) β 1,4 xylan 34 35 42 36 c) β 1,4 Mannan. Adopted from 37 38 131 39 40 41 132 Few examples of xylans are glucoronoxylans and arabinoxylans and they can be found in straw, 42 43 133 stalks, husk etc. Mannans can be classified as gluco and galactomannans which can be extracted 44 45 134 form gaur, locust bean etc. Xyloglucans are used as thickening and gelling agent in foods and 46 47 43 48 135 can be isolated from tamarind seeds. As reported in the literature, it is known that 49 50 136 hemicelluloses play a key role in facilitating the fibrillation process.44,45 The reason is most 51 52 137 likely because of the hydrogen bonding and negative charges on hemicelluloses. As realised 53 54 55 138 from figure 4, hemicellulose surrounds cellulose microfibrils through numerous hydrogen 56 57 58 59 60 ACS Paragon Plus Environment ACS Sustainable Chemistry & Engineering Page 10 of 70
1 2 3 139 bonding which in turn seals the gap between the microfibrils and hinders the fibrils from 4 5 6 140 aggregation. Also, hemicelluloses contain glucuronic acid with carboxyl groups which enables 7 45 8 141 the delamination of fibers by means of electrostatic repulsion forces. 9 10 11 142 LIGNIN: 12 13 14 143 Lignin is a heterogeneous and irregular cross linked polymer of phenyl propane. It is amorphous 15 16 144 and optically inactive material with three different monomers namely Coumaryl alcohol, 17 18 145 Coniferyl alcohol and Sinapyl alcohol whose structure is shown in figure 6.46 Lignin is derived 19 20 21 146 by the enzyme mediated polymerization. The molecular weight of isolated lignin is typically in 22 23 147 the range of 1000 20,000 g/mol, though the degree of polymerisation in nature is difficult to 24 25 148 arrive on the account that lignin is highly fragmented during isolation and it also contains many 26 27 47 28 149 repeating substructures in a seemingly haphazard manner. 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 Figure 6. Structural units of lignin. Reprinted with permission.46 Copyright 2014 American 44 45 Chemical Society. 46 150 47 48 49 151 Lignin is used in multiple applications as emulsifiers, dyes, synthetic flooring, binding, 50 51 152 thermosets, paints etc. The sulfur free and water soluble lignin is used for automotive brakes, 52 53 153 wood panel products, bio dispersants, polyurethane foams, and epoxy resins for printed circuit 54 55 154 48 56 boards. 57 58 59 60 ACS Paragon Plus Environment Page 11 of 70 ACS Sustainable Chemistry & Engineering
1 2 3 155 4 5 6 156 Nanocellulose: 7 8 9 157 The plant cell wall can be classified into two namely primary and secondary. The primary cell 10 11 158 12 wall is the external thin layer (less than 1 µm) and the secondary cell wall chiefly contains 13 49 14 159 cellulose microfibrils. The Hierarchical configuration of wood to cellulose nanocrystals are 15 16 160 shown in figure 7. Generally, either length or diameter of the cellulose particles are in the nano 17 18 161 size (1 100nm) are called as NC. The plant cell wall consisting bundles of the cellulose fibrils 19 20 21 162 and their diameter is in few microns. Each cellulose bundle is consisting millions of micro 22 23 163 fibrils, these micro fibrils are composed with elementary fibrils or nano fibrils. The diameter of 24 25 164 the nanofibrils is about 5nm, whereas in the case of the micro fibrils the diameter will vary from 26 27 28 165 10 50nm. Every nano fibers are composed of flexible amorphous and strong crystalline parts. 29 30 31 32 33 34 35 36 37 38 39 40 41 42 Figure 7. Hierarchical structure of cellulose and its derivatives in nanoscale. 43 44 166 45 46 167 Several cellulosic derivatives are isolated from these microfibrils and depending on their 47 48 1 49 168 isolation methods, source, dimensions they are called , NC, whiskers, nanofibrils. Depending on 50 51 169 their method of preparation, NC is classified into 1) cellulose nanocrystals (CNC) and 2) nano 52 53 170 fibrillated cellulose (NFC). The other type of NC called bacterial cellulose (BC) and electro spun 54 55 56 171 cellulose nanofibers (ECNF) can also be isolated. Nevertheless, CNC and NFC are considered as 57 58 59 60 ACS Paragon Plus Environment ACS Sustainable Chemistry & Engineering Page 12 of 70
1 2 3 172 the more common and they are produced by top down process i.e. by disintegration of cellulose 4 5 6 173 fibers to nanoscale particles whereas BC and ECNF are produced by bottom up process in which 7 8 174 nanofibers are formed from low molecular weight sugars by bacteria or from dissolved cellulose 9 10 175 by electrospinning respectively.11 The morphological images of four different NC from corn 11 12 176 husk (figure 8a), tunicate (figure 8b), bacterial cellulose (figure 8c) and electro spun cellulose 13 14 50–53 15 177 nanofibers (figure 8d) is shown in figure 8. 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 Figure 8. Micrographs of NC a) NFC from corn husk. Reprinted with permission.50 Copyright 45 46 2015 Elsevier. b) CNC from tunicate. Reprinted with permission.51 Copyright 2014 American 47 48 52 49 Chemical Society c) Bacterial cellulose. Reprinted with permission. Copyright 2006 American 50 53 51 Chemical Society and, d) electro spun cellulose nanofibers. Reprinted with permission. 52 53 Copyright Intech, DOI: 10.5772/8153. 54 55 178 56 57 58 59 60 ACS Paragon Plus Environment Page 13 of 70 ACS Sustainable Chemistry & Engineering
1 2 3 179 NANOFIBRILLATED CELLULOSE: 4 5 6 180 The cellulose fibers are fibrillated usually by mechanical breakdown to achieve clusters of 7 8 181 9 cellulose microfibrils due to shear forces called nanofibrillated cellulose. The nomenclature can 10 11 182 be different for these nanofibrils as a) nano fibrillated cellulose (NFC) b) micro fibrillated 12 13 183 cellulose (MFC) c) cellulose nanofibrils (CNF) d) cellulose filaments (CF). The diameter of NFC 14 15 184 is in nanoscale i.e. less than 100 nm and the length can be of few micrometers. The structural 16 17 18 185 morphology of NFC from corn husk is shown in figure 8a. 19 20 21 186 The NFC was first obtained by Turbak et al., 1983 and Herrick et al., 1983 by means of a Gaulin 22 23 187 laboratory homogenizer.54, 55The specific surface area and the number of hydrogen bonds 24 25 188 ensuing from the surface hydroxyl groups is increased during fibrillation or delamination. Owing 26 27 28 189 to this, NFCs are inclined to form gels showing increased viscosity. The major impairment of 29 30 190 NFCs are they tend to form gels once produced, their hydrophilicity restricts the dispersion with 31 32 191 few hydrophobic polymers. Importantly, the extraction process consumes high energy. All these 33 34 192 difficulties can be overcome with some pre treatments and surface modifications. Besides the 35 36 37 193 drawbacks, NFCs are commercially produced and used in plenitude applications including 38 39 194 composites, coatings, personal care, constructions etc.8 40 41 42 195 CELLULOSE NANOCRYSTALS: 43 44 45 196 Cellulose nanocrystals, also termed nano whiskers, are spherical “rod” or “needle” like highly 46 47 197 crystalline structures with diameter of 2 25 nm and length from 100 750 nm depending on the 48 49 50 198 source. The morphology of CNC from tunicate is shown in figure 8b. CNCs are first obtained by 51 56 52 199 acid hydrolysis by Ranby in 1949. As discussed in the structure of cellulose, it contains both 53 54 55 56 57 58 59 60 ACS Paragon Plus Environment ACS Sustainable Chemistry & Engineering Page 14 of 70
1 2 3 200 crystalline and amorphous regions. During the acid hydrolysis, the amorphous region is removed 4 5 6 201 leaving behind the crystalline particles as displayed in figure 9. 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 Figure 9. Isolation of CNC from cellulose by sulphuric acid hydrolysis. Reprinted with 22 permission.57 Copyright 2017 Royal Society of Chemistry. 23 24 202 25 26 27 203 The amorphous regions present in the cellulose chain is the first and easily accessible to the acid 28 29 204 for the hydrolytic action due to kinetic force and steric hindrance however the crystalline 30 31 205 regions are more unaffected by the hydrolysis. 13, 56 The size, morphology and degree of 32 33 206 crystallinity will vary depends on the source. The acid hydrolysis can be achieved using 34 35 36 207 hydrochloric acid (HCL) and sulphuric acid. However, HCL does not result in stable suspensions 37 38 208 due to the absence of the surface charge. Whereas in the case of sulphuric acid hydrolysis, the 39 40 209 surface of the cellulose attains the half ester sulfate groups resulting in high negative charge. 59 It 41 42 43 210 was reported that the length and surface charge of CNC fibers depends on the hydrolysis period 44 45 211 by Dong et al.60The length of CNC fibers decreased while increasing the hydrolysis time by 46 47 212 increasing the surface charge. 48 49 50 213 Another interesting aspect was studied by R.H. Marchessault et al. which showed the 51 52 214 61 53 birefringent liquid crystalline phases. Revol et al. in 1992 proved that CNC formed chiral 54 55 215 nematic phases. The authors stated that cellulose, in the form of fibrillar fragments was dispersed 56 57 58 59 60 ACS Paragon Plus Environment Page 15 of 70 ACS Sustainable Chemistry & Engineering
1 2 3 216 in water and above critical concentration, the self organization of cellulose crystallites into chiral 4 5 6 217 nematic liquid crystalline phase (parallel alignments of the anisotropic crystallites) was observed. 7 62 8 218 9 10 11 219 BACTERIAL CELLULOSE: 12 13 14 220 Evident from figure 1, cellulose is not only found in plant cell walls but also can be obtained 15 16 221 from bacteria and are named as bacterial cellulose (BC). The bacterial cellulose is also referred 17 18 222 as microbial cellulose, bacterial NC or bio cellulose.1 BC can be synthesized from Acetobacter, 19 20 63 21 223 Rhizobium, Agrobacterium, and Sarcina by aqueous culture media cultivation. The 22 23 224 morphology of the bacterial cellulose is shown in the figure 8c. 24 25 26 225 ELECTROSPUN CELLULOSE NANOFIBERS: 27 28 29 226 In this method, cellulose is dissolved in a suitable solvent and a high voltage is applied through 30 31 227 the solution so that the particles are charged and repulsive force is created. The network of the 32 33 228 34 ECNF is shown in the figure 8d. At a critical voltage, the repulsive forces overcome the surface 35 36 229 tension of the solution. When it is passed through air, the solvent evaporates resulting in fiber 37 38 230 formation which are then collected on an electrically grounded plate.64 ECNF is used invarious 39 40 231 applications.65 41 42 43 232 IMPORTANCE OF AGRICULTURE BIOMASS: 44 45 46 233 Agriculture sector is producing huge volume of wastes which is menace to the environment as 47 48 49 234 they are either burnt in the fields causing air pollution or accumulated in the soil. The recovery of 50 51 235 this waste makes it possible to protect the environment. But at the same time, it will also create 52 53 236 new economy. Agriculture waste is the richest form of natural fiber and it is more promising and 54 55 56 237 sustainable material. Towards the advancement of the materials, scientists and researchers need 57 58 59 60 ACS Paragon Plus Environment ACS Sustainable Chemistry & Engineering Page 16 of 70
1 2 3 238 to elaborate new materials and new technology based on intelligent and eco conscious materials. 4 5 6 239 In other words, materials have greater impact on environment and thus choosing them reflects on 7 8 240 the technologies they are used. On that account, materials can be an important part of solution to 9 10 241 the problem that created by specific technology. Aforesaid solution could be developing a new 11 12 242 material that works better based on eco designed or bio based products.66 Hence, interest 13 14 15 243 towards sustainable materials produced using crop waste is increasing among researchers. 16 17 244 Compared to wood in which case cellulose is present in secondary cell wall, it is more facile to 18 19 245 isolate cellulose from agriculture fibers wherein cellulose is found in primary cell wall and the 20 21 67 22 246 fibrillation in the latter case is done with low energy consumption. 23 24 25 247 As per the OECD FAO (Organisation for Economic Co operation and Development and 38 the 26 27 248 Food and Agriculture Organization) agriculture outlook, every year farmers are harvesting 39.35 28 29 249 million tons of natural fibres from plants.68 Considering the amount of production, the waste 30 31 250 32 outcome is also a lot out of which fibers can be obtained. Correspondingly, few millions of 33 34 251 metric tons of fibers are available every year and the sum increases annually. Converting these 35 36 252 waste materials into wealth is ongoing interest of the researchers. NC from plant origin alone or 37 38 253 with mixture of another materials can be used in quite a lot of applications. Natural fibers serving 39 40 41 254 as agri based raw material for the extraction of NC can be obtained from all parts of the plant 42 43 255 like stem, leaves, bark, seeds. Fibers gained from the stem are called ‘bast fibers’ and few 44 45 256 examples of bast fibers are flax, hemp, kenaf etc. Pineapple, banana, date palm, Sisal are 46 47 48 257 examples of leaf fiber and cotton, kapok & coir falls under the seed fibers. 49 50 258 The quality of the fibers depends on different factors like production location, climatic 51 52 259 conditions, plant species as presented in figure 10.69 Consequently, it is a requisite to have better 53 54 260 55 understanding of the properties of vegetal waste fiber. 56 57 58 59 60 ACS Paragon Plus Environment Page 17 of 70 ACS Sustainable Chemistry & Engineering
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 Figure 10. Factors that affect the quality of the fiber at various stages of production. Adopted 20 69 21 with permission. Copyrights 2011 Elsevier. 22 23 24 261 ISOLATION OF NANOCELLULOSE FROM AGRICULTURE WASTE: 25 26 27 262 The chemical composition of NC consists of cellulose, lignin, hemicellulose, pectins and others 28 29 263 as discussed earlier. It is indispensable to remove lignin and other components to get pure 30 31 32 264 cellulose. Figure 11 shows the exact picture of diverse techniques involved in the production of 33 34 265 NC. Alkali treatment followed by delignification (bleaching) is the first process in the extraction 35 36 266 of NC from any fiber. NC can be extracted from countless agriculture biomass by means of 37 38 39 267 chemical, mechanical or enzymatic treatment. The isolation of cellulose nanocrystals can be 40 41 268 attained by acid hydrolysis directly after the purification of biomass. Whereas nanofibrillated 42 43 269 cellulose is produced typically by mechanical treatments like homogenization, grinding, steam 44 45 270 46 explosion, Cryocrushing etc. The detailed procedures of these methods are discussed in the 47 48 271 following sections. 49 50 51 52 53 54 55 56 57 58 59 60 ACS Paragon Plus Environment ACS Sustainable Chemistry & Engineering Page 18 of 70
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 Figure 11. Different methods of nanocellulose production from agriculture waste. Reprinted 44 with permission with slight modification. © 2015 Rojas J, Bedoya M, Cito Y. Published in 45 Intech under CC BY 3.0 license. Available from: http://dx.doi.org/10.5772/61334 46 272 47 48 273 Since the mechanical treatment involves high energy consumption pre treatments like chemical/ 49 50 51 274 enzymatic are carried prior mechanical treatments. Table 2 presents the extraction of NC from 52 53 275 different crop biomass, method of purification, pre treatments, their production methods, type of 54 55 276 NC obtained is reported. 56 57 58 59 60 ACS Paragon Plus Environment Page 19 of 70 ACS Sustainable Chemistry & Engineering
1 2 3 277 Table 2. Agriculture biomass source, purification method, Pre treatments, mechanical 4 278 treatments, type of nanocellulose and references. 5 6 7 8 9 Biomass Purification Pre-treatment Extraction Type of References 10 11 technique method nanocellulose 12 13 Sugar beet Sodium hydroxide, homogenization Blending Cellulose 67 14 15 pulp sodium chlorite Cryocrushing, microfibrils 16 17 treatments 18 19 70 20 Hemp/spring Sodium hydroxide, Cryocrushing Cellulose 21 22 flax, hydrochloric acid nanofibers 23 24 /rutabaga treatments/kraft 25 process 26 27
28 29 30 Soybean Sodium hydroxide, Refining (PFI Homogenization Nanofibers 71 31 32 pods hydrochloric acid, mill) 33 34 chlorine dioxide 35 36 treatments 37 38 Banana Sodium hydroxide, Biological Chemical and Cellulose 72 39 40 rachis Hydrogen peroxide, retting / mechanical microfibrils 41 42 Potassium mechanical treatments 43 44 hydroxide processing 45 46 Sodium chlorite 47 48 treatments 49 50 Peel of Bleaching Toluene, Homogenization Cellulose 73 51 52 prickly pear ethanol microfibrils 53 54 fruits 55 56 57 58 59 60 ACS Paragon Plus Environment ACS Sustainable Chemistry & Engineering Page 20 of 70
1 2 3 Mulberry Sodium hydroxide Acid hydrolysis Cellulose 24 4 5 barks treatment whiskers 6 7 8 Pineapple Sodium Steam Nanocellulose 74 9 10 leaf hydroxideAcetic explosion 11 12 acid, Sodium Blending 13 14 hypochlorite, Oxalic 15 16 acid treatments 17 18 Coconut Sodium hydroxide Acid hydrolysis Cellulose Nano 75 19 20 husk fiber Acid hydrolysis whiskers 21 22 Bleaching with 23 24 Sodium chlorite and 25 26 glacial acetic acid 27
28 76 29 Cassava Acid hydrolysis Cellulose 30 bagasse whiskers 31 32 33 Banana Sodium hydroxide Steam explosion, Cellulose 77 34 35 Acetic acid Sodium nanofibers 36 37 hypochlorite and 38 39 oxalic acid 40 41 treatments 42 43 Oat straw Homogenisation Nanofibrillated 78 44 45 Quarterisation cellulose 46 47 48 Jute fibers Ball milling Nanocellulose 79 49 50 Mercerisation 51 52 Rice husk Sodium hydroxide Acid hydrolysis Cellulose 80 53 54 treatment, Bleaching nanocrystals 55 56 57 58 59 60 ACS Paragon Plus Environment Page 21 of 70 ACS Sustainable Chemistry & Engineering
1 2 3 chardonnay Toluene, ethanol Acid hydrolysis Cellulose 81 4 5 grape skins nanocrystals 6 7 8 Sugar cane Sodium hydroxide Ionic liquid Homogenization Nanocellulose 82 9 10 bagasse treatment 11 12 Sesame husk Sodium hydroxide, Acid hydrolysis Cellulose 83 13 14 Bleaching nanocrystals 15 16 sodium chlorite 17 18 treatments 19 20 21 Sugar cane Sodium hydroxide Ionic liquid Homogenization Nanocellulose 82 22 23 bagasse treatment 24 25 84 Potato peel Sodium hydroxide Acid hydrolysis Cellulose 26 27 waste treatment, Bleaching nanocrystals 28 29 30 Raw cotton Acid hydrolysis Cellulose 85 31 32 linter nanowhiskers 33 34 Bleached Bleaching Grinding Nanofibrillated 86 35 36 Eucalyptus cellulose 37 38 pulp 39 40 41 Rice straw Toluene, ethanol, Carboxylation Blending Cellulose 87 42 43 sodium chlorite, (TEMPO) nanocrystals 44 45 potassium hydroxide and cellulose 46 47 treatments nanofibers 48 49 Maize straw Soxhlet extraction Bleaching with Acid hydrolysis Cellulose 88 50 51 using hexane, ethyl H2O2 and whiskers 52 53 alcohol and DI water TAED solution. 54 55 56 57 58 59 60 ACS Paragon Plus Environment ACS Sustainable Chemistry & Engineering Page 22 of 70
1 2 3 Acetic acid and 4 5 nitric acid 6 7 treatment 8 9 10 Oil palm Acid hydrolysis Microcrystalline 89 11 12 biomass followed by cellulose 13 14 residue NH4OH 15 16 treatment 17 18 Pomelo Sodium hydroxide Acid hydrolysis Cellulose 90 19 20 (Citrus treatment, Bleaching nanocrystals 21 22 grandis) 23 24 Albedo 25
26 91 27 Kenaf bast Sodium hydroxide, Grinding Cellulose 28 29 fibers Bleaching and nanofiber 30 anthraquinone 31 32 treatment 33 34 35 Mango seed Sodium hydroxide Acid hydrolysis Cellulose 92 36 37 treatment, Bleaching nanocrystals 38 39 Orange waste Sodium hydroxide, Sonification Nanocellulose 93 40 41 sodium chlorite 42 43 treatments 44 45 46 Alfa and Sodium chlorite, Carboxylation Blending Nanofibrillated 45 47 48 sunflower Acetic acid (TEMPO) Homogenization cellulose 49 50 Sodium hydroxide 51 52 treatments 53 54 Corn cob Sodium hydroxide Acid hydrolysis Cellulose 94 55 56 57 58 59 60 ACS Paragon Plus Environment Page 23 of 70 ACS Sustainable Chemistry & Engineering
1 2 3 Treatment, nanocrystals 4 5 Bleaching 6 7 8 Wheat Straw Hydrogen peroxide Acetic Grinding Cellulose 95 9 10 treatment acid/formic nanofibrils 11 12 acid, water 13 14 Agave Sodium hydroxide, Acid hydrolysis Cellulose 96 15 16 tequilana and Bleaching nanocrystals 17 18 barley sodium chlorite and 19 20 acetic acid 21 22 treatments 23 24 28 25 Garlic skin Alkali treatment Acid hydrolysis Cellulose 26 27 nanocrystals 28 29 Corn husk Benzene, ethanol Ultra sonication Nanofibrillated 50 30 31 Bleaching cellulose 32 33 68 34 Chilli Sodium hydroxide, Acid hydrolysis Cellulose 35 36 leftover acetic acid, nanocrystals 37 38 Bleaching 39 40 Citrus waste Sodium hydroxide Enzymatic Cellulose 97 41 42 and Sodium chlorite hydrolysis nanofibers 43 44 98 45 Lotus leaf Toluene, ethanol, High intensity Nanocellulose 46 47 stalk Bleaching ultra sonication 48 sodium chlorite, 49 50 potassium hydroxide 51 52 treatments 53 54 55 56 57 58 59 60 ACS Paragon Plus Environment ACS Sustainable Chemistry & Engineering Page 24 of 70
1 2 3 Tomato peel Sodium hydroxide, Acid hydrolysis Cellulose 99 4 5 Bleaching and nanocrystals 6 7 Sodium chlorite 8 9 10 Flax fibers Sodium hydroxide, Ultrasonication Cellulose 100 11 12 Bleaching,sodium and acid nanowhiskers 13 14 chlorite, hydrolysis 15 16 potassiumhydroxide 17 18 treatments 19 20 Carrot Sodium hydroxide Grinding nanofibers 101 21 22 residue Treatment, 23 24 Bleaching 25
26 28 27 Onion skin Sodium hydroxide Acid hydrolysis Cellulose 28 29 waste Treatment, nanocrystals 30 Bleaching 31 32 33 Groundnut Benzene, ethanol Acid hydrolysis Cellulose 27 34 35 shells Bleaching nanocrystals 36
37 102 38 Flax fibers Sodium hydroxide Acid hydrolysis Cellulose 39 Treatment, nanocrystals 40 41 Bleaching 42 43 44 Miscanthus Sodium chlorite, Acid hydrolysis Cellulose 103 45 46 x. Giganteus Bleaching, Acetic nanocrystals 47 48 acid 49 50 Sodium hydroxide 51 52 treatments 53 54 Citrus waste Toluene, ethanol, Acid hydrolysis Nanocellulose 104 55 56 57 58 59 60 ACS Paragon Plus Environment Page 25 of 70 ACS Sustainable Chemistry & Engineering
1 2 3 279 Bleaching, sodium 4 5 chlorite, 6 280 7 potassium hydroxide 8 9 treatments 10 11 12 Garlic straw Sodium hydroxide Acid hydrolysis Cellulose 25 13 14 Treatment, nanocrystals 15 16 Bleaching 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 ACS Paragon Plus Environment ACS Sustainable Chemistry & Engineering Page 26 of 70
1 2 3 281 PURIFICATION OF BIOMASS: 4 5 6 282 The first interest involved in the extraction of NC is purification of biomass to remove non 7 8 283 9 cellulosic (hemicellulose, lignin) to get the pure cellulose fibers. Firstly, raw materials treated 10 67,105 106 88 11 284 with alkali (NaOH or KOH), organic solvents , Soxhlet or mineral acids in order to 12 13 285 remove the hemicellulose, lignin, pectin’s and waxes (This step also called as pulping). 14 15 286 Secondly, delignification often called as bleaching is usually done by chemical process. The 16 17 18 287 bleaching step involves single or multiple stages depending the end use applications. The most 19 20 288 frequent bleaching agents used are sodium chlorite,75 hydrogen peroxide, 72 oxygen or ozone. 21 22 289 Additional process like Kraft process also called as sulfite process is also carried in the 23 24 70 25 290 purification process. 26 27 28 291 EXTRACTION OF CNC: 29 30 31 292 Classical extraction of cellulose nanocrystals includes 60 65 wt.% of sulfuric acid hydrolysis 32 33 293 (H2SO4) at temperature less than 50 ºC followed by purification of biomass as shown in figure 34 35 294 11. Acid hydrolysis benefits to disintegrate the fibers into nanoscale and helps in preferential 36 37 295 acid hydrolysis of the amorphous parts of cellulose leaving behind the crystalline parts of 38 39 33 40 296 cellulose. The hydrolysis is followed by repeated cycles of sonication and dialysis against 41 42 297 ionized water yielding the pure CNC. CNC can also be produced by the acid hydrolysis using 43 44 298 hydrochloric acid (HCL), phosphoric acid and hydrobromic acid.107–109Apart these, CNC was 45 46 110 47 299 also isolated by microbial hydrolysis. One of the recent study showed the isolation of CNC 48 49 300 using catalytic ionic liquid hydrolysis.111The downside of producing CNC using HCL is that the 50 51 301 suspension is unstable leading to the flocculation112 wherein during sulfuric acid hydrolysis, the 52 53 - 54 302 sulfate ester (-OSO3 ) are randomly spread on the surface of the nanoparticles resulting in the 55 56 303 electrostatic layer which promotes the dispersion of CNCs in water. 57 58 59 60 ACS Paragon Plus Environment Page 27 of 70 ACS Sustainable Chemistry & Engineering
1 2 3 304 Importantly, the acid hydrolysis conditions like hydrolysis time, concentration of the acid, 4 5 ͦ 6 305 temperature affect the properties of CNC. The influence of temperature ranging from 45 to 72 C 7 8 306 on the sulfuric acid hydrolysis of cotton was studied by Elazzouzi Hafraoui et al. The authors 9 10 307 reported that increase in temperature resulted in shorter crystals. Though there was no clear 11 12 308 effect on width was reported.113 These studies were carried out on the wood/cotton based NC. 13 14 15 309 However they can also be applicable to the crop and industrial waste based NC. 16 17 18 310 In literature, CNCs were obtained from agriculture waste like mulberry barks, coconut husk, 19 20 311 cassava bagasse, rice husk, onion skin waste, citrus waste etc. The dimensions and structural 21 22 312 morphology of these CNCs are tabulated in table 3 and figure 13 respectively. Of vital 23 24 25 313 importance in the production of CNC, the industries are trying to reuse the sulfuric acid. The cost 26 27 314 of sulfuric acid is 4 6 times more than that of the market pulp. Hence recovering the acid by 28 29 315 centrifugation and reusing the sulfuric acid can provide an extensive cost advantage.114 30 31 32 316 EXTRACTION OF NFC: 33 34 35 317 Unlike the extraction of cellulose nanocrystals which could be extracted in single step after 36 37 318 purification of the cellulose fibers. NFC is extracted in different steps like homogenization,54 38 39 115 116 117 98 40 319 cryocrushing, grinding , micro fluidization , and ultra sonication. Since the mechanical 41 42 320 treatment consumes high energy, chemical and enzymatic pre treatments have been followed 43 44 118 321 prior. Chemical pre treatment includes tempo oxidation, quarterisation, refining etc. and in the 45 46 119 47 322 enzymatic pre treatment, enzymes like endo and/or exoglucanase were used previously. In this 48 49 323 section, initially the pre treatments are discussed in detail followed by the mechanical process 50 51 324 involved in the production of NFC. 52 53 54 325 55 56 57 58 59 60 ACS Paragon Plus Environment ACS Sustainable Chemistry & Engineering Page 28 of 70
1 2 3 326 PRETREATMENTS: 4 5 6 327 Pre treatment is the very important step for the extraction of the NFC. Chemical or enzymatic 7 8 328 9 pretreatment helps to overcome the recalcitrance of plant cell wall. Recalcitrance in other words 10 11 329 is the resistance of the cell wall breakdown. The deconstruction of cellulose and non cellulosic 12 13 330 materials like lignin and hemicellulose from the cell wall is not a very simple process because 14 15 331 the recalcitrance results from the extreme crystalline structure of cellulose surrounded with lignin 16 17 18 332 and hemicellulose. An ideal cleavage of biomass to extract pure cellulose must prevent the loss 19 20 333 of cellulose, be cost effective and consume less energy and produce less toxic wastes and hence 21 22 334 pre treatments should comply all these criteria.120 Mechanical extraction of NFC consumes high 23 24 25 335 energy from 20,000–30,000 kWh/ton. That being said, chemical or enzyme pre treatments bring 26 121 27 336 down the energy consumption 20times less, i.e. 1000 kWh/ton. 28 29 30 337 CHEMICAL PRE-TREATMENT: 31 32 33 338 The chemical pre treatment comprises 1. Acid hydrolysis 2. Alkaline hydrolysis 3. Oxidation 34 35 339 and 4. Organic solvents/ionic liquids. Acid hydrolysis breaks the hydronium ions in the biomass 36 37 340 and inter and intra molecular bonding between hemicelluloses and lignin leaving behind the pure 38 39 40 341 cellulose. Acids like sulfuric acid (H2SO4), hydrochloric acid (HCL), nitric acid (HNO3) and 41 42 342 phosphoric acid (H3PO4) are often used for the pre treatments. Rosa et al. used H2SO4 acid 43 44 343 hydrolysis to treat coconut husk fibers, Wang et al. used HCL to treat soy pods.75,86 Strong acid 45 46 47 344 hydrolysis is not eco friendly. Moreover, it is difficult to recover the acid after the hydrolysis. On 48 49 345 the other hand, the dilute acids at moderate temperature achieve better hydrolysis.122 50 51 52 346 The alkali treatment is mainly to remove the hemicellulose and it also helps in breaking the 53 54 347 bonds between cellulose, hemicellulose and lignin. The alkali treatment involves the 55 56 57 58 59 60 ACS Paragon Plus Environment Page 29 of 70 ACS Sustainable Chemistry & Engineering
1 2 3 348 saponification of intermolecular ester bond between lignin and hemicelluloses. Normally, alkalis 4 5 6 349 like NaOH, KOH, Ca (OH)2, hydrazine and ammonium hydroxide. Most of the crop waste 7 8 350 biomass like rice husk, mulberry barks, onion skin waste, and mango seed were treated with 9 10 351 sodium hydroxide to remove lignin. The alkali treatment also causes swelling of the cellulose 11 12 352 which leads to the increase in the surface area and decrease in the degree of crystallinity. In 2006 13 14 15 353 Saito et al. used TEMPO (2,2,6,6 tetramethylpiperidine N oxyl) to oxidise cellulose while 16 17 354 extracting NFC by blending process.118 Organic solvents like methanol, ethanol, acetone, 18 19 355 ethylene glycol are also used in removing lignin and hemicelluloses. 20 21 22 356 ENZYMATIC PRE-TREATMENT: 23 24 25 357 Biological enzymes catalyse the hydrolysis of cellulose fibers which makes the fibrillation much 26 27 28 358 easier. Pääkkö et al., 2007 used endoglucanase to hydrolyse cellulose fibers and they carried out 29 30 359 three following steps before the isolation of NFC using micro fluidizer. 1) Refining the fibers to 31 32 360 swell the cellulose making it more available for the enzymes 2) enzymatic hydrolysis for the 33 34 361 delamination of fibers and 3) Washing and yet again refining.119 Mayra Mariño et al. (2015) used 35 36 37 362 Xanthomonas axonopodis pv. citri (Xac 306) enzyme for the degradation of citrus waste fibers 38 39 363 to yield cellulose nanofibers.97 40 41 42 364 MECHANICAL TREATMENT: 43 44 45 365 It is worth to note that in this section authors covered the mechanical treatments used for the 46 47 366 extraction of NFC from agriculture biomass though there are other mechanical treatments. In the 48 49 50 367 literature, we can find that nanofibrillated cellulose have been extracted from number of agri 51 52 368 biomass like alfa and sunflower, carrot, kenaf bast fibers, jute fibers, peel of prickly pear fibers, 53 54 369 soybean pods, oats straw etc. as shown in table 5. Regardless of the source, NFC is produced 55 56 57 58 59 60 ACS Paragon Plus Environment ACS Sustainable Chemistry & Engineering Page 30 of 70
1 2 3 370 chiefly using mechanical treatment. The mechanical treatment comprises 1. Homogenization, 2. 4 5 6 371 Micro fluidization, 3. Grinding, 4. Cryocrushing and 5. Ultra sonication. All these treatments 7 8 372 work under high shear forces cleaving the cellulose fibers resulting in the fibrillation. Following 9 10 373 is the detailed description of these different mechanical treatments. 11 12 13 374 REFINING AND HOMOGENIZATION: 14 15 16 375 Refining in most cases is performed prior homogenization. Different refiners like PFI mills, disk 17 18 376 refiners are used to refine the pulp.71,123 In 2011, Karande et al., extracted NFC from cotton 19 20 124 21 377 fibers by using only disk refiner. The working principle of homogenizer is shown in figure 12 22 23 378 a. 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 125 46 Figure 12. Diagram for working principle of a) homogenizer adopted from b) micro 126 47 fluidizer. Adopted with permission. c) grinding adopted from www.masuko.com and d) 48 Cryocrushing from 127 49 50 51 379 In this method, the cellulose suspension is passed through a vessel between two valve seats and 52 53 54 380 high pressure is applied because of which high shear forces are generated causing the fibrillation 55 56 381 of cellulose. This procedure is repeated number of times to increase the degree of fibrillation. 57 58 59 60 ACS Paragon Plus Environment Page 31 of 70 ACS Sustainable Chemistry & Engineering
1 2 3 382 The isolation of micro fibrillated cellulose using homogenization was first done by Turbak et al. 4 5 54 6 383 in 1985 using Gaulin homogenizer. Dufresne et al. (1997) produced cellulose micro fibrils 7 8 384 from sugar beet pulp using homogenization. The purified sugar beet pulp suspension was poured 9 10 385 into the vessel and high pressure (500 bars) was applied for 0.5 3 hours resulting in the 11 12 386 invidualization of micro fibrils.67 In 2007, Wang and Sain used soybean pods as a raw material to 13 14 15 387 produce NFC. The pre treated soybean fibers were first beaten and refined in PFI mill at 12000 16 17 388 revolution which reduced the fiber length. The sample was then homogenized at high pressure 18 19 389 (500 1000 bars) for 20 passes to delaminate the cellulose fibers into nanofibers.71 NFC from Alfa 20 21 22 390 and sunflower was extracted in 2013 by Chaker et al. using high pressure homogenization. The 23 24 391 delignified pulp was pumped into GEA homogenizer processor. In this case, the fibrillation was 25 26 392 done in two steps. During the first step, 1.5 wt. % of the fiber suspension was passed through the 27 28 29 393 slits at 300 bars for several times to increase the viscosity of the slurry. Then the pressure was 30 128 31 394 increased to 600 bars for the defibrillation process. The main drawback of this method is 32 33 395 clogging of the system and so the fiber size should be reduced before performing high pressure 34 35 396 homogenization.10 The other downside of this treatment is the excessive energy consumption for 36 37 38 397 which few pre treatments were developed as discussed in the previous section. 39 40 41 398 MICROFLUIDIZATION: 42 43 44 399 Micro fluidization is another mechanical treatment to manufacture NFC and this method was 45 46 400 first used by Zimmermann et al. at 2004.117 In this method, the cellulosic suspension is passed 47 48 401 through a Z or Y shaped chamber as shown in figure 12b with channel sizes usually 200 400 49 50 51 402 µm and by applying high pressure through intensifier pump, the fibers are delaminated by the 52 53 403 resulting shear forces against the colliding suspension and the channel walls. Ferrer et al. 54 55 404 extracted NFC from empty palm fruit bunch fibers (EPFBF) using microfluidizer.129The 56 57 58 59 60 ACS Paragon Plus Environment ACS Sustainable Chemistry & Engineering Page 32 of 70
1 2 3 405 clogging of fibers in homogenizer can be overcome in micro fluidization process because it has 4 5 130 6 406 no in line moving parts, and it can easily be resolved by reverse flow through the chamber. 7 8 9 407 GRINDING: 10 11 408 Another method to produce NFC is grinding process in which the sample slurry is passed 12 13 14 409 through an ultrafine grinder as in figure 12c. The principle is that the fibers are ground between a 15 16 410 static and a rotating stone (disc) rotor. The distance of the discs can be adjusted based on the type 17 18 411 of the raw material. The cell wall structure, bonds are cleaved down by the shear forces produced 19 20 21 412 during grinding causing the NFC production. In 2012, Wang et al. produced NFC for first time 22 23 413 from bleached eucalyptus pulp using Super Mass Colloider (Model: MKZA6 2, Disk Model: 24 25 414 MKGA6 80#, Masuko Sangyo Co., Ltd, Japan) grinder at 1500 rpm. They used the energy input 26 27 28 415 from 5 and 30 kWh/kg to study the relation between consumed energy and the fibrillation by 29 86 30 416 means of crystallinity and degree of polymerisation. Karimi et al., Jossel et al., Siquiera et al. 31 32 417 extracted cellulose nanofibers from kenaf bast fibers, wheat straw and carrot residue respectively 33 34 418 using grinding process.26,91,95 35 36 37 38 419 CRYO CRUSHING: 39 40 420 In 1997, Dufresne et al. isolated NFC from sugar beet pulp using cryocrushing.67 In this 41 42 421 treatment, the cellulosic fibers are frozen in liquid nitrogen and then crushed by high shearing 43 44 45 422 forces which causes the release of exert pressure of ice crystals on the cell wall breakdown 46 47 423 leading to the nanofiber formation. Figure 12d shows the working principle of Cryocrushing. 48 49 424 Bhatnagar and Sain extracted NFC from hemp, flax and rutabaga in 2005 using cryocrushing.70 50 51 52 425 53 54 55 426 56 57 58 59 60 ACS Paragon Plus Environment Page 33 of 70 ACS Sustainable Chemistry & Engineering
1 2 3 427 ULTRASONICATION: 4 5 6 428 Ultra sonication is another strategy of producing NFC in which the suspension is exposed to the 7 8 429 9 ultra sonic waves. During this process, alternating low and high pressure waves are produced 10 11 430 creating, expanding and colliding the gas bubbles. These hydrodynamic forces are used to 12 13 431 liberate cellulose nanofibers. Junko Tsukamoto et al. isolated NFC from citrus processing waste 14 15 432 from oranges (CPWO) using ultrasonic processor, Sonics at 750 Watt, 20 kHz and 4J. The 16 17 93 18 433 residue from enzymatic hydrolysis of CPWO was used as a raw material here. 19 20 21 434 STEAM EXPLOSION: 22 23 435 Steam explosion is a thermomechanical process in which the heat carried by the steam penetrates 24 25 26 436 sample by diffusion and the sudden release of pressure generates shear forces cleaving the 27 28 437 glyosidic and hydrogen bonds leading to the isolation of nanofibers. This method was used by 29 30 438 Cherian et al. to isolate NFC from pineapple leaf and by Deepa et al. in the production of NFC 31 32 439 74,77 33 from banana fibers. 34 35 36 440 BALL MILLING: 37 38 441 In this technique, the sample is placed in a cylindrical, hollow jar partly filled with metal, 39 40 442 ceramic or zirconia ball and when the jar rotates, the collision between fibers, ball and the walls 41 42 43 443 of the container causes the fibrillation. Using ball milling Baheti et al. prepared NFC from jute 44 45 444 fibers.79 46 47 48 445 CHARACTERISATION OF NANOCELLULOSE: 49 50 51 446 In this section, the important characterizations of NC produced from agriculture biomass are 52 53 447 discussed. The quality assessment of produced NC is done by studying morphology, chemical 54 55 56 57 58 59 60 ACS Paragon Plus Environment ACS Sustainable Chemistry & Engineering Page 34 of 70
1 2 3 448 composition, crystallinity and thermal properties few of them are discussed in the following 4 5 6 449 section. 7 8 9 450 MORPHOLOGY: 10 11 451 12 Morphology is the key parameter to check the fibrillation of the NFC. It is imperative to study 13 14 452 the morphology of the obtained NC to understand the sizes, smoothness and fibrillation. The 15 16 453 morphology in usual depends on the source and extraction methods. The size and roughness of 17 18 454 the fibers is reduced during the production process possibly because of the removal of lignin, 19 20 21 455 hemicellulose, lignin and other non cellulosic materials during the alkali and bleaching stages. 22 23 456 Morphology is studied using many microscopic techniques like scanning electronic microscopy 24 25 457 (SEM), field emission scanning electron microscopy (FE SEM), transmission electron 26 27 28 458 microscopy (TEM) and Atomic force microscopy (AFM). Few of the micrographs of nano 29 30 459 fibrillated cellulose and cellulose nanocrystals produced from different agriculture biomass 31 32 460 sources are shown in figure 13. 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 ACS Paragon Plus Environment Page 35 of 70 ACS Sustainable Chemistry & Engineering
1 2 3 4 Figure 13. Micrographs of nanocellulose produced from different agriculture biomass 5 6 7 461 8 9 10 462 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 ACS Paragon Plus Environment ACS Sustainable Chemistry & Engineering Page 36 of 70
1 2 3 463 Table 3. Source, diameter and reference of NC obtained from different crop waste. 4 5 6 464 7 NFC 8 9 465 Source Diameter (nm) References 10 11 72 12 466 Banana rachis 3–5 13 14 Prickly pear fruits 2–5 73 15 467 16 17 468 Wheat straw 10–80 115 18 469 19 89 20 Oil palm 5–40 21 470 22 Soy hull 20–120 131 23 471 24 25 CNC 472 26 27 Source Diameter (nm) length (nm) References 28 473 29 30 Coconut husk 5.5 ± 1.4 58 75 31 474 32 Chilli leftover 4 6 90 180 132 33 475 34 35 Garlic straw 6 480 25 36 476 37 27 38 Groundnut shells 5 18 111 477 39 40 Mulberry bark 25 30 400 500 24 41 478 42 43 44 479 It is worth noting that size and morphology of NC varies much depending on the source from 45 46 480 which they are extracted. The sizes of NFC and CNC produced from various agri biomass 47 48 49 481 sources are listed in the table 3. 50 51 52 482 Beside source, the morphology of NFC depends on the number of passes (cycle time) and pre 53 54 483 treatments involved in the isolation. As stated earlier, the homogenization is repeated for 55 56 57 58 59 60 ACS Paragon Plus Environment Page 37 of 70 ACS Sustainable Chemistry & Engineering
1 2 3 484 different passes to get maximum fibrillation. On that note, Lee et al. in 2009 studied the effect of 4 5 6 485 cycle time (1 20 passes) of homogenization on the size of NFC obtained from commercial 7 8 486 microcrystalline cellulose. With the 1 5 passes they reported that the fibrillation was limited only 9 10 487 to the surface as shown in figure below. However, with mechanical treatment of 10 15 passes the 11 12 488 fibrils were split into smaller fibrils with increased aspect ratio. When passed the suspension 13 14 15 489 further for 20 passes, the fibrils were more chopped into thinner fibers. Having said that, the 16 17 490 fibers tend to aggregate due to the higher surface area and high density of hydroxyl groups. 18 19 491 Hence the authors concluded that increasing the cycle time may result in the decreased 20 21 133 22 492 mechanical strength. 23 24 25 493 Zuluaga et al. (2009) investigated the effect of pre treatments of banana rachis on the 26 27 494 morphology of NFC obtained by using TEM shown in figure 14. They pre treated the banana 28 29 495 rachis using peroxide alkaline (PA) (figure 14a), peroxide alkaline HCL (PA HCL) (figure 14b), 30 31 496 32 5 wt.% potassium hydroxide (KOH) (figure 14c) and 18 wt. % KOH (figure 14d). The PA and 5 33 34 497 wt.% KOH treated sample showed loose networks whereas PA HCL treatment resulted in 35 36 498 shorter fibrils and finally with 18 wt.% KOH the microfibrils were even shorter and interestingly 37 38 499 part of cellulose I was changed into cellulose II.72 39 40 41 500 42 43 44 501 45 46 47 502 48 49 50 503 51 52 53 504 54 55 56 57 58 59 60 ACS Paragon Plus Environment ACS Sustainable Chemistry & Engineering Page 38 of 70
1 2 3 4 5 6 Table 4. Crystallinity of raw, NFC and CNC obtained from various biomass. 7 8 9 10 11 12 13 14 15 16 17 18 19 20 505 21 22 23 506 Figure 14. TEM images of cellulose microfibrils after a) PA b) PA–HCl c) 5 wt. % KOH and d) 24 25 72 26 507 18 wt. % (KOH 18) treatments. Reprinted with permission. Copyright 2017 Elsevier. 27 28 29 508 The morphology of CNC depends on source, hydrolysis time, temperature, acid concentration 30 31 509 and different acids like hydrochloric acid, phosphoric acid or acetic acid. The effect of pre 32 33 510 treatments and the hydrolysis time on the morphology of CNC obtained from coconut husk fibers 34 35 75 36 511 were inspected by Rosa et al., 2010. 37 38 39 512 CRYSTALLINITY: 40 41 42 513 The crystallinity study of produced NC is necessary to understand the effect of production 43 44 514 methods on the crystal structure of the cellulose. The crystallinity is usually studied by X ray 45 46 515 diffraction (XRD) technique. It is explained elsewhere that cellulose is made of highly crystalline 47 48 516 and disordered amorphous regions. It is believed that during extraction the disordered amorphous 49 50 51 517 regions are removed resulting in the increased crystallinity. The degree of crystallinity of NFC 52 53 518 and CNC gained from different crop waste sources is shown in the table 4. 54 55 56 57 58 59 60 ACS Paragon Plus Environment Page 39 of 70 ACS Sustainable Chemistry & Engineering
1 2 3 NFC 4 CNC 5 6 Source Crystallinity (%) References 7 Coconut husk fibers 8 75 9 RiceUntreated straw (Stem) 38.9 ± 0.3 10 11 Original fibres 50.9 12 Purified cellulose fibers 63.8 106 13 14 Cellulose nanofibers 63.4 15 16 17 Corn husk 18 19 Original corn husk 35.9 50 20 21 Corn husk NFC 64.8 22 23 Oil palm residue 24 25 89 OPEFB pulp 80 26 27 OPEFB MCC 87 28 29 30 Pineapple leaf 31 74 32 Raw – 33 34 Steam exploded 35.97 35 36 Bleached 54.18 37 38 Acid treated 73.62 39 40 Oat straw 41 42 Starting cellulose material 70 134 43 44 Non modified CNC 64 45 46 519 47 48 49 50 51 52 53 54 55 56 57 58 59 60 ACS Paragon Plus Environment ACS Sustainable Chemistry & Engineering Page 40 of 70
1 2 3 CNC (1B at 150 min) 62.2 ± 0.5 4 5 6 Garlic straw 7 8 Raw 37.4 25 9 10 Bleached 47.1 11 12 CNC 68.8 13
14 132 15 Chilli leftover 16 17 Alkali treated 52 18 Bleached fibers 68 19 20 CNC 78.5 21 22 23 Groundnut shell 24 25 Raw 56 27 26 27 Purified 68 28 29 CNC 74 30 31 Mulberry bark 32 33 Original mulberry barks 46.9 24 34 35 Pre treated mulberry barks 58.8 36 37 Cellulose whiskers 73.4 38 39 520 40 41 42 521 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 ACS Paragon Plus Environment Page 41 of 70 ACS Sustainable Chemistry & Engineering
1 2 3 522 The crystallinity of NC is higher compared to that of starting material and this is due to the 4 5 6 523 removal of lignin, hemicellulose, pectin or any non cellulosic materials. In some cases, the fibers 7 8 524 can partially contain both cellulose I and II. Normally, cellulose I can be identified at 2θ=14.9º 9 10 525 (110), 2θ=16.6º (110), 2θ=22.7º (200) and 2θ=34.4º (004). 11 12 13 526 THERMAL PROPERTIES: 14 15 16 527 The thermal property of NC is indispensable to use them in the composites. Cellulosic materials 17 18 528 degrade below 400ºC 135and the degradation temperature depends on the structure and chemical 19 20 21 529 composition. The degradation starts at lower temperature owing to the decomposition of 22 23 530 hemicellulose, lignin and then pyrolysis of cellulose occurs after which charring happens. The 24 25 531 thermal stability of NFC in most of the cases increases due to the removal of hemicelluloses and 26 27 136 28 532 lignin. In contrast, the thermal stability of CNC decreases when compared to that of raw 29 30 533 material because of the introduction of sulfate groups. The sulfate groups degrade at around 31 32 534 120ºC and they decrease the defense of cellulose pyrolysis thereby decreasing the thermal 33 34 535 stability. 35 36 37 536 APPLICATIONS: 38 39 40 537 The applications of NC from different sources are discussed in this section. NC is of growing 41 42 43 538 interest on the grounds of innumerous applications, for example in various realm from paper 44 45 539 industry, composites, biomedicine, textile, construction to aerospace, automotive, and sensors 46 47 540 etc.137,138. Recently few studies reported the substantial role of NC in the field of filter 48 49 50 541 application as shown in figure 15c. 51 52 53 54 55 56 57 58 59 60 ACS Paragon Plus Environment ACS Sustainable Chemistry & Engineering Page 42 of 70
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 Figure 15. Multitude applications of nanocellulose a) Extruded PP/CNC and M CNC 31 32 139 33 nanocomposite film. Reprinted with permission. Copyright 2016 American Chemical Society 34 35 b) Bio based pouches from VTT technical research.140 c) Nanocellulose filter. Image obtained 36 37 from nanografi.com 141. d) Cellulose nanofibril aerogels from rice straw absorbing dyed 38 39 142 40 chloroform from water. Reprinted with permission. Copyright 2014 Royal Chemical Society. 41 143 42 e) Alginate oxidized nanocellulose sponge. Reprinted with permission. Copyright 2012 43 44 American chemical Society. f) Fabricated transparent and flexible Nano paper transistor. 45 46 Reprinted with permission.144 Copyright 2013 American Chemical Society. g) 3D printed small 47 48 145 49 grids and human ear from NFC and alginate. Reprinted with permission. Copyright 2015 50 51 American Chemical Society. 52 53 54 542 55 56 57 58 59 60 ACS Paragon Plus Environment Page 43 of 70 ACS Sustainable Chemistry & Engineering
1 2 3 543 Importantly, the properties like high mechanical properties and low density with high aspect ratio 4 5 6 544 facilitate to use NC in composite field for the fabrication of lightweight and high performance 7 8 545 materials. The high water holding capacity due to the enlarged surface area enables their use as a 9 10 546 rheology modifier mainly in paints and personal care products and this field need to be explored 11 12 547 further for better understanding. Recently hydrophobic aerogels produced from rice straw 13 14 15 548 (agricultural waste) was developed and results shown the great tendency of absorption of 16 17 549 hydrophobic solvents as shown in figure 15d. NC has attractive optical properties this could be 18 19 550 an added benefit in the fields of electronics, ultra filter papers, sensors and transparent solar 20 21 22 551 cells. Due to their biodegradability, compatibility NC can play vital role in biomedical field for 23 24 552 the progress of drug delivery, artificial body parts and tissue engineering. 25 26 27 553 Composites: 28 29 30 554 Production of high mechanical performance composites can be achieved by the reinforcement of 31 32 555 nano fillers into polymers. In this case, NC is an appropriate candidate for composites 33 34 556 preparation compared to the non biodegradable nano fillers like carbon nanotubes, nano clays 35 36 139 37 557 etc. However, it is challenging to prepare nanocomposites by using NC for the reason of poor 38 39 558 dispersion of CNC and NFC up on drying and low compatibility with hydrophobic matrices. It 40 41 559 can be overcome by introducing hydrophobic groups through surface modification and grafting. 42 43 44 560 Iwatake et al. has described the cellulose nanofiber reinforcement on polylactic acid (PLA). The 45 46 561 goal of this study was to prepare green composites. The nanofiber reinforcement increased the 47 48 562 Young’s modulus and tensile strength of PLA by 40% and 25% respectively.146Recently, high 49 50 51 563 dispersion and thermal stability was achieved for the quaternary salt modified CNC reinforced 52 139 53 564 with polypropylene as shown in the figure 15a. The first application of NC in composite 54 55 565 reinforcement was done by Favier and group wherein poly(S co BuA) was reinforced by using 56 57 58 59 60 ACS Paragon Plus Environment ACS Sustainable Chemistry & Engineering Page 44 of 70
1 2 3 566 cellulose whiskers. The authors found that the mechanical properties were increased 4 5 147 6 567 significantly. 7 8 9 568 10 11 569 12 Packaging: 13 14 570 In the modern world, usage of packaged food is increased. Most of the food is packed in the 15 16 17 571 petro based polymers. Therefore, industries are very keen to develop biodegradable and 18 19 572 lightweight food packaging materials. This kind of materials can preserve the quality in terms of 20 21 573 freshness and taste. In this aspect VTT technical research center produced bio based packaging 22 23 24 574 materials as shown in figure 15b. Moreover, the shelf life of the food also will increase which is 25 26 575 important for both consumers and industries.148 27 28 576 Previously, paper substrate was coated with mixture of microfibrillarted cellulose and 29 30 31 577 chlorhexidine digluconate (anti bacterial molecule) and quality of the food packed with these 32 149 33 578 materials also reported. Elsewhere reported the antimicrobial activity of the nisin grafted CNF 34 35 579 has shown promising anti bacterial activity against Bacillus subtilis and Staphylococcus aureus 36 37 580 .150 38 bacteria NC materials increases the fiber fiber bond strength and increases the reinforcement 39 40 581 effect on paper materials with only less amount of cellulose pulp as a filler resulting in the light 41 42 582 weight packaging. 43 44 45 583 Paints and coatings: 46 47 48 584 NC is an ideal material to use in the paint and coating industry. Thanks to their high surface area 49 50 585 which helps to hold the water hence acting as a highly viscous material. It is used in improving 51 52 53 586 the durability of paints and protects paints and varnishes from wear and tear caused by UV rays. 54 55 587 They can alter the viscosity of paints and coatings. The VTT group, Finland used NC in 56 57 58 59 60 ACS Paragon Plus Environment Page 45 of 70 ACS Sustainable Chemistry & Engineering
1 2 3 588 polyurethane varnishes and paints as additives, which increased the durability of coatings of 4 5 151 6 589 paints. Some other company called Cellu Comp from United Kingdom claimed, the NC 7 152 8 590 extracted from carrot improved the hardness, flexibility and crack resistance of the paints. 9 10 11 591 Optical materials: 12 13 14 592 Nanofibrillated cellulose possess great optical properties considering the size of the NFC is less 15 16 593 than the wavelength of the visible light. Hence the paper prepared with nanofibrils are 17 18 594 transparent.153 This can be added benefit to the different applications like electronics, sensors and 19 20 21 595 solar panels. Adequate research results have been reported in the literature. Jia Huang and team 22 23 596 reported the flexible field effect transistors printing on the nano paper for the green electronic 24 25 597 transistor applications as shown in figure 15f.144 The other research group studied the deposition 26 27 28 598 of tin doped indium oxide along with silver nano wires and carbon nanotubes for solar cell 29 153 30 599 applications. 31 32 600 Biomedicine: 33 34 35 601 NC has antiquity of application in biomedicine as excipients, in drug delivery, for 36 37 602 enzyme/protein immobilization, implants, skin and bone tissue repair and others. The 38 39 134 40 603 competence of NC in drug delivery was studied by Letchford et al. . This study proved that 41 42 604 nanocrystalline cellulose could bind the significant amount of ionizable water soluble antibiotics 43 44 605 tetracycline and doxorubicin by surface modification using cationic surfactant called CTAB 45 46 47 606 (cetyl trimethylammonium bromide). In other study reported by Alain dufresne and his group the 48 49 607 cross linking between the alginate and oxidised nano fibrillated cellulose hydrogels for the drug 50 51 608 delivery system was produced as shown in figure 15e.143 Same group also reported the double 52 53 54 609 membrane hydrogels using cationic cellulose nanocrystals and alginate for quick and slow drug 55 154 56 610 release from first layer and second layer respectively. Nanomaterials have wide applications as 57 58 59 60 ACS Paragon Plus Environment ACS Sustainable Chemistry & Engineering Page 46 of 70
1 2 3 611 hydrogels in tissue engineering. In 2015, Markstedt et al. reported the novel method to produce 4 5 6 612 3D bioprinting with living cells. They combined nanofibrillated cellulose with alginate for the 7 145 8 613 3D bioprinting of living soft tissue with cells as shown in figure 15g. 9 10 11 614 NANOCELLULOSE TOWARDS INDUSTRIALIZATION: 12 13 14 615 The scientific abilities of the NC were progressed from last six decades. The attractive properties 15 16 616 of the tiny fibers and particles play vital role for the creation of the new bio economy. Few 17 18 617 decades ago, microcrystalline cellulose (MCC) emerged as new material, which is widely used in 19 20 21 618 pharma, composites and chemical fields. Subsequently, NC is emerging as a key material in 22 23 619 industrialization.155 According to the global market outlook for NC, by 2022, the annual turnover 24 25 620 can reach 808.29 million dollars. The significant mechanical, optical and rheological properties 26 27 28 621 of these materials attracted the both researchers and industries. The journey of the NC from last 29 30 622 seven decades is shown in figure 16 along with the major research findings. 31 32 33 623 The enticements for the NC industries are because it is a new source with wide range of 34 35 624 applications that need to be established. Hence producing new products resulting in new business 36 37 625 breakthroughs. In addition, they can be extracted from easily available sources and are bearable 38 39 40 626 and renewable. The first pilot plant to produce NC was started in 2011 by Innventia at 41 42 627 Sweden.156The industrialization of NC can be parted into three main segments viz. products, 43 44 628 applications and areas where there are produced. The products of NC are cellulose nanocrystals, 45 46 47 629 nanofibrillated cellulose, bacterial cellulose and electro spun cellulose nanofibers. Applications 48 49 630 of NC includes paper industry, composites, personal care, biomedical, electronics, paints etc. 50 51 631 Figure 16 shows the pioneering work during the journey of NC towards industrialization. 52 53 54 55 56 57 58 59 60 ACS Paragon Plus Environment Page 47 of 70 ACS Sustainable Chemistry & Engineering
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 Figure 16. Past, present and future research and industrial trends of nanocellulose 29 30 632 31 32 33 633 The pronounced market of NC is seen in areas of North America, Europe, middle East. Table 5 34 35 36 634 indicates the company producing NC across the world with the quantity produced and the type of 37 9 38 635 the product based on the TAPPI NANO outlook 2015. Industries collaborate with other 39 40 636 universities or institutes to develop new Nano cellulosic materials. The detailed study of 41 42 637 industrial turnover and industrial methods is discussed in the following section. 43 44 45 638 46 47 48 639 49 50 51 640 52 53 54 641 55 56 57 58 59 60 ACS Paragon Plus Environment ACS Sustainable Chemistry & Engineering Page 48 of 70
1 2 3 4 Table 5. Company producing nanocellulose, product type and the production capacity/day 5 in kilograms. 6 7 Production unit Production capacity/day (Kg) Product type 8 9 10 CelluForce CANADA 1000 CNC 11 12 Paper logic USA 2000 NFC and CNC 13 14 University of Maine USA 1000 NFC and CNC (dry &wet) 15 16 Borregaard NORWAY 1000 NFC 17 18 American process USA 500 to 1000 NFC, CNC 19 20 Nippon paper JAPAN 150 500 Tempo CNC, NFC and CNC 21 22 Innventia SWEDEN 100 NFC 23 24 CTP/ FCBA FRANCE 100 Enzi. NFC, T CNF 25 OHI paper JAPAN 100 NFC 26 27 Stora Enso FINLAND unknown NFC 28 29 UPM FINLAND unknown NFC 30 31 SAPPI NETHERLANDS unknown NFC 32 33 Lulea university SWEDEN unknown NFC 34 35 Holmen SWEDEN 100 CNC 36 37 Alberta innovates CANADA 20 CNC 38 39 India council for Ag. research 10 CNC 40 41 Melodea Israel unknown CNC 42 43 FP Innovations CANADA unknown CNC, NFC 44 45 Blue goose refineries CANADA 10 CNC 46 47 642 48 49 50 643 51 52 53 644 54 55 56 57 58 59 60 ACS Paragon Plus Environment Page 49 of 70 ACS Sustainable Chemistry & Engineering
1 2 3 645 INDUSTRIAL TURNOVER AND METHODS: 4 5 6 7 646 Every material invention starts at research table and it will take decades to commercialize. 8 9 647 Similarly, commercial NC production was started in 2012, nearly six decades after first 10 11 648 invention. From thereon, focus on the biomaterials increased due to the awareness of the 12 13 649 biodegradable and renewable materials for the betterment of the society. This might be the main 14 15 16 650 reason behind the production activities of the NC. All over the world more than 40 companies 17 18 651 was established with their allied organizations to produce the NC. However, the potential 19 20 652 application was not yet established. Industries are currently under research to find the key 21 22 23 653 advancements in the fields of the concretes, paints, composites and packaging. Authors 24 25 654 attempted to shortlist all the production sites of NC, nature of material manufactured, their 26 27 655 production capacity and methods of the preparation in table 6 based on the TAPPI NANO, 2015 28 29 157 30 656 ISO/TC 6/TG 1 study. 31 32 657 33 Table 6. Industries producing nanocellulose, product type, their production capacity and method 34 157 35 658 of production across the world. Reproduced with permission. TAPPI NANO, 2015 ISO/TC 36 37 659 6/TG 1 study. 38 39 40 660 Cellulose Nanocrystals (CNCs) Production activities 41 Country Company Product/ Trade Production Source/Method 42 name Capacity 43 44 45 CelluForce* NCCTM 1 ton/day Bleached kraft pulp Sulfuric 46 acid hydrolysis 47 48 CANADA Alberta Innovates CNCs 20 kg/day MCC, bleached kraft pulps 49 (AITF) (softwood and hardwood), 50 dissolving pulp Sulfuric acid 51 hydrolysis 52 53 54 55 56 57 58 59 60 ACS Paragon Plus Environment ACS Sustainable Chemistry & Engineering Page 50 of 70
1 2 3 Blue Goose CNCs 10 kg/day Lignocellulosic feedstocks 4 Biorefineries Inc. including wood, grasses and 5 cereal straws Oxidative, 6 nanocatalytic process 7 8 9 10 11 FP Innovations CNCs 2 kg/day Bleached chemical pulp and 12 others Sulfuric acid hydrolysis 13 14 15 16 USA American Process Nanocellulose 0.5 ton/day Wood chips, Agricultural 17 Inc.** BioPlusTM CNCs (est.) residues Bamboo, grasses 18 Lignin coated USA Sulfur dioxide and 19 hydrophobic ethanol pretreatment (Patented 20 CNCs AVAP® technology) 21 22 23 24 25 USDA‐Forest Aqueous 50 kg/week Wood pulp, Sulfuric acid 26 Service‐Forest suspensions hydrolysis 27 Products Laboratory Freeze‐dried 28 (FPL) CNCs 29 30 31 SWEDEN MoRe Research Nanocrystalline 0.1 ton/day Paper industry sludge 32 backed by Holmen cellulose pilot plant in Controlled sulfuric acid 33 Pulp and Paper and place during hydrolysis + washing, 34 SP Technical first half of sonication 35 Research Institute of 2016 Based on technology by 36 Sweden Melodea 37 38 39 40 41 42 ISRAEL Melodea Ltd. backed Nanocrystalline Paper industry sludge 43 by Holmen Pulp and cellulose (NCC) Bleached pulp 44 Paper, Sweden NCC foam Flax, Hemp 45 Hydrolysis + washing, 46 sonication 47 48 49 50 51 52 53 54 55 56 57 58 59 60 ACS Paragon Plus Environment Page 51 of 70 ACS Sustainable Chemistry & Engineering
1 2 3 IRAN Nano Novin Bacterial Bacterial cellulose 4 Polymer Co nanocellulose Production of cellulose 5 nanofibers using bottom up 6 approach of bacterial synthesis 7 Provide nanocellulose and other 8 bio based nanopolymers using 9 top down approaches 10 11 12 13 14 Tianjin Haojia CNCs Dissolving pulp 15 CHINA Cellulose Co., Ltd. Suspension Cotton 16 Spray dried Bleached kraft pulp 17 Freeze dried (softwood, hardwood) 18 Chemically Mechanical shearing + 19 modified? combined enzymatic and acidic 20 hydrolysis 21 22 23 24 25 INDIA Indian Council of CNCs 10 kg/day Cotton linters 26 Agricultural and CNFs MCC from short staple cotton 27 Research Central fibers 28 Institute for Sugarcane bagasse, other 29 Research on Cotton agro-biomass 30 Technology Novel microbial, enzymatic and 31 (ICAR CIRCOT) chemo mechanical processes, 32 e.g. in membrane reactor for 33 continuous hydrolysis and 34 removal of nanocellulose 35 without substrate inhibition 36 37 661 38 39 40 662 41 42 43 663 44 45 46 664 47 48 49 665 50 51 666 52 53 54 667 55 56 57 58 59 60 ACS Paragon Plus Environment ACS Sustainable Chemistry & Engineering Page 52 of 70
1 2 3 668 Nanofibrillated cellulose (NFCs) - Production activities 4 5 669 6 7 8 Country Company Product/ Trade Production Source/Method 9 name Capacity 10 11 12 Kruger Bioproducts Cellulose 5 tons/day Bleached kraft pulp or 13 Inc.** FILOCELL filaments TMP 14 15 CANADA Mechanical treatment 16 17 Performance Cellulose Bleached kraft pulp or 18 BioFilaments Inc.** filaments TMP 19 20 Wet fluff form or Mechanical treatment 21 rolls of dried film
22 23 24 GreenCore NCellTM Wood or agricultural 25 Composites Inc.** fibers Natural fiber 26 reinforced “In situ generation of 27 thermoplastics lignocellulosic 28 microfibers” 29 30 PP or PE matrix 31 reinforced with up to 32 40% natural cellulosic 33 microfibers 34 35 American Process Nanocellulose 0.5 ton/day (est.) Wood chips 36 Inc. BioPlusTM 37 USA Agricultural residues 38 (AVAPCO)** CNFs SO2/ethanol pulping 39 Lignin coated 40 hydrophobic Mechanical treatment 41 CNFs 42 43 USDA‐Forest CNFs 1 kg/week Wood pulp 44 Service‐Forest 45 Aqueous TEMPO oxidation and 46 Products Laboratory (FPL) suspensions mechanical treatment 47 Freeze‐dried 48 49 50 UMaine CNFs 1 ton/week Wood pulp 51 Aqueous Mass colloider grinder 52 suspensions 53 54 55 56 57 58 59 60 ACS Paragon Plus Environment Page 53 of 70 ACS Sustainable Chemistry & Engineering
1 2 3 paperlogic CNFs Wood pulp 4 5 Planned for first Mechanical treatment 6 half of 2015 7 8 9 Borregaard CMFs ~3 ton/day “Specialty cellulose” 10 “Exilva MFC” planned for mid Mechanical treatment 11 NORWAY 2016 12 13 14 Norske Skog CMFs/ Pilot plant Thermomechanical 15 Saugbrugs pulp nanocellulose planned as of 16 Dec 2013 High pressure treatment 17 18 19 20 SWEDEN Innventia AB CMFs 100 kg/day Wood fibers 21 pilot plant Chemical and/or 22 enzyme pre treatment, 23 Mobile demo Mechanical treatment 24 plant (homogenization) 25 July 2014, 26 planned with 27 BillerudKorsnäs 28 29 30 UPM Kymmene BiofibrilsTM Pilot scale Wood fibers 31 Ltd.* FINLAND demo plant Mechanical treatment 32 33 “For trials at 34 UPM mills” 35 36 VTT* CNFs Pilot scale Birch fibril pulp 37 38 collaboration with Roll to roll film Mechanical treatment 39 Aalto U, UPM 40 41 Stora Enso Ltd. CMFs Pilot plant Wood fibers 42 43 “Microcellulose” started up end Mechanical treatment 44 2011 45 46 47 670 48 49 50 671 51 52 53 54 55 56 57 58 59 60 ACS Paragon Plus Environment ACS Sustainable Chemistry & Engineering Page 54 of 70
1 2 3 UK Zelfo MFC Cellulose fibres, fibre- 4 Technology based waste (recycled) 5 GmbH 6 CORE technology 7 enables modification of 8 cellulose fibres using 9 minimum energy 10 11 BASF SE owns exclusive rights to 12 industrialise Zelfo MFC 13 fibre technology within 14 pulp, paper and board 15 industries 16 17 18 CelluComp CNFs Small plant Waste streams of root running vegetables 19 11 partners in 5 Curran® 20 countries, “Proprietary 21 Paste/slurry technology” 22 supported by 23 Strathclyde U Powder 24 and Reading U, Thin sheets 25 coordinated by 26 Institute of Composites 27 Nanotechnology 28 UK 29 30 Imerys FibreLean MFC 1000 to > Range of (wood) pulp 31 10,000 species 32 combination of kaolin or tons/year calcium carbonate with No fiber pretreatment; 33 MFCs co grinding mineral 34 with fiber 35 36 On trial by Imerys 37 customers in a wide 38 range of papers 39 40 FRANCE CTP/FCBA CMFs/CNFs ~ 0.1 Lignocellulosics 41 ton/day 42 InTechFibres TEMPO catalyzed 43 capacity oxidation 44 partnership (to 100 g to 80 summer 2014) Meca enzymatic pre 45 kg treatments 46 CMF/CNF 47 Other pre treatments 48 49 Ariete NS3075H 50 1000 L/h, 55 kW motor, 51 1500 bars maxi 52 53 Semi industrial 54 production 55 For research 56 57 58 59 60 ACS Paragon Plus Environment Page 55 of 70 ACS Sustainable Chemistry & Engineering
1 2 3 applications: Panther 4 homogenizer 50 L/h and 5 lab microfluidizer 6 7 8 InoFib CMFs unavailable Cellulosic fibres 9 LGP2 start up Modified CMFs Mechanical treatment 10 11 12 13 14 15 SWITZERLAND Swiss Federal CNFs 15 kg/day Wood and other 16 Laboratories for lignocellulosic fiber 17 Materials sources 18 Science and 19 Technology Enzymatic pre treatment 20 Empa 21 Microfluidizer 22 23 GERMANY J. Rettenmaier CMFs 24 & Söhne GmbH 25 (maybe) 26 27 28 29 NETHERLANDS/UK Sappi CNFs 8 tons/year Wood fibres target 30 in partnership dry powder readily re “New low cost process” 31 with Edinburgh dispersed in water (pilot plant) 32 Napier CNFs with unique 33 University, on planned for morphology, 34 Brightlands early 2016 specifically modified for 35 Chemelot either hydrophobic or 36 Campus in hydrophilic applications 37 Sittard Geleen, 38 the Netherlands 39 40 IRAN Nano Novin Industry Bacterial cellulose 41 Polymer Co 42 Production of cellulose 43 nanofibers using 44 bottom up approach of 45 bacterial synthesis 46 Provide nanocellulose 47 and other bio based 48 nanopolymers using top 49 down approaches 50 51 52 53 54 55 56 57 58 59 60 ACS Paragon Plus Environment ACS Sustainable Chemistry & Engineering Page 56 of 70
1 2 3 CHINA Tianjin Haojia CNFs Dissolving cotton pulp 4 Cellulose Co., Bleached sulfate pulp 5 Ltd. Modified CNFs (soft- and hardwood) 6 7 TEMPO oxidized, High pressure 8 cationized, homogenizer 9 carboxymethylated, 10 polymer grafted or 11 Super micro grinder 12 13 14 Indian Council CNFs 10 kg/day Cotton linters 15 of Agricultural 16 INDIA Research and CNCs Pilot plant MCC from short staple 17 Central Institute cotton fibers 18 for Research on Sugarcane bagasse 19 Cotton 20 Technology Other agro-biomass 21 22 (ICAR Novel microbial, 23 CIRCOT) enzymatic and chemo 24 mechanical processes, 25 e.g. in membrane reactor 26 for continuous 27 hydrolysis and 28 simultaneous removal of 29 nano cellulose without 30 substrate inhibition 31 32 33 JAPAN Daicel** Nano CelishTM Purified pulp 34 filtration/food/industrial 10 35% Mechanical treatment 35 grades solids 36 37 38 39 40 41 42 43 Dai ichi Kogyo “Cellulose single 50 ton/year NO INFO 44 Seiyaku Co., nanofiber”: 45 Ltd. 2% solids TEMPO oxidation 46 RheocrystaTM 47 48 49 Daio Paper CNFs NO INFO 50 51 Mechanical treatment, 52 etc. 53 54 55 56 57 58 59 60 ACS Paragon Plus Environment Page 57 of 70 ACS Sustainable Chemistry & Engineering
1 2 3 Sugino Machine BiNFi s NO INFO 4
5 Biomass nanofiber 2, 5, 10% Ultra high pressure 6 solids water jet 7 8 9 Chuetsu Pulp & CNFs Bleached kraft pulp: 10 Paper CNF/plastic composites Bamboo, 11 Softwood/Hardwood 12 13 Aqueous counter 14 collision 15 16 Nippon Paper CNFs > 30 Wood pulp 17 Industries* ton/year 18 CellenpiaTM TEMPO oxidation 19 (> 0.1 Carboxymethylation 20 ton/day) 21 Mechanical treatment 22 23 Oji Holdings CNFs Chemical modification 24 25 Mechanical treatment 26 27 28 Asahi Kasei** PreciséTM -- 29 30 (non woven
31 containing CNFs) 32
33 34 35 Seiko PMC CNF nanocomposites Wood pulp
36 Mentioned in slide from Mechanical treatment + 37 TAPPI Nano 38 conference, holds patent Hydrophobization 39 with DIC Products 40 41 42 DIC CNF/plastic -- 43 Corporation nanocomposites 44 45 Tokushu Tokai Absorbent products No information on 46 Paper company website 47 (SAP and CNF) 48 49 672 50 51 52 673 Though the nanocellulose could be commercially available, the preparation methods of 53 54 674 nanocellulose involves multiple steps and demands many harsh chemicals. The recovery 55 56 57 58 59 60 ACS Paragon Plus Environment ACS Sustainable Chemistry & Engineering Page 58 of 70
1 2 3 675 methods should also be developed. These short comings should be overcome and single step 4 5 6 676 preparation methods should be developed by the researchers. In recent times, the researchers also 7 8 677 concentrate on the recovery of lignin and hemicelluloses that are removed during the purification 9 10 678 process for their further use in different applications. The new sources like agriculture and 11 12 679 industrial wastes should be considered for the preparation of NC industrially. The properties of 13 14 15 680 the NC from these sources are also promising when compared to that of NC from wood sources. 16 17 681 Since the crop and industrial wastes are abundant everywhere in the world, they can be used in 18 19 682 number of applications worldwide. 20 21 22 683 CONCLUSION: 23 24 25 684 This review has presented the detailed study on the preparation and properties of the 26 27 28 685 nanocellulose obtained from the crop and industrial wastes, application of NC from various 29 30 686 sources and the most recent industrial trend of wood based NC. This review emphasizes the use 31 32 687 of agriculture and industrial wastes in the field of nanotechnology and it should be explored 33 34 688 more by the researchers and industries. The fore mentioned sources are not only easily available, 35 36 37 689 cost effective and diverse in properties but also, they can produce the value added nanomaterials 38 39 690 which will create new economy and acts as most suitable raw material for the NC production. 40 41 691 While the applications of NC have been explored in different fields as composites, films, 42 43 44 692 hydrogels and aerogels, many new age applications in the form of smart materials, stiffer carbon 45 46 693 fibers, printing ink and electronic devices should be explored. With the ever increasing 47 48 694 environment concerns and moving towards green materials, the researchers should think about 49 50 51 695 outside the box applications to move the cellulose nanomaterials forward considering the 52 53 696 alternative sustainable raw materials like agriculture and industrial wastes. 54 55 56 697 57 58 59 60 ACS Paragon Plus Environment Page 59 of 70 ACS Sustainable Chemistry & Engineering
1 2 3 698 4 5 6 699 7 8 9 700 10 11 12 701 13 14 15 702 16 17 18 703 19 20 21 704 22 23 24 705 25 26 27 706 28 29 30 707 31 32 33 708 34 35 36 709 37 38 39 710 Author information: 40 41 711 Corresponding Authors 42 43 712 *Email: [email protected] 44 45 46 713 *Email: [email protected] 47 48 714 Address: 730 Rue Bernard, Granby, Quebec, J2J 0H6, Canada. 49 50 715 Note: The authors declare no competing financial interest. 51 52 53 716 Biographies: 54 55 717 56 57 58 59 60 ACS Paragon Plus Environment ACS Sustainable Chemistry & Engineering Page 60 of 70
1 2 3 718 Malladi Rajinipriya is a PhD student, under Prof. Mathieu Robert and Prof. Said Elkoun at 4 5 6 719 University of Sherbrooke, Canada. She is a master graduate from University Joseph Fourier in 7 8 720 Nano chemistry and nanomaterials. She worked as a Research chemist in analytical department 9 10 721 at Gland Pharma Ltd, Hyderabad, India. She is currently working on extraction of nanocellulose 11 12 722 from agriculture and industrial wastes and its applications. 13 14 15 723 16 17 724 18 19 725 Dr. Malladi Nagalakshmaiah currently postdoctoral researcher at University of 20 21 22 726 Sherbrooke, Canada. He received his PhD in 2016 from university of Grenoble 23 24 727 Alpes, France. His PhD research was on the melt processing of cellulose 25 26 728 nanocrystals: thermal, mechanical and rheological properties of nanocomposites. 27 28 29 729 His research interests are Biorefinery, Biomaterials, Nanocellulose, Surface modification, 30 31 730 Polymer nano composites. 32 33 731 Prof. Saïd Elkoun 34 35 732 Pr. Saïd Elkoun is Professor and head of the Mechanical Engineering 36 37 38 733 Department at the Faculty of Engineering of Université de Sherbrooke, Canada 39 40 734 (UdeS). Pr Elkoun is also co founder and scientific co director of the Center for 41 42 735 Innovation in Technological Eco design (CITE). His expertise is on polymer crystallization, 43 44 45 736 processing microstructure property relationships of polymers, biopolymers and nanocomposites. 46 47 737 48 49 738 Dr. Mathieu Robert is Professor at the Faculty of Engineering of Université de 50 51 52 739 Sherbrooke, Canada (UdeS). Pr Robert is also Chair holder of the Canada 53 54 740 research chair on polymer Eco composites and scientific co director of the 55 56 57 58 59 60 ACS Paragon Plus Environment Page 61 of 70 ACS Sustainable Chemistry & Engineering
1 2 3 741 Center for Innovation in Technological Eco design (CITE). He is a material scientist with an 4 5 6 742 expertise in the elaboration, characterization and durability study of bio based composite 7 8 743 materials. His current research interests deal with the extraction, pre treatment, functionalization 9 10 744 and characterization of bio sourced reinforcements from agriculture wastes. 11 12 13 745 ACKNOWLEDGEMENTS: 14 15 16 746 The authors want to thank National Science and Engineering Research Council” (NSERC) of 17 18 19 747 Canada, the “Centre québecois des matériaux fonctionnels” (CQMF) and the “Consortium de 20 21 748 Recherché ET Innovations en Bioprocédés Industriels du Québec” (CRIBIQ) of Fonds de 22 23 749 recherche du Québec – Nature ET technologies (FRQNT). 24 25 26 750 27 28 29 751 30 31 32 752 33 34 35 753 REFERENCES: 36 37 38 754 (1) Klemm, D.; Kramer, F.; Moritz, S.; Lindström, T.; Ankerfors, M.; Gray, D.; Dorris, A. 39 755 Nanocelluloses: A New Family of Nature-Based Materials. Angew. Chem. Int. Ed. 2011, 50 (24), 40 756 5438–5466 DOI: 10.1002/anie.201001273. 41 757 (2) Charreau, H.; L Foresti, M.; Vázquez, A. Nanocellulose Patents Trends: A Comprehensive Review 42 43 758 on Patents on Cellulose Nanocrystals, Microfibrillated and Bacterial Cellulose. Recent Pat. 44 759 Nanotechnol. 2013, 7 (1), 56–80. 45 760 (3) Yano, H.; Nakahara, S. Bio-Composites Produced from Plant Microfiber Bundles with a 46 761 Nanometer Unit Web-like Network. J. Mater. Sci. 2004, 39 (5), 1635–1638. 47 762 (4) de Souza Lima, M. M.; Borsali, R. Rodlike Cellulose Microcrystals: Structure, Properties, and 48 763 Applications. Macromol. Rapid Commun. 2004, 25 (7), 771–787 DOI: 10.1002/marc.200300268. 49 764 (5) Chen, H. Chemical Composition and Structure of Natural Lignocellulose. In Biotechnology of 50 765 lignocellulose; Springer, 2014; pp 25–71. 51 52 766 (6) Dungani, R.; Karina, M.; . S.; Sulaeman, A.; Hermawan, D.; Hadiyane, A. Agricultural Waste Fibers 2016 53 767 Towards Sustainability and Advanced Utilization: A Review. Asian J. Plant Sci. , 15 (1), 42– 54 768 55 DOI: 10.3923/ajps.2016.42.55. 55 769 (7) Doree, C. Methods in Cellulose Chemistry. 1947. 56 57 58 59 60 ACS Paragon Plus Environment ACS Sustainable Chemistry & Engineering Page 62 of 70
1 2 3 770 (8) Abitbol, T.; Rivkin, A.; Cao, Y.; Nevo, Y.; Abraham, E.; Ben-Shalom, T.; Lapidot, S.; Shoseyov, O. 4 771 Nanocellulose, a Tiny Fiber with Huge Applications. Curr. Opin. Biotechnol. 2016, 39, 76–88 DOI: 5 772 10.1016/j.copbio.2016.01.002. 6 7 773 (9) Jack Miller. NANOCELLULOSE STATE OF THE INDUSTRY. Tappi Nano.org December 2015. 8 774 (10) Abdul Khalil, H. P. S.; Davoudpour, Y.; Islam, M. N.; Mustapha, A.; Sudesh, K.; Dungani, R.; 9 775 Jawaid, M. Production and Modification of Nanofibrillated Cellulose Using Various Mechanical 10 776 Processes: A Review. Carbohydr. Polym. 2014, 99, 649–665 DOI: 10.1016/j.carbpol.2013.08.069. 11 777 (11) Nechyporchuk, O.; Belgacem, M. N.; Bras, J. Production of Cellulose Nanofibrils: A Review of 12 778 Recent Advances. Ind. Crops Prod. 2016, 93, 2–25 DOI: 10.1016/j.indcrop.2016.02.016. 13 779 (12) Habibi, Y.; Lucia, L. A.; Rojas, O. J. Cellulose Nanocrystals: Chemistry, Self-Assembly, and 14 780 Applications. Chem. Rev. 2010, 110 (6), 3479–3500 DOI: 10.1021/cr900339w. 15 781 (13) Mariano, M.; El Kissi, N.; Dufresne, A. Cellulose Nanocrystals and Related Nanocomposites: 16 2014 17 782 Review of Some Properties and Challenges. J. Polym. Sci. Part B Polym. Phys. , 52 (12), 791– 18 783 806 DOI: 10.1002/polb.23490. 19 784 (14) Trache, D.; Hussin, M. H.; Haafiz, M. K. M.; Thakur, V. K. Recent Progress in Cellulose 20 785 Nanocrystals: Sources and Production. Nanoscale 2017, 9 (5), 1763–1786 DOI: 21 786 10.1039/C6NR09494E. 22 787 (15) Kalia, S.; Kaith, B. S.; Kaur, I. Pretreatments of Natural Fibers and Their Application as 23 788 Reinforcing Material in Polymer Composites-A Review. Polym. Eng. Sci. 2009, 49 (7), 1253–1272 24 789 DOI: 10.1002/pen.21328. 25 26 790 (16) Moon, R. J.; Martini, A.; Nairn, J.; Simonsen, J.; Youngblood, J. Cellulose Nanomaterials Review: 27 791 Structure, Properties and Nanocomposites. Chem. Soc. Rev. 2011, 40 (7), 3941 DOI: 28 792 10.1039/c0cs00108b. 29 793 (17) Mohammadinejad, R.; Karimi, S.; Iravani, S.; Varma, R. S. Plant-Derived Nanostructures: Types 30 794 and Applications. Green Chem 2016, 18 (1), 20–52 DOI: 10.1039/C5GC01403D. 31 795 (18) García, A.; Gandini, A.; Labidi, J.; Belgacem, N.; Bras, J. Industrial and Crop Wastes: A New 32 796 Source for Nanocellulose Biorefinery. Ind. Crops Prod. 2016, 93, 26–38 DOI: 33 797 10.1016/j.indcrop.2016.06.004. 34 35 798 (19) Faruk, O.; Bledzki, A. K.; Fink, H.-P.; Sain, M. Biocomposites Reinforced with Natural Fibers: 2012 36 799 2000–2010. Prog. Polym. Sci. , 37 (11), 1552–1596 DOI: 37 800 10.1016/j.progpolymsci.2012.04.003. 38 801 (20) Madison, W. Density, Fiber Length, and Yields of Pulp for Various Species of Wood. 1953. 39 802 (21) Martí-Ferrer, F.; Vilaplana, F.; Ribes-Greus, A.; Benedito-Borrás, A.; Sanz-Box, C. Flour Rice Husk 40 803 as Filler in Block Copolymer Polypropylene: Effect of Different Coupling Agents. J. Appl. Polym. 41 804 Sci. 2006, 99 (4), 1823–1831 DOI: 10.1002/app.22717. 42 805 (22) Hoareau, W.; Trindade, W. G.; Siegmund, B.; Castellan, A.; Frollini, E. Sugar Cane Bagasse and 43 806 Curaua Lignins Oxidized by Chlorine Dioxide and Reacted with Furfuryl Alcohol: Characterization 44 2004 45 807 and Stability. Polym. Degrad. Stab. , 86 (3), 567–576 DOI: 46 808 10.1016/j.polymdegradstab.2004.07.005. 47 809 (23) Mohanty, A. K.; Misra, M.; Drzal, L. T. Natural Fibers, Biopolymers, and Biocomposites; CRC 48 810 press, 2005. 49 811 (24) Li, R.; Fei, J.; Cai, Y.; Li, Y.; Feng, J.; Yao, J. Cellulose Whiskers Extracted from Mulberry: A Novel 50 812 Biomass Production. Carbohydr. Polym. 2009, 76 (1), 94–99 DOI: 10.1016/j.carbpol.2008.09.034. 51 813 (25) Kallel, F.; Bettaieb, F.; Khiari, R.; García, A.; Bras, J.; Chaabouni, S. E. Isolation and Structural 52 814 Characterization of Cellulose Nanocrystals Extracted from Garlic Straw Residues. Ind. Crops 53 2016 54 815 Prod. , 87, 287–296 DOI: 10.1016/j.indcrop.2016.04.060. 55 56 57 58 59 60 ACS Paragon Plus Environment Page 63 of 70 ACS Sustainable Chemistry & Engineering
1 2 3 816 (26) Siqueira, G.; Oksman, K.; Tadokoro, S. K.; Mathew, A. P. Re-Dispersible Carrot Nanofibers with 4 817 High Mechanical Properties and Reinforcing Capacity for Use in Composite Materials. Compos. 5 818 Sci. Technol. 2016, 123, 49–56 DOI: 10.1016/j.compscitech.2015.12.001. 6 7 819 (27) Bano, S.; Negi, Y. S. Studies on Cellulose Nanocrystals Isolated from Groundnut Shells. 2017 8 820 Carbohydr. Polym. , 157, 1041–1049 DOI: 10.1016/j.carbpol.2016.10.069. 9 821 (28) Rhim, J.-W.; Reddy, J. P.; Luo, X. Isolation of Cellulose Nanocrystals from Onion Skin and Their 10 822 Utilization for the Preparation of Agar-Based Bio-Nanocomposites Films. Cellulose 2015, 22 (1), 11 823 407–420 DOI: 10.1007/s10570-014-0517-7. 12 824 (29) Klemm, D.; Heublein, B.; Fink, H.-P.; Bohn, A. Cellulose: Fascinating Biopolymer and Sustainable 13 825 Raw Material. Angew. Chem. Int. Ed. 2005, 44 (22), 3358–3393 DOI: 10.1002/anie.200460587. 14 826 (30) George, J.; S N, S. Cellulose Nanocrystals: Synthesis, Functional Properties, and Applications. 15 827 Nanotechnol. Sci. Appl. 2015, 45 DOI: 10.2147/NSA.S64386. 16 17 828 (31) Cave, I.; Walker, J. Stiffness of Wood in Fast-Grown Plantation Softwoods: The Influence of 18 829 Microfibril Angle. For. Prod. J. 1994, 44 (5), 43. 19 830 (32) Yokouchi, M.; Sakakibara, Y.; Chatani, Y.; Tadokoro, H.; Tanaka, T.; Yoda, K. Structures of Two 20 831 Crystalline Forms of Poly (Butylene Terephthalate) and Reversible Transition between Them by 21 832 Mechanical Deformation. Macromolecules 1976, 9 (2), 266–273. 22 833 (33) Habibi, Y.; Lucia, L. A.; Rojas, O. J. Cellulose Nanocrystals: Chemistry, Self-Assembly, and 23 834 Applications. Chem. Rev. 2010, 110 (6), 3479–3500 DOI: 10.1021/cr900339w. 24 835 (34) Gaffey, M. J. Spectral Reflectance Characteristics of the Meteorite Classes. J. Geophys. Res. 25 1976 26 836 , 81 (5), 905–920. 27 837 (35) HATTORI. New Solvents for Cellulose. II. Ethylenediamine/Thiocyanate Salt System. 2003. 28 838 (36) Kuga, S.; Takagi, S.; Brown, R. M. Native Folded-Chain Cellulose II. Polymer 1993, 34 (15), 3293– 29 839 3297 DOI: 10.1016/0032-3861(93)90404-X. 30 840 (37) Marrinan, H. J.; Mann, J. Infrared Spectra of the Crystalline Modifications of Cellulose. J. Polym. 31 841 Sci. 1956, 21 (98), 301–311. 32 842 (38) Gardiner, E. S.; Sarko, A. Packing Analysis of Carbohydrates and Polysaccharides. 16. The Crystal 33 843 Structures of Celluloses IVI and IVII. Can. J. Chem. 1985, 63 (1), 173–180. 34 35 844 (39) Estela, R.; Luis, J. Hydrolysis of Biomass Mediated by Cellulases for the Production of Sugars. In 36 845 Sustainable Degradation of Lignocellulosic Biomass - Techniques, Applications and 37 846 Commercialization; Chandel, A., Ed.; InTech, 2013. 38 847 (40) Scheller, H. V.; Ulvskov, P. Hemicelluloses. Annu. Rev. Plant Biol. 2010, 61 (1), 263–289 DOI: 39 848 10.1146/annurev-arplant-042809-112315. 40 849 (41) Ebringerová, A.; Hromádková, Z.; Heinze, T. Hemicellulose. In Polysaccharides I; Heinze, T., Ed.; 41 850 Springer-Verlag: Berlin/Heidelberg, 2005; Vol. 186, pp 1–67. 42 851 (42) Eero Kontturi. Hemicellulose: Structure, Characterization, Dissolution, Modification, 2015. 43 852 (43) Kozioł, A.; Cybulska, J.; Pieczywek, P. M.; Zdunek, A. Evaluation of Structure and Assembly of 44 45 853 Xyloglucan from Tamarind Seed (Tamarindus Indica L.) with Atomic Force Microscopy. Food 46 854 Biophys. 2015, 10 (4), 396–402 DOI: 10.1007/s11483-015-9395-2. 47 855 (44) Arola, S.; Malho, J.; Laaksonen, P.; Lille, M.; Linder, M. B. The Role of Hemicellulose in 48 856 Nanofibrillated Cellulose Networks. Soft Matter 2013, 9 (4), 1319–1326 DOI: 49 857 10.1039/C2SM26932E. 50 858 (45) Chaker, A.; Alila, S.; Mutjé, P.; Vilar, M. R.; Boufi, S. Key Role of the Hemicellulose Content and 51 859 the Cell Morphology on the Nanofibrillation Effectiveness of Cellulose Pulps. Cellulose 2013, 20 52 860 (6), 2863–2875 DOI: 10.1007/s10570-013-0036-y. 53 54 861 (46) Zhang, J.; Chen, Y.; Brook, M. A. Reductive Degradation of Lignin and Model Compounds by 2014 55 862 Hydrosilanes. ACS Sustain. Chem. Eng. , 2 (8), 1983–1991 DOI: 10.1021/sc500302j. 56 57 58 59 60 ACS Paragon Plus Environment ACS Sustainable Chemistry & Engineering Page 64 of 70
1 2 3 863 (47) Doherty, W. O. S.; Mousavioun, P.; Fellows, C. M. Value-Adding to Cellulosic Ethanol: Lignin 4 864 Polymers. Ind. Crops Prod. 2011, 33 (2), 259–276 DOI: 10.1016/j.indcrop.2010.10.022. 5 865 (48) Lora, J. H.; Glasser, W. G. Recent Industrial Applications of Lignin: A Sustainable Alternative to 6 2002 7 866 Nonrenewable Materials. J. Polym. Environ. , 10 (1), 39–48. 8 867 (49) E Sjostrom. Wood Chemistry: Fundamentals and Applications. 1981. 9 868 (50) Xiao, S.; Gao, R.; Gao, L.; Li, J. Poly(vinyl Alcohol) Films Reinforced with Nanofibrillated Cellulose 10 869 (NFC) Isolated from Corn Husk by High Intensity Ultrasonication. Carbohydr. Polym. 2016, 136, 11 870 1027–1034 DOI: 10.1016/j.carbpol.2015.09.115. 12 871 (51) Sacui, I. A.; Nieuwendaal, R. C.; Burnett, D. J.; Stranick, S. J.; Jorfi, M.; Weder, C.; Foster, E. J.; 13 872 Olsson, R. T.; Gilman, J. W. Comparison of the Properties of Cellulose Nanocrystals and Cellulose 14 873 Nanofibrils Isolated from Bacteria, Tunicate, and Wood Processed Using Acid, Enzymatic, 15 874 Mechanical, and Oxidative Methods. ACS Appl. Mater. Interfaces 2014, 6 (9), 6127–6138 DOI: 16 17 875 10.1021/am500359f. 18 876 (52) Yoon, S. H.; Jin, H.-J.; Kook, M.-C.; Pyun, Y. R. Electrically Conductive Bacterial Cellulose by 19 877 Incorporation of Carbon Nanotubes. Biomacromolecules 2006, 7 (4), 1280–1284 DOI: 20 878 10.1021/bm050597g. 21 879 (53) Lim, Y.-M.; Gwon, H.-J.; Jeun, J. P.; Nho, Y.-C. Preparation of Cellulose-Based Nanofibers Using 22 880 Electrospinning. In Nanofibers; InTech, 2010. 23 881 (54) Turbak, A. .; Snyder, F.W.; Sandberg, K.R. Microfibrillated Cellulose, a New Cellulose Product: 24 882 Properties, Uses, and Commercial Potential. 1983. 25 26 883 (55) Herrick, F. W.; Casebier, R. L.; Hamilton, J. K.; Sandberg, K. R. Microfibrillated Cellulose: 27 884 Morphology and Accessibility; ITT Rayonier Inc., Shelton, WA, 1983; Vol. 37. 28 885 (56) Ranby. Aqeous Colliodal Solutions of Cellulose Micelles. 1949. 29 886 (57) Ehmann, H. M. A.; Mohan, T.; Koshanskaya, M.; Scheicher, S.; Breitwieser, D.; Ribitsch, V.; Stana- 30 887 Kleinschek, K.; Spirk, S. Design of Anticoagulant Surfaces Based on Cellulose Nanocrystals. Chem 31 888 Commun 2014, 50 (86), 13070–13072 DOI: 10.1039/C4CC05254D. 32 889 (58) Nickerson, R. F.; Habrle, J. A. Cellulose Intercrystalline Structure. Ind. Eng. Chem. 1947, 39 (11), 33 890 1507–1512. 34 35 891 (59) Dugan, J. M.; Gough, J. E.; Eichhorn, S. J. Bacterial Cellulose Scaffolds and Cellulose 2013 36 892 Nanowhiskers for Tissue Engineering. Nanomed. , 8 (2), 287–298 DOI: 37 893 10.2217/nnm.12.211. 38 894 (60) Dong, X. M.; Revol, J.-F.; Gray, D. G. Effect of Microcrystallite Preparation Conditions on the 39 895 Formation of Colloid Crystals of Cellulose. Cellulose 1998, 5 (1), 19–32. 40 896 (61) Marchessault et al. Liquid Crystal Systems from Fibrillar Polysaccharides. 1959. 41 897 (62) Revol, J.-F.; Bradford, H.; Giasson, J.; Marchessault, R.; Gray, D. Helicoidal Self-Ordering of 42 898 Cellulose Microfibrils in Aqueous Suspension. Int. J. Biol. Macromol. 1992, 14 (3), 170–172. 43 899 (63) El-Saied, H.; Basta, A. H.; Gobran, R. H. Research Progress in Friendly Environmental Technology 44 45 900 for the Production of Cellulose Products (Bacterial Cellulose and Its Application). Polym.-Plast. 46 901 Technol. Eng. 2004, 43 (3), 797–820 DOI: 10.1081/PPT-120038065. 47 902 (64) Ramakrishna, S.; Fujihara, K.; Teo, W.-E.; Yong, T.; Ma, Z.; Ramaseshan, R. Electrospun 48 903 Nanofibers: Solving Global Issues. Mater. Today 2006, 9 (3), 40–50. 49 904 (65) Konwarh, R.; Karak, N.; Misra, M. Electrospun Cellulose Acetate Nanofibers: The Present Status 50 905 and Gamut of Biotechnological Applications. Biotechnol. Adv. 2013, 31 (4), 421–437 DOI: 51 906 10.1016/j.biotechadv.2013.01.002. 52 907 (66) Graedel, T. E.; Allwood, J.; Birat, J.-P.; Buchert, M.; Hagelüken, C.; Reck, B. K.; Sibley, S. F.; 53 54 908 Sonnemann, G.; United Nations Environment Programme; Working Group on the Global Metal 55 909 Flows. Recycling Rates of Metals: A Status Report; United Nations Environment Programme: 56 910 Nairobi, Kenya, 2011. 57 58 59 60 ACS Paragon Plus Environment Page 65 of 70 ACS Sustainable Chemistry & Engineering
1 2 3 911 (67) Dufresne, A.; Cavaill�, J.-Y.; Vignon, M. R. Mechanical Behavior of Sheets Prepared from Sugar 4 912 Beet Cellulose Microfibrils. J. Appl. Polym. Sci. 1997, 64 (6), 1185–1194 DOI: 10.1002/(SICI)1097- 5 913 4628(19970509)64:6<1185::AID-APP19>3.0.CO;2-V. 6 7 914 (68) Nagalakshmaiah, M.; kissi, N. E.; Mortha, G.; Dufresne, A. Structural Investigation of Cellulose 8 915 Nanocrystals Extracted from Chili Leftover and Their Reinforcement in Cariflex-IR Rubber Latex. 9 916 Carbohydr. Polym. 2016, 136, 945–954 DOI: 10.1016/j.carbpol.2015.09.096. 10 917 (69) Dittenber, D. B.; GangaRao, H. V. S. Critical Review of Recent Publications on Use of Natural 11 918 Composites in Infrastructure. Compos. Part Appl. Sci. Manuf. 2012, 43 (8), 1419–1429 DOI: 12 919 10.1016/j.compositesa.2011.11.019. 13 920 (70) Bhatnagar, A. Processing of Cellulose Nanofiber-Reinforced Composites. J. Reinf. Plast. Compos. 14 921 2005, 24 (12), 1259–1268 DOI: 10.1177/0731684405049864. 15 16 922 (71) Wang, B.; Sain, M. Isolation of Nanofibers from Soybean Source and Their Reinforcing Capability 2007 17 923 on Synthetic Polymers. Compos. Sci. Technol. , 67 (11–12), 2521–2527 DOI: 18 924 10.1016/j.compscitech.2006.12.015. 19 925 (72) Zuluaga, R.; Putaux, J. L.; Cruz, J.; Vélez, J.; Mondragon, I.; Gañán, P. Cellulose Microfibrils from 20 926 Banana Rachis: Effect of Alkaline Treatments on Structural and Morphological Features. 21 927 Carbohydr. Polym. 2009, 76 (1), 51–59 DOI: 10.1016/j.carbpol.2008.09.024. 22 928 (73) Habibi, Y.; Mahrouz, M.; Vignon, M. R. Microfibrillated Cellulose from the Peel of Prickly Pear 23 929 Fruits. Food Chem. 2009, 115 (2), 423–429 DOI: 10.1016/j.foodchem.2008.12.034. 24 930 (74) Cherian, B. M.; Leão, A. L.; de Souza, S. F.; Thomas, S.; Pothan, L. A.; Kottaisamy, M. Isolation of 25 2010 26 931 Nanocellulose from Pineapple Leaf Fibres by Steam Explosion. Carbohydr. Polym. , 81 (3), 27 932 720–725 DOI: 10.1016/j.carbpol.2010.03.046. 28 933 (75) Rosa, M. F.; Medeiros, E. S.; Malmonge, J. A.; Gregorski, K. S.; Wood, D. F.; Mattoso, L. H. C.; 29 934 Glenn, G.; Orts, W. J.; Imam, S. H. Cellulose Nanowhiskers from Coconut Husk Fibers: Effect of 30 935 Preparation Conditions on Their Thermal and Morphological Behavior. Carbohydr. Polym. 2010, 31 936 81 (1), 83–92 DOI: 10.1016/j.carbpol.2010.01.059. 32 937 (76) Pasquini, D.; Teixeira, E. de M.; Curvelo, A. A. da S.; Belgacem, M. N.; Dufresne, A. Extraction of 33 938 Cellulose Whiskers from Cassava Bagasse and Their Applications as Reinforcing Agent in Natural 34 2010 35 939 Rubber. Ind. Crops Prod. , 32 (3), 486–490 DOI: 10.1016/j.indcrop.2010.06.022. 36 940 (77) Deepa, B.; Abraham, E.; Cherian, B. M.; Bismarck, A.; Blaker, J. J.; Pothan, L. A.; Leao, A. L.; de 37 941 Souza, S. F.; Kottaisamy, M. Structure, Morphology and Thermal Characteristics of Banana Nano 38 942 Fibers Obtained by Steam Explosion. Bioresour. Technol. 2011, 102 (2), 1988–1997 DOI: 39 943 10.1016/j.biortech.2010.09.030. 40 944 (78) Xiao, S.; Gao, R.; Gao, L.; Li, J. Poly(vinyl Alcohol) Films Reinforced with Nanofibrillated Cellulose 41 945 (NFC) Isolated from Corn Husk by High Intensity Ultrasonication. Carbohydr. Polym. 2016, 136, 42 946 1027–1034 DOI: 10.1016/j.carbpol.2015.09.115. 43 44 947 (79) Baheti, V.; Abbasi, R.; Militky, J. Ball Milling of Jute Fibre Wastes to Prepare Nanocellulose. 2012 45 948 World J. Eng. , 9 (1), 45–50. 46 949 (80) Johar, N.; Ahmad, I.; Dufresne, A. Extraction, Preparation and Characterization of Cellulose 47 950 Fibres and Nanocrystals from Rice Husk. Ind. Crops Prod. 2012, 37 (1), 93–99 DOI: 48 951 10.1016/j.indcrop.2011.12.016. 49 952 (81) Lu, P.; Hsieh, Y.-L. Cellulose Isolation and Core–shell Nanostructures of Cellulose Nanocrystals 50 953 from Chardonnay Grape Skins. Carbohydr. Polym. 2012, 87 (4), 2546–2553 DOI: 51 954 10.1016/j.carbpol.2011.11.023. 52 955 (82) Li, J.; Wei, X.; Wang, Q.; Chen, J.; Chang, G.; Kong, L.; Su, J.; Liu, Y. Homogeneous Isolation of 53 54 956 Nanocellulose from Sugarcane Bagasse by High Pressure Homogenization. Carbohydr. Polym. 55 957 2012, 90 (4), 1609–1613 DOI: 10.1016/j.carbpol.2012.07.038. 56 57 58 59 60 ACS Paragon Plus Environment ACS Sustainable Chemistry & Engineering Page 66 of 70
1 2 3 958 (83) Purkait, B. S.; Ray, D.; Sengupta, S.; Kar, T.; Mohanty, A.; Misra, M. Isolation of Cellulose 4 959 Nanoparticles from Sesame Husk. Ind. Eng. Chem. Res. 2011, 50 (2), 871–876 DOI: 5 960 10.1021/ie101797d. 6 7 961 (84) Chen, D.; Lawton, D.; Thompson, M. R.; Liu, Q. Biocomposites Reinforced with Cellulose 2012 8 962 Nanocrystals Derived from Potato Peel Waste. Carbohydr. Polym. , 90 (1), 709–716 DOI: 9 963 10.1016/j.carbpol.2012.06.002. 10 964 (85) Morais, J. P. S.; Rosa, M. de F.; de Souza Filho, M. de sá M.; Nascimento, L. D.; do Nascimento, D. 11 965 M.; Cassales, A. R. Extraction and Characterization of Nanocellulose Structures from Raw Cotton 12 966 Linter. Carbohydr. Polym. 2013, 91 (1), 229–235 DOI: 10.1016/j.carbpol.2012.08.010. 13 967 (86) Wang, Q. Q.; Zhu, J. Y.; Gleisner, R.; Kuster, T. A.; Baxa, U.; McNeil, S. E. Morphological 14 968 Development of Cellulose Fibrils of a Bleached Eucalyptus Pulp by Mechanical Fibrillation. 15 969 Cellulose 2012, 19 (5), 1631–1643 DOI: 10.1007/s10570-012-9745-x. 16 17 970 (87) Jiang, F.; Hsieh, Y.-L. Chemically and Mechanically Isolated Nanocellulose and Their Self- 18 971 Assembled Structures. Carbohydr. Polym. 2013, 95 (1), 32–40 DOI: 19 972 10.1016/j.carbpol.2013.02.022. 20 973 (88) Rehman, N.; de Miranda, M. I. G.; Rosa, S. M. L.; Pimentel, D. M.; Nachtigall, S. M. B.; Bica, C. I. 21 974 D. Cellulose and Nanocellulose from Maize Straw: An Insight on the Crystal Properties. J. Polym. 22 975 Environ. 2013 DOI: 10.1007/s10924-013-0624-9. 23 976 (89) Mohamad Haafiz, M. K.; Eichhorn, S. J.; Hassan, A.; Jawaid, M. Isolation and Characterization of 24 977 Microcrystalline Cellulose from Oil Palm Biomass Residue. Carbohydr. Polym. 2013, 93 (2), 628– 25 26 978 634 DOI: 10.1016/j.carbpol.2013.01.035. 27 979 (90) Mat Zain, N. F. Preparation and Characterization of Cellulose and Nanocellulose From Pomelo 28 980 (Citrus Grandis) Albedo. J. Nutr. Food Sci. 2014, 05 (01) DOI: 10.4172/2155-9600.1000334. 29 981 (91) Karimi, S.; Tahir, P. M.; Karimi, A.; Dufresne, A.; Abdulkhani, A. Kenaf Bast Cellulosic Fibers 30 982 Hierarchy: A Comprehensive Approach from Micro to Nano. Carbohydr. Polym. 2014, 101, 878– 31 983 885 DOI: 10.1016/j.carbpol.2013.09.106. 32 984 (92) Henrique, M. A.; Silvério, H. A.; Flauzino Neto, W. P.; Pasquini, D. Valorization of an Agro- 33 985 Industrial Waste, Mango Seed, by the Extraction and Characterization of Its Cellulose 34 2013 35 986 Nanocrystals. J. Environ. Manage. , 121, 202–209 DOI: 10.1016/j.jenvman.2013.02.054. 36 987 (93) Tsukamoto, J.; Durán, N.; Tasic, L. Nanocellulose and Bioethanol Production from Orange Waste 37 988 Using Isolated Microorganisms. J. Braz. Chem. Soc. 2013 DOI: 10.5935/0103-5053.20130195. 38 989 (94) Silvério, H. A.; Flauzino Neto, W. P.; Pasquini, D. Effect of Incorporating Cellulose Nanocrystals 39 990 from Corncob on the Tensile, Thermal and Barrier Properties of Poly(Vinyl Alcohol) 40 991 Nanocomposites. J. Nanomater. 2013, 2013, 1–9 DOI: 10.1155/2013/289641. 41 992 (95) Josset, S.; Orsolini, P.; Siqueira, G.; Tejado, A.; Tingaut, P.; Zimmermann, T. Energy Consumption 42 993 of the Nanofibrillation of Bleached Pulp, Wheat Straw and Recycled Newspaper through a 43 994 Grinding Process. Nord Pulp Pap Res J 2014, 29 (1), 167–175. 44 45 995 (96) Espino, E.; Cakir, M.; Domenek, S.; Román-Gutiérrez, A. D.; Belgacem, N.; Bras, J. Isolation and 46 996 Characterization of Cellulose Nanocrystals from Industrial by-Products of Agave Tequilana and 47 997 Barley. Ind. Crops Prod. 2014, 62, 552–559 DOI: 10.1016/j.indcrop.2014.09.017. 48 998 (97) Mariño, M.; Lopes da Silva, L.; Durán, N.; Tasic, L. Enhanced Materials from Nature: 49 999 Nanocellulose from Citrus Waste. Molecules 2015, 20 (4), 5908–5923 DOI: 50 1000 10.3390/molecules20045908. 51 1001 (98) Chen, Y.; Wu, Q.; Huang, B.; Huang, M.; Ai, X. Isolation and Characteristics of Cellulose and 52 1002 Nanocellulose from Lotus Leaf Stalk Agro-Wastes. BioResources 2014, 10 (1), 684–696. 53 54 1003 (99) Jiang, F.; Hsieh, Y.-L. Cellulose Nanocrystal Isolation from Tomato Peels and Assembled 2015 55 1004 Nanofibers. Carbohydr. Polym. , 122, 60–68 DOI: 10.1016/j.carbpol.2014.12.064. 56 57 58 59 60 ACS Paragon Plus Environment Page 67 of 70 ACS Sustainable Chemistry & Engineering
1 2 3 1005 (100) Mtibe, A.; Mandlevu, Y.; Linganiso, L. Z.; Anandjiwala, R. D. Extraction of Cellulose Nanowhiskers 4 1006 from Flax Fibres and Their Reinforcing Effect on Poly (Furfuryl) Alcohol. J. Biobased Mater. 5 1007 Bioenergy 2015, 9 (3), 309–317. 6 7 1008 (101) Siqueira, G.; Tapin-Lingua, S.; Bras, J.; da Silva Perez, D.; Dufresne, A. Morphological 8 1009 Investigation of Nanoparticles Obtained from Combined Mechanical Shearing, and Enzymatic 9 1010 and Acid Hydrolysis of Sisal Fibers. Cellulose 2010, 17 (6), 1147–1158 DOI: 10.1007/s10570-010- 10 1011 9449-z. 11 1012 (102) Barbosa, A.; Robles, E.; Ribeiro, J.; Lund, R.; Carreño, N.; Labidi, J. Cellulose Nanocrystal 12 1013 Membranes as Excipients for Drug Delivery Systems. Materials 2016, 9 (12), 1002 DOI: 13 1014 10.3390/ma9121002. 14 1015 (103) Cudjoe, E.; Hunsen, M.; Xue, Z.; Way, A. E.; Barrios, E.; Olson, R. A.; Hore, M. J. A.; Rowan, S. J. 15 1016 Miscanthus Giganteus: A Commercially Viable Sustainable Source of Cellulose Nanocrystals. 16 2017 17 1017 Carbohydr. Polym. , 155, 230–241 DOI: 10.1016/j.carbpol.2016.08.049. 18 1018 (104) Naz, S.; Ahmad, N.; Akhtar, J.; Ahmad, N. M.; Ali, A.; Zia, M. Management of Citrus Waste by 19 1019 Switching in the Production of Nanocellulose. IET Nanobiotechnol. 2016, 10 (6), 395–399 DOI: 20 1020 10.1049/iet-nbt.2015.0116. 21 1021 (105) Ludueña, L.; Fasce, D.; Alvarez, V. A. Nanocellulose from Ricehusk Following Alkaline Treatment 22 1022 to Remove Silica. 2011. 23 1023 (106) Chen, W.; Yu, H.; Liu, Y.; Hai, Y.; Zhang, M.; Chen, P. Isolation and Characterization of Cellulose 24 1024 Nanofibers from Four Plant Cellulose Fibers Using a Chemical-Ultrasonic Process. Cellulose 2011, 25 26 1025 18 (2), 433–442 DOI: 10.1007/s10570-011-9497-z. 27 1026 (107) Yu, H.; Qin, Z.; Liang, B.; Liu, N.; Zhou, Z.; Chen, L. Facile Extraction of Thermally Stable Cellulose 28 1027 Nanocrystals with a High Yield of 93% through Hydrochloric Acid Hydrolysis under Hydrothermal 29 1028 Conditions. J. Mater. Chem. A 2013, 1 (12), 3938 DOI: 10.1039/c3ta01150j. 30 1029 (108) Koshizawa, T. Degradation of Wood Cellulose and Cotton Linters in Phosphoric Acid. 1960. 31 1030 (109) Sadeghifar, H.; Filpponen, I.; Clarke, S. P.; Brougham, D. F.; Argyropoulos, D. S. Production of 32 1031 Cellulose Nanocrystals Using Hydrobromic Acid and Click Reactions on Their Surface. J. Mater. 33 1032 Sci. 2011, 46 (22), 7344–7355 DOI: 10.1007/s10853-011-5696-0. 34 35 1033 (110) Satyamurthy, P.; Jain, P.; Balasubramanya, R. H.; Vigneshwaran, N. Preparation and 36 1034 Characterization of Cellulose Nanowhiskers from Cotton Fibres by Controlled Microbial 37 1035 Hydrolysis. Carbohydr. Polym. 2011, 83 (1), 122–129 DOI: 10.1016/j.carbpol.2010.07.029. 38 1036 (111) Iskak, N. A. M.; Julkapli, N. M.; Hamid, S. B. A. Understanding the Effect of Synthesis Parameters 39 1037 on the Catalytic Ionic Liquid Hydrolysis Process of Cellulose Nanocrystals. Cellulose 2017, 24 (6), 40 1038 2469–2481 DOI: 10.1007/s10570-017-1273-2. 41 1039 (112) Araki, J.; Wada, M.; Kuga, S.; Okano, T. Influence of Surface Charge on Viscosity Behavior of 42 1040 Cellulose Microcrystal Suspension. J. Wood Sci. 1999, 45 (3), 258–261. 43 1041 (113) Elazzouzi-Hafraoui, S.; Nishiyama, Y.; Putaux, J.-L.; Heux, L.; Dubreuil, F.; Rochas, C. The Shape 44 45 1042 and Size Distribution of Crystalline Nanoparticles Prepared by Acid Hydrolysis of Native 46 1043 Cellulose. Biomacromolecules 2007, 9 (1), 57–65. 47 1044 (114) Kargarzadeh, H.; Ahmad, I.; Thomas, S.; Dufresne, A. Handbook of Nanocellulose and Cellulose 48 1045 Nanocomposites, 2 Volume Set; John Wiley & Sons, 2017. 49 1046 (115) Alemdar, A.; Sain, M. Isolation and Characterization of Nanofibers from Agricultural Residues – 50 1047 Wheat Straw and Soy Hulls. Bioresour. Technol. 2008, 99 (6), 1664–1671 DOI: 51 1048 10.1016/j.biortech.2007.04.029. 52 1049 (116) Taniguchi, T.; Okamura, K. New Films Produced from Microfibrillated Natural Fibres. 1998. 53 54 1050 (117) Zimmermann, T.; Pöhler, E.; Geiger, T. Cellulose Fibrils for Polymer Reinforcement. Adv. Eng. 2004 55 1051 Mater. , 6 (9), 754–761 DOI: 10.1002/adem.200400097. 56 57 58 59 60 ACS Paragon Plus Environment ACS Sustainable Chemistry & Engineering Page 68 of 70
1 2 3 1052 (118) Saito, T.; Isogai, A. Introduction of Aldehyde Groups on Surfaces of Native Cellulose Fibers by 4 1053 TEMPO-Mediated Oxidation. Colloids Surf. Physicochem. Eng. Asp. 2006, 289 (1–3), 219–225 5 1054 DOI: 10.1016/j.colsurfa.2006.04.038. 6 7 1055 (119) Pääkkö, M.; Vapaavuori, J.; Silvennoinen, R.; Kosonen, H.; Ankerfors, M.; Lindström, T.; 8 1056 Berglund, L. A.; Ikkala, O. Long and Entangled Native Cellulose I Nanofibers Allow Flexible 9 1057 Aerogels and Hierarchically Porous Templates for Functionalities. Soft Matter 2008, 4 (12), 2492 10 1058 DOI: 10.1039/b810371b. 11 1059 (120) Lee, H. V.; Hamid, S. B. A.; Zain, S. K. Conversion of Lignocellulosic Biomass to Nanocellulose: 12 1060 Structure and Chemical Process. Sci. World J. 2014, 2014, e631013 DOI: 10.1155/2014/631013. 13 1061 (121) Siró, I.; Plackett, D. Microfibrillated Cellulose and New Nanocomposite Materials: A Review. 14 1062 Cellulose 2010, 17 (3), 459–494 DOI: 10.1007/s10570-010-9405-y. 15 1063 (122) Sun, Y.; Cheng, J. Hydrolysis of Lignocellulosic Materials for Ethanol Production: A Review. 16 2002 17 1064 Bioresour. Technol. , 83 (1), 1–11. 18 1065 (123) Nakagaito, A. N.; Yano, H. The Effect of Morphological Changes from Pulp Fiber towards Nano- 19 1066 Scale Fibrillated Cellulose on the Mechanical Properties of High-Strength Plant Fiber Based 20 1067 Composites. Appl. Phys. Mater. Sci. Process. 2004, 78 (4), 547–552 DOI: 10.1007/s00339-003- 21 1068 2453-5. 22 1069 (124) Karande, V. S.; Bharimalla, A. K.; Hadge, G. B.; Mhaske, S. T.; Vigneshwaran, N. Nanofibrillation 23 1070 of Cotton Fibers by Disc Refiner and Its Characterization. 2011. 24 1071 (125) Homogenization (Chemistry). 25 26 1072 (126) Piorkowski, D. T.; McClements, D. J. Beverage Emulsions: Recent Developments in Formulation, 27 1073 Production, and Applications. Food Hydrocoll. 2014, 42, 5–41 DOI: 28 1074 10.1016/j.foodhyd.2013.07.009. 29 1075 (127) D Yashwanth Reddy. Cryogenicgrindingrenew-130914065822-phpapp01.pptx. 30 1076 (128) Chaker, A.; Alila, S.; Mutjé, P.; Vilar, M. R.; Boufi, S. Key Role of the Hemicellulose Content and 31 1077 the Cell Morphology on the Nanofibrillation Effectiveness of Cellulose Pulps. Cellulose 2013, 20 32 1078 (6), 2863–2875 DOI: 10.1007/s10570-013-0036-y. 33 1079 (129) Ferrer, A.; Filpponen, I.; Rodríguez, A.; Laine, J.; Rojas, O. J. Valorization of Residual Empty Palm 34 35 1080 Fruit Bunch Fibers (EPFBF) by Microfluidization: Production of Nanofibrillated Cellulose and 2012 36 1081 EPFBF Nanopaper. Bioresour. Technol. , 125, 249–255 DOI: 10.1016/j.biortech.2012.08.108. 37 1082 (130) Spence, K. L.; Venditti, R. A.; Rojas, O. J.; Habibi, Y.; Pawlak, J. J. A Comparative Study of Energy 38 1083 Consumption and Physical Properties of Microfibrillated Cellulose Produced by Different 39 1084 Processing Methods. Cellulose 2011, 18 (4), 1097–1111 DOI: 10.1007/s10570-011-9533-z. 40 1085 (131) Alemdar, A.; Sain, M. Isolation and Characterization of Nanofibers from Agricultural Residues – 41 1086 Wheat Straw and Soy Hulls. Bioresour. Technol. 2008, 99 (6), 1664–1671 DOI: 42 1087 10.1016/j.biortech.2007.04.029. 43 1088 (132) Nagalakshmaiah, M.; kissi, N. E.; Mortha, G.; Dufresne, A. Structural Investigation of Cellulose 44 45 1089 Nanocrystals Extracted from Chili Leftover and Their Reinforcement in Cariflex-IR Rubber Latex. 46 1090 Carbohydr. Polym. 2016, 136, 945–954 DOI: 10.1016/j.carbpol.2015.09.096. 47 1091 (133) Lee, S.-Y.; Chun, S.-J.; Kang, I.-A.; Park, J.-Y. Preparation of Cellulose Nanofibrils by High-Pressure 48 1092 Homogenizer and Cellulose-Based Composite Films. J. Ind. Eng. Chem. 2009, 15 (1), 50–55 DOI: 49 1093 10.1016/j.jiec.2008.07.008. 50 1094 (134) Letchford; Jackson; Wasserman, B.; Ye; Hamad, W.; Burt, H. The Use of Nanocrystalline Cellulose 51 1095 for the Binding and Controlled Release of Drugs. Int. J. Nanomedicine 2011, 321 DOI: 52 1096 10.2147/IJN.S16749. 53 54 1097 (135) Hajaligol, M.; Waymack, B.; Kellogg, D. Low Temperature Formation of Aromatic Hydrocarbon 2001 55 1098 from Pyrolysis of Cellulosic Materials. Fuel , 80 (12), 1799–1807 DOI: 10.1016/S0016- 56 1099 2361(01)00063-1. 57 58 59 60 ACS Paragon Plus Environment Page 69 of 70 ACS Sustainable Chemistry & Engineering
1 2 3 1100 (136) Jonoobi, M.; Oladi, R.; Davoudpour, Y.; Oksman, K.; Dufresne, A.; Hamzeh, Y.; Davoodi, R. 4 1101 Different Preparation Methods and Properties of Nanostructured Cellulose from Various Natural 5 1102 Resources and Residues: A Review. Cellulose 2015, 22 (2), 935–969 DOI: 10.1007/s10570-015- 6 7 1103 0551-0. 8 1104 (137) Qiu, X.; Hu, S. “Smart” Materials Based on Cellulose: A Review of the Preparations, Properties, 9 1105 and Applications. Materials 2013, 6 (3), 738–781 DOI: 10.3390/ma6030738. 10 1106 (138) Kim, J.-H.; Shim, B. S.; Kim, H. S.; Lee, Y.-J.; Min, S.-K.; Jang, D.; Abas, Z.; Kim, J. Review of 11 1107 Nanocellulose for Sustainable Future Materials. Int. J. Precis. Eng. Manuf.-Green Technol. 2015, 12 1108 2 (2), 197–213 DOI: 10.1007/s40684-015-0024-9. 13 1109 (139) Nagalakshmaiah, M.; El Kissi, N.; Dufresne, A. Ionic Compatibilization of Cellulose Nanocrystals 14 1110 with Quaternary Ammonium Salt and Their Melt Extrusion with Polypropylene. ACS Appl. Mater. 15 1111 Interfaces 2016, 8 (13), 8755–8764 DOI: 10.1021/acsami.6b01650. 16 17 1112 (140) VTT to Reduce Food Loss with Stand-up Pouches. 18 1113 (141) Incredible Uses of Nanocellulose. 19 1114 (142) Jiang, F.; Hsieh, Y.-L. Amphiphilic Superabsorbent Cellulose Nanofibril Aerogels. J Mater Chem A 20 1115 2014, 2 (18), 6337–6342 DOI: 10.1039/C4TA00743C. 21 1116 (143) Lin, N.; Bruzzese, C.; Dufresne, A. TEMPO-Oxidized Nanocellulose Participating as Crosslinking 22 1117 Aid for Alginate-Based Sponges. ACS Appl. Mater. Interfaces 2012, 4 (9), 4948–4959 DOI: 23 1118 10.1021/am301325r. 24 1119 (144) Huang, J.; Zhu, H.; Chen, Y.; Preston, C.; Rohrbach, K.; Cumings, J.; Hu, L. Highly Transparent and 25 2013 26 1120 Flexible Nanopaper Transistors. ACS Nano , 7 (3), 2106–2113 DOI: 10.1021/nn304407r. 27 1121 (145) Markstedt, K.; Mantas, A.; Tournier, I.; Martínez Ávila, H.; Hägg, D.; Gatenholm, P. 3D 28 1122 Bioprinting Human Chondrocytes with Nanocellulose–Alginate Bioink for Cartilage Tissue 29 1123 Engineering Applications. Biomacromolecules 2015, 16 (5), 1489–1496 DOI: 30 1124 10.1021/acs.biomac.5b00188. 31 1125 (146) Iwatake, A.; Nogi, M.; Yano, H. Cellulose Nanofiber-Reinforced Polylactic Acid. Compos. Sci. 32 1126 Technol. 2008, 68 (9), 2103–2106 DOI: 10.1016/j.compscitech.2008.03.006. 33 1127 (147) Favier, V.; Canova, G. R.; Cavaillé, J. Y.; Chanzy, H.; Dufresne, A.; Gauthier, C. Nanocomposite 34 1995 35 1128 Materials from Latex and Cellulose Whiskers. Polym. Adv. Technol. , 6 (5), 351–355. 36 1129 (148) Johansson, C.; Julien, B.; Mondragon, I. Renewable Fibers and Bio-Based Materials for Packaging 37 1130 Applications - A Review of Recent Developments. 2012. 38 1131 (149) Lavoine, N.; Desloges, I.; Manship, B.; Bras, J. Antibacterial Paperboard Packaging Using 39 1132 Microfibrillated Cellulose. J. Food Sci. Technol. 2015, 52 (9), 5590–5600 DOI: 10.1007/s13197- 40 1133 014-1675-1. 41 1134 (150) Saini, S.; Sillard, C.; Naceur Belgacem, M.; Bras, J. Nisin Anchored Cellulose Nanofibers for Long 42 1135 Term Antimicrobial Active Food Packaging. RSC Adv 2016, 6 (15), 12422–12430 DOI: 43 1136 10.1039/C5RA22748H. 44 45 1137 (151) VTT; Technical Research Centre of Finland, Espoo, Finland,. VTT, Innovation and 46 1138 Competitiveness from Nanocellulose. 2011. 47 1139 (152) Markham, D. Cellucomp, Cellulose Nano-Fiber from Carrots Is Twice as Strong as Carbon Fiber. 48 1140 (153) Hu, L.; Zheng, G.; Yao, J.; Liu, N.; Weil, B.; Eskilsson, M.; Karabulut, E.; Ruan, Z.; Fan, S.; Bloking, J. 49 1141 T.; others. Transparent and Conductive Paper from Nanocellulose Fibers. Energy Environ. Sci. 50 1142 2013, 6 (2), 513–518. 51 1143 (154) Lin, N.; Gèze, A.; Wouessidjewe, D.; Huang, J.; Dufresne, A. Biocompatible Double-Membrane 52 1144 Hydrogels from Cationic Cellulose Nanocrystals and Anionic Alginate as Complexing Drugs 53 2016 54 1145 Codelivery. ACS Appl. Mater. Interfaces , 8 (11), 6880–6889 DOI: 10.1021/acsami.6b00555. 55 56 57 58 59 60 ACS Paragon Plus Environment ACS Sustainable Chemistry & Engineering Page 70 of 70
1 2 3 1146 (155) Rebouillat, S.; Pla, F. State of the Art Manufacturing and Engineering of Nanocellulose: A Review 4 1147 of Available Data and Industrial Applications. J. Biomater. Nanobiotechnology 2013, 04 (02), 5 1148 165–188 DOI: 10.4236/jbnb.2013.42022. 6 7 1149 (156) paperage.com. World’s First Pilot Plant for Production of Nanocellulose Inaugurated. 2011. 8 1150 (157) TAPPI NANO, I. 6/TG 1 – C. N. Summary of International Activities on Cellulosic Nanomaterials. 9 1151 July 2015. 10 1152 11 12 13 1153 14 15 16 1154 17 18 19 1155 20 21 22 1156 23 24 25 1157 26 27 28 1158 29 30 31 1159 For Table of contents use only 32 33 34 1160 Role of agricultural and industrial waste in the field of nanocellulose and their multifunctional 35 1161 applications for sustainable development. 36 37 1162 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 ACS Paragon Plus Environment 本文献由“学霸图书馆-文献云下载”收集自网络，仅供学习交流使用。
学霸图书馆（www.xuebalib.com）是一个“整合众多图书馆数据库资源，
提供一站式文献检索和下载服务”的24 小时在线不限IP 图书馆。 图书馆致力于便利、促进学习与科研，提供最强文献下载服务。
图书馆导航：
图书馆首页 文献云下载 图书馆入口 外文数据库大全 疑难文献辅助工具