1) Nanocellulose

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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
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Page 1 of 70 ACS Sustainable Chemistry & Engineering
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3 1 IMPORTANCE OF AGRICULTURAL AND INDUSTRIAL WASTE IN THE FIELD OF
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6 2 NANOCELLULOSE AND RECENT INDUSTRIAL DEVELOPMENTS OF WOOD
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8 3 BASED NANOCELLULOSE: A REVIEW
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4 Rajinipriya Malladi, Malladi Nagalakshmaiah*, Mathieu Robert and Saïd Elkoun*
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13 5 Center for Innovation in Technological Eco-design (CITE), University of Sherbrooke, Quebec,
14 6 Canada.
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16 7 Abstract:
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19 8 The nano sized cellulose materials is topical in the sphere of sustainable materials lately. The two
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9 key groups of nanocellulose (NC) are 1) Nanofibrillated cellulose (NFC) and 2) Cellulose
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24 10 nanocrystals (CNC). They are often considered as a second-generation renewable resource,
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26 11 which also serves as a better replacement for the petroleum-based products. The major attention
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28 12 on these materials are increasing because of their low density, high mechanical, renewable and
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31 13 biodegradable properties. There are many literatures on the isolation of NFC and CNC from
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33 14 different sources like hard/soft wood and agriculture biomass. However, this is a comprehensive
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35 15 review dedicated to the extraction and properties of NFC and CNC only from the agriculture and
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16 industrial waste using mechanical, chemical and enzymatic methods. This article explores in
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40 17 detail about the importance of agriculture waste and the pre-treatments, methods involved in the
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42 18 production of nanocellulose, the properties of NC prepared from crop and industrial wastes. The
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19 potential applications of nanocellulose from different sources are discussed. The current
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47 20 extensive industrial activities in the production of nanocellulose had been presented. This review
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49 21 will likely draw attention of researchers towards crop and industrial wastes as a new source in
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51 22 the realm of nanocellulose.
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ACS Sustainable Chemistry & Engineering Page 2 of 70
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3 23 Keywords: Nanocellulose (NC), Nanofibrillated cellulose (NFC), Cellulose nanocrystals (CNC),
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6 24 Agriculture biomass and Industrial developments.
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9 25 INTRODUCTION:
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12 26 The production of cellulosic material increases tremendously to fulfil the need for renewable and
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27 eco-friendly sustainable materials.1 Cellulose is often considered as one of the most important
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17 28 natural resource. With the advent of nanoscience, the researchers and industries focus in the
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19 29 production of NC in huge quantities and it is evident from increasing number of publications and
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30 patents in this field.2The trailing purpose behind the growth of research in NC lies in their
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24 31 promising properties such as low density and high mechanical strength.3 Cellulose can be found
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26 32 in different sources like wood, natural fibers (agriculture biomass), marine animal (tunicate),
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28 33 algae and fungi.4 The composition of cellulose is highly dependent on the source.5 This review
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31 34 deals with the crop waste as a core source for the extraction of NC.
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34 35 With the ever-increasing demand for renewable resource, the crop waste is meant to be an
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36 36 appropriate material. The recovery of waste makes it possible to protect the environment and to
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38 37 benefit from low cost reinforcements. Agriculture waste biomass is significant resource for the
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38 reason it is environmental friendly, low cost, readily available, renewable and exhibit somehow
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43 39 acceptable mechanical properties.6 The crop waste constitutes abundant natural fibers.7 The
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45 40 agriculture waste fibers can be obtained from cotton stalk, pineapple leaf, rice straw, flax, hemp,
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47 41 soy pods, rice husk, garlic straw, potato peel, grape skin etc. Agri biomass can be used in
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50 42 multitude applications like paper, textile industry, composites, building, furniture and medical
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52 43 fields.
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3 44 The NC market is currently emphasized because of the augmented focus of the governments,
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6 45 industries, funding agencies and Universities. The bio-based economy is rapidly increasing
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8 46 resulting in the higher investments. The NC production includes high value added applications
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10 47 like composites, paper industry, packaging, paints, oil &gas, personal care, medical care etc.8
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48 The NC is first commercialised by celluforce Inc. in Quebec; a joint-venture between FP
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15 49 innovations and Domtar.9 The NC industries are prominent in the areas of Asia Pacific, North
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17 50 America, Europe, Latin America and Middle East and Africa including leading names like
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51 Paperlogic, University of Maine, Borregaard Norway, American Process, Nippon Paper Japan,
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22 52 Innventia Sweden, CTP/FCBA France, Oji Paper, Japan.
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25 53 This article aims to deliver the consolidate details on structure and multiple sources of cellulose,
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27 54 NC, their extraction from agri-based sources and the current industrial developments on NC
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29 55 production and applications. There are numerous literature which deal with various aspects of
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32 56 NC like source, production of nanofibrillated cellulose,10,11 production of nanocrystals,12–14
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34 57 extraction methods,11 pre-treatments,15 properties16 and applications.17 However, there is only
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36 58 limited review on the agriculture biomass for the extraction of NC.6,18 Since the urge of
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59 converting agriculture waste into wealth is increasing for the reasons of waste management,
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41 60 improve ecofriendly resource and creating new source of economy, this review paper
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43 61 concentrates on the inside story of the agriculture biomass, extraction of NC from crop waste,
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62 different treatments, pre-treatments involved. It also deals with the properties of isolated NC. To
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48 63 conclude, the applications and industrial evolution in the production of NC are also addressed.
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51 64 SOURCE OF CELLULOSE:
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54 65 Cellulose is the amplest resource of natural fibers. Annually, the extraction of cellulose is
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56 66 assessed to be over 7.5 x 1010 tons.12 Cellulose is extracted from various sources including wood
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3 67 (Hard or soft wood), seed (cotton), bast (Flax, hemp), cane (bamboo, bagasse), leaf (Sisal), straw
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6 68 (rice, wheat), fruit (Coir), tunicate, algae, fungi, bacteria and minerals.19 Figure 1 shows the
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8 69 hierarchical representation of the chief sources from which cellulose can be extracted.
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32 78 Figure 1. Hierarchical representation various sources of cellulose.
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35 79 The source is placed in the order of conventional source like wood and cotton, which is
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37 80 considered as the primary origin. Wood can be classified as soft/hard wood based on their
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81 structural aspect.20 Then comes the agriculture waste which are the unprocessed wastes that are
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42 82 coming directly from the field residues like rice straw, banana rachis, corncob etc. The crop
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44 83 waste is becoming the second highest source of cellulose. The industrial waste is the processed
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84 waste produced by the industries like sugarcane bagasse, tomato and garlic peels etc. which is
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49 85 another source of cellulose emerging lately. Cellulose can be obtained from some other small
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51 86 class of sources like marine animal (tunicate), algae, fungi and bacteria. The interest of this
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53 87 review lies on the second and third grid of the pyramid representation i.e. Crop and industrial
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56 88 waste for the fact that this source needs to be explored more. The basic constitution of the
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3 89 foretold fibers is cellulose, lignin and hemicelluloses. However, the chemical composition differs
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6 90 for each some of which are tabulated in table 1 on dry basis. Besides cellulose lignin and
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8 91 hemicelluloses, some sources contain pectin, waxes and other water-soluble components.
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15 Table 1. Chemical composition of different sources on dry basis.
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18 Source Cellulose Hemicellulose Lignin Reference
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(wt.%) (wt.%) (wt.%)
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24 Pine (softwood) 44.0 27.0 28.0
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28 Yellow birch 47.0 31.0 21.0
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30 (hardwood)
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34 Jute 73.2 13.6 13.4
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37 Wheat straw 48.8 35.4 17.1
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41 Rice husk 45.0 19.0 19.5
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44 22
45 Bagasse 55.2 16.8 25.3
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48 Banana 63–64 10 5
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51 23
52 Flax 71 18.6-20.6 2.2
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4 Hemp 70-74 17.9-22.4 3.7-5.7
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7 Mulberry barks 37.38 ± 2.31 25.32 ± 2.45 9.99 ± 0.82 24
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11 Garlic straw 41 18 6.3
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15 Carrot residue 81 9 2.5
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18 Ground nut shells 38.31 27.62 21.10 27
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22 Onion skin 41.1 ± 1.1 16.2 ± 0.6 38.9 ± 1.3
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25 92
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28 93 CELLULOSE:
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31 94 Cellulose is the natural polysaccharide first isolated by Anselme Payen in 1838 from wood when
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95 treated with nitric acid.12 They exist as microfibrils in the plant cell wall of multiple sources. The
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36 96 diameter of the fibrils varies from 3-35 nm depending on the source.29 Cellulose contains linear
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38 97 polymer chain comprised of glucose monomer named β-1,4-linked anhydro-D-glucose units as
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98 shown in figure 2. The degree of polymerization of cellulose is up to 20000 units. For wood and
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43 99 cotton it is approximately 10000 and 15000 glucose units respectively.30
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45 100 Anhydroglucose is the monomer and cellobiase is the dimer of cellulose. Each glucopyranose
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47 101 unit contains 3 highly reactive hydroxyl groups which are responsible for the hydrophilicity,
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50 102 chirality, biodegradability etc. of cellulose. The individual cellulose chain contains reducing end
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52 103 because of the hemiacetal unit with both aliphatic and carbonyl group and the non-reducing end
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3 104 with closed end group.31 The higher mechanical properties of each microfibrils result from the
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6 105 strong hydrogen bonds.
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25 Figure 2. a) 3D structure of cellulose.b) structure formula of cellulose. Adopted from Cave
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and Walker (1994).31
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30 106 The β-1,4-glycosidic bonds builds an ordered crystalline structure by Vander Waals forces and
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32 107 inter & intra molecular hydrogen bonding.32 In these regions, the cellulose chains are strongly
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108 arranged into crystallites. The hydrogen bond existing between cellulose chains make it highly
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37 109 stable but poorly soluble in water and other solvents. These hydrogen bonding network and the
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39 110 molecular arrangement results in polymorphs or allomorphs of cellulose. There are six
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41 111 interconvertible polymorphs of cellulose had been identified id Est cellulose I, II,IIII,IIIII,IVI and
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44 112 IV II.33 In 1984 Atalla and Vander Hart proved that the native cellulose I can be subdivided into
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46 113 Iα and Iβ.34 Cellulose II can be obtained from the chemical regeneration35 or by mercerization.36
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48 114 Cellulose III is formed when cellulose I or II is treated with ammonia or various amines37 and the
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115 polymorphs IVI and IVII are produced by heating cellulose IIII or IIIII respectively at 260ºC in
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53 116 glycerol.38
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3 117 The amorphous region results from the breakage and disordered hydrogen bonds.39 Figure 3
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6 118 shows the crystalline and amorphous regions of cellulose. The hydrogen bonding and orientation
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8 119 of cellulose differs extensively for the different source.
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Figure 3. Crystalline and amorphous regions of cellulose.
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27 120
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30 121 HEMICELLULOSE:
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33 122 Plant cell wall is mainly made up of cellulose, hemicellulose and lignin as stated before.
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35 123 Hemicellulose is the second major component accounting 15-30% of the cell wall.40 They are
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37 124 entrenched around the microfibrils bundles as shown in figure 4.
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Figure 4. Cellulose bundles embedded by hemicelluloses and lignin.
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3 125 Hemicellulose can be divided into four different classes based on their structure as 1) Xylans, 2)
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6 126 Mannans, 3) β-glucans and 4) Xyloglucans. Hemicelluloses are branched polysaccharides
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8 127 containing β-1→4-linked backbones of glucose, mannose or xylose in equatorial configuration at
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10 128 C1 and C4 and the structure varies with the side chain type and the distribution of these
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12 41
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129 backbones. The figure 5 shows the structure of some backbones of hemicellulose like β 1,4-
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15 130 glucan (figure 5a) β 1,4-xylan (figure 5b) and β 1,4-Mannan (figure 5b).42
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33 Figure 5. Structural backbone of hemicellulose a) β 1,4-glucan b) β 1,4-xylan
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36 c) β 1,4-Mannan. Adopted from 42
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38 131
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41 132 Few examples of xylans are glucoronoxylans and arabinoxylans and they can be found in straw,
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43 133 stalks, husk etc. Mannans can be classified as gluco and galactomannans which can be extracted
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134 form gaur, locust bean etc. Xyloglucans are used as thickening and gelling agent in foods and
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48 135 can be isolated from tamarind seeds.43 As reported in the literature, it is known that
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50 136 hemicelluloses play a key role in facilitating the fibrillation process.44,45 The reason is most
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52 137 likely because of the hydrogen bonding and negative charges on hemicelluloses. As realised
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55 138 from figure 4, hemicellulose surrounds cellulose microfibrils through numerous hydrogen
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3 139 bonding which in turn seals the gap between the microfibrils and hinders the fibrils from
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6 140 aggregation. Also, hemicelluloses contain glucuronic acid with carboxyl groups which enables
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8 141 the delamination of fibers by means of electrostatic repulsion forces. 45
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11 142 LIGNIN:
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14 143 Lignin is a heterogeneous and irregular cross-linked polymer of phenyl propane. It is amorphous
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16 144 and optically inactive material with three different monomers namely Coumaryl alcohol,
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145 Coniferyl alcohol and Sinapyl alcohol whose structure is shown in figure 6.46 Lignin is derived
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21 146 by the enzyme mediated polymerization. The molecular weight of isolated lignin is typically in
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23 147 the range of 1000-20,000 g/mol, though the degree of polymerisation in nature is difficult to
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25 148 arrive on the account that lignin is highly fragmented during isolation and it also contains many
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28 149 repeating substructures in a seemingly haphazard manner.47
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Figure 6. Structural units of lignin. Reprinted with permission.46 Copyright 2014 American
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45 Chemical Society.
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49 151 Lignin is used in multiple applications as emulsifiers, dyes, synthetic flooring, binding,
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51 152 thermosets, paints etc. The sulfur-free and water soluble lignin is used for automotive brakes,
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53 153 wood panel products, bio dispersants, polyurethane foams, and epoxy resins for printed circuit
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56 154 boards.48
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6 156 Nanocellulose:
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9 157 The plant cell wall can be classified into two namely primary and secondary. The primary cell
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158 wall is the external thin layer (less than 1 µm) and the secondary cell wall chiefly contains
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14 159 cellulose microfibrils.49 The Hierarchical configuration of wood to cellulose nanocrystals are
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16 160 shown in figure 7. Generally, either length or diameter of the cellulose particles are in the nano
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161 size (1-100nm) are called as NC. The plant cell wall consisting bundles of the cellulose fibrils
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21 162 and their diameter is in few microns. Each cellulose bundle is consisting millions of micro
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23 163 fibrils, these micro fibrils are composed with elementary fibrils or nano fibrils. The diameter of
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25 164 the nanofibrils is about 5nm, whereas in the case of the micro fibrils the diameter will vary from
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28 165 10-50nm. Every nano fibers are composed of flexible amorphous and strong crystalline parts.
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42 Figure 7. Hierarchical structure of cellulose and its derivatives in nanoscale.
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167 Several cellulosic derivatives are isolated from these microfibrils and depending on their
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49 168 isolation methods, source, dimensions they are called , NC, whiskers, nanofibrils.1 Depending on
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51 169 their method of preparation, NC is classified into 1) cellulose nanocrystals (CNC) and 2) nano
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170 fibrillated cellulose (NFC). The other type of NC called bacterial cellulose (BC) and electro spun
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56 171 cellulose nanofibers (ECNF) can also be isolated. Nevertheless, CNC and NFC are considered as
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3 172 the more common and they are produced by top-down process i.e. by disintegration of cellulose
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6 173 fibers to nanoscale particles whereas BC and ECNF are produced by bottom-up process in which
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8 174 nanofibers are formed from low molecular weight sugars by bacteria or from dissolved cellulose
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10 175 by electrospinning respectively.11 The morphological images of four different NC from corn
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176 husk (figure 8a), tunicate (figure 8b), bacterial cellulose (figure 8c) and electro spun cellulose
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15 177 nanofibers (figure 8d) is shown in figure 8. 50–53
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44 Figure 8. Micrographs of NC a) NFC from corn husk. Reprinted with permission.50 Copyright
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46 2015 Elsevier. b) CNC from tunicate. Reprinted with permission.51 Copyright 2014 American
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49 Chemical Society c) Bacterial cellulose. Reprinted with permission.52 Copyright 2006 American
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51 Chemical Society and, d) electro spun cellulose nanofibers. Reprinted with permission.53
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53 Copyright Intech, DOI: 10.5772/8153.
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56 178
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1
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3 179 NANOFIBRILLATED CELLULOSE:
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6 180 The cellulose fibers are fibrillated usually by mechanical breakdown to achieve clusters of
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9 181 cellulose microfibrils due to shear forces called nanofibrillated cellulose. The nomenclature can
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11 182 be different for these nanofibrils as a) nano fibrillated cellulose (NFC) b) micro fibrillated
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13 183 cellulose (MFC) c) cellulose nanofibrils (CNF) d) cellulose filaments (CF). The diameter of NFC
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184 is in nanoscale i.e. less than 100 nm and the length can be of few micrometers. The structural
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18 185 morphology of NFC from corn husk is shown in figure 8a.
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21 186 The NFC was first obtained by Turbak et al., 1983 and Herrick et al., 1983 by means of a Gaulin
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23 187 laboratory homogenizer.54, 55
The specific surface area and the number of hydrogen bonds
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25 188 ensuing from the surface hydroxyl groups is increased during fibrillation or delamination. Owing
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28 189 to this, NFCs are inclined to form gels showing increased viscosity. The major impairment of
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30 190 NFCs are they tend to form gels once produced, their hydrophilicity restricts the dispersion with
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32 191 few hydrophobic polymers. Importantly, the extraction process consumes high-energy. All these
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192 difficulties can be overcome with some pre-treatments and surface modifications. Besides the
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37 193 drawbacks, NFCs are commercially produced and used in plenitude applications including
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39 194 composites, coatings, personal care, constructions etc.8
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42 195 CELLULOSE NANOCRYSTALS:
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45 196 Cellulose nanocrystals, also termed nano whiskers, are spherical “rod” or “needle” like highly
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47 197 crystalline structures with diameter of 2-25 nm and length from 100-750 nm depending on the
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50 198 source. The morphology of CNC from tunicate is shown in figure 8b. CNCs are first obtained by
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52 199 acid hydrolysis by Ranby in 1949.56 As discussed in the structure of cellulose, it contains both
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3 200 crystalline and amorphous regions. During the acid hydrolysis, the amorphous region is removed
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6 201 leaving behind the crystalline particles as displayed in figure 9.
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21 Figure 9. Isolation of CNC from cellulose by sulphuric acid hydrolysis. Reprinted with
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permission.57 Copyright 2017 Royal Society of Chemistry.
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27 203 The amorphous regions present in the cellulose chain is the first and easily accessible to the acid
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29 204 for the hydrolytic action due to kinetic force and steric hindrance however the crystalline
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31 205 regions are more unaffected by the hydrolysis. 13, 56
The size, morphology and degree of
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206 crystallinity will vary depends on the source. The acid hydrolysis can be achieved using
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36 207 hydrochloric acid (HCL) and sulphuric acid. However, HCL does not result in stable suspensions
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38 208 due to the absence of the surface charge. Whereas in the case of sulphuric acid hydrolysis, the
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209 surface of the cellulose attains the half ester sulfate groups resulting in high negative charge. 59 It
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43 210 was reported that the length and surface charge of CNC fibers depends on the hydrolysis period
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45 211 by Dong et al.60The length of CNC fibers decreased while increasing the hydrolysis time by
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47 212 increasing the surface charge.
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50 213 Another interesting aspect was studied by R.H. Marchessault et al. which showed the
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53 214 birefringent liquid crystalline phases. Revol et al. in 1992 proved that CNC formed chiral
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55 215 nematic phases. The authors stated that cellulose, in the form of fibrillar fragments was dispersed
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3 216 in water and above critical concentration, the self-organization of cellulose crystallites into chiral
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6 217 nematic liquid crystalline phase (parallel alignments of the anisotropic crystallites) was observed.
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8 218
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11 219 BACTERIAL CELLULOSE:
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14 220 Evident from figure 1, cellulose is not only found in plant cell walls but also can be obtained
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16 221 from bacteria and are named as bacterial cellulose (BC). The bacterial cellulose is also referred
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222 as microbial cellulose, bacterial NC or bio cellulose.1 BC can be synthesized from Acetobacter,
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21 223 Rhizobium, Agrobacterium, and Sarcina by aqueous culture media cultivation.63 The
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23 224 morphology of the bacterial cellulose is shown in the figure-8c.
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26 225 ELECTROSPUN CELLULOSE NANOFIBERS:
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29 226 In this method, cellulose is dissolved in a suitable solvent and a high voltage is applied through
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31 227 the solution so that the particles are charged and repulsive force is created. The network of the
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34 228 ECNF is shown in the figure 8d. At a critical voltage, the repulsive forces overcome the surface
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36 229 tension of the solution. When it is passed through air, the solvent evaporates resulting in fiber
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38 230 formation which are then collected on an electrically grounded plate.64 ECNF is used invarious
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231 applications.65
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232 IMPORTANCE OF AGRICULTURE BIOMASS:
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233 Agriculture sector is producing huge volume of wastes which is menace to the environment as
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49 234 they are either burnt in the fields causing air pollution or accumulated in the soil. The recovery of
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51 235 this waste makes it possible to protect the environment. But at the same time, it will also create
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53 236 new economy. Agriculture waste is the richest form of natural fiber and it is more promising and
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56 237 sustainable material. Towards the advancement of the materials, scientists and researchers need
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3 238 to elaborate new materials and new technology based on intelligent and eco-conscious materials.
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6 239 In other words, materials have greater impact on environment and thus choosing them reflects on
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8 240 the technologies they are used. On that account, materials can be an important part of solution to
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10 241 the problem that created by specific technology. Aforesaid solution could be developing a new
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242 material that works better based on eco-designed or bio based products.66 Hence, interest
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15 243 towards sustainable materials produced using crop waste is increasing among researchers.
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17 244 Compared to wood in which case cellulose is present in secondary cell wall, it is more facile to
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245 isolate cellulose from agriculture fibers wherein cellulose is found in primary cell wall and the
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22 246 fibrillation in the latter case is done with low energy consumption.67
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
32 250 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
55 260 understanding of the properties of vegetal waste fiber.
56
57
58
59
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20 Figure 10. Factors that affect the quality of the fiber at various stages of production. Adopted
21 with permission.69 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
46 270 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
1
2
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8
9
10
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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
49
273 Since the mechanical treatment involves high energy consumption pre-treatments like chemical/
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
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 72
Banana Sodium hydroxide, Biological Chemical and Cellulose
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 73
51 Peel of Bleaching Toluene, - Homogenization Cellulose
52
prickly pear ethanol microfibrils
53
54
fruits
55
56
57
58
59
1
2
3 24
Mulberry Sodium hydroxide - Acid hydrolysis Cellulose
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
79
48 Jute fibers - Ball milling Nanocellulose
49
50 Mercerisation
51
52 80
Rice husk Sodium hydroxide - Acid hydrolysis Cellulose
53
54 treatment, Bleaching nanocrystals
55
56
57
58
59
1
2
3 81
chardonnay Toluene, ethanol - Acid hydrolysis Cellulose
4
5
grape skins nanocrystals
6
7
8 Sugar cane Sodium hydroxide Ionic liquid Homogenization Nanocellulose 82
9
10 bagasse treatment
11
12 83
13 Sesame husk Sodium hydroxide, - Acid hydrolysis Cellulose
14
Bleaching nanocrystals
15
16
sodium chlorite
17
18 treatments
19
20
82
21 Sugar cane Sodium hydroxide Ionic liquid Homogenization Nanocellulose
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 86
Bleached Bleaching - Grinding Nanofibrillated
35
36
Eucalyptus cellulose
37
38 pulp
39
40
87
41 Rice straw Toluene, ethanol, Carboxylation Blending Cellulose
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
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 93
Orange waste Sodium hydroxide, - Sonification Nanocellulose
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
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 96
Agave Sodium hydroxide, - Acid hydrolysis Cellulose
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
49 sodium chlorite,
50
potassium hydroxide
51
52
treatments
53
54
55
56
57
58
59
1
2
3 99
Tomato peel Sodium hydroxide, - Acid hydrolysis Cellulose
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
1
2
3 279 Bleaching, sodium
4
5
chlorite,
6 280
7 potassium hydroxide
8
9 treatments
10
11
25
12 Garlic straw Sodium hydroxide - Acid hydrolysis Cellulose
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
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
9 283 cellulosic (hemicellulose, lignin) to get the pure cellulose fibers. Firstly, raw materials treated
10
11 284 with alkali67,105 (NaOH or KOH), organic solvents106, Soxhlet88 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
16
286 Secondly, delignification often called as bleaching is usually done by chemical process. The
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
25 290 purification process.70
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
38
295 acid hydrolysis of the amorphous parts of cellulose leaving behind the crystalline parts of
39
40 296 cellulose.33 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
47 299 also isolated by microbial hydrolysis.110One 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
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
13
308 effect on width was reported.113 These studies were carried out on the wood/cotton based NC.
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
38
318 purification of the cellulose fibers. NFC is extracted in different steps like homogenization,54
39
40 319 cryocrushing,115 grinding116 , micro fluidization 117
, and ultra-sonication.98Since the mechanical
41
42 320 treatment consumes high energy, chemical and enzymatic pre-treatments have been followed
43
44
321 prior. Chemical pre-treatment includes tempo-oxidation,118 quarterisation, refining etc. and in the
45
46
47 322 enzymatic pre-treatment, enzymes like endo and/or exoglucanase were used previously.119 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
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
9 328 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
16
331 the recalcitrance results from the extreme crystalline structure of cellulose surrounded with lignin
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
27 336 down the energy consumption 20times less, i.e. 1000 kWh/ton.121
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
38
340 and inter and intra molecular bonding between hemicelluloses and lignin leaving behind the pure
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
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
13
352 which leads to the increase in the surface area and decrease in the degree of crystallinity. In 2006
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
35
361 delamination of fibers and 3) Washing and yet again refining.119 Mayra Mariño et al. (2015) used
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
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
21 377 fibers by using only disk refiner.124 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
46 Figure 12. Diagram for working principle of a) homogenizer adopted from 125b) micro
47 fluidizer. Adopted with permission.126c) grinding adopted from www.masuko.com and d)
48 Cryocrushing from 127
49
50
51
52
379 In this method, the cellulose suspension is passed through a vessel between two valve seats and
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
1
2
3 382 The isolation of micro fibrillated cellulose using homogenization was first done by Turbak et al.
4
5
6 383 in 1985 using Gaulin homogenizer.54 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
13
386 invidualization of micro fibrils.67 In 2007, Wang and Sain used soybean pods as a raw material to
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
31 394 increased to 600 bars for the defibrillation process.128 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
36
396 homogenization.10 The other downside of this treatment is the excessive energy consumption for
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
1
2
3 405 clogging of fibers in homogenizer can be overcome in micro fluidization process because it has
4
5
6 406 no in-line moving parts, and it can easily be resolved by reverse flow through the chamber.130
7
8
9 407 GRINDING:
10
11
12
408 Another method to produce NFC is grinding process in which the sample slurry is passed
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
30 416 means of crystallinity and degree of polymerisation.86 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
35
418 using grinding process.26,91,95
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
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
9 429 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
16
432 from oranges (CPWO) using ultrasonic processor, Sonics at 750 Watt, 20 kHz and 4J. The
17
18 433 residue from enzymatic hydrolysis of CPWO was used as a raw material here.93
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
33 439 from banana fibers.74,77
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
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
12
451 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
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
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40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
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 73
Prickly pear fruits 2–5
15 467
16
17 468 Wheat straw 10–80 115
18
19 469 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
32 132
33 Chilli leftover 4-6 90-180
475
34
35 Garlic straw 6 480 25
36 476
37
27
38 Groundnut shells 5-18 111
477
39
40 24
Mulberry bark 25-30 400-500
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
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
13
488 fibrils were split into smaller fibrils with increased aspect ratio. When passed the suspension
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
22 492 mechanical strength.133
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
32 496 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
39
499 part of cellulose I was changed into cellulose II.72
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
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
24
506 Figure 14. TEM images of cellulose microfibrils after a) PA b) PA–HCl c) 5 wt. % KOH and d)
25
26 507 18 wt. % (KOH-18) treatments. Reprinted with permission. 72 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
36 511 were inspected by Rosa et al., 2010.75
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
49
516 and disordered amorphous regions. It is believed that during extraction the disordered amorphous
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
1
2
3
4 NFC
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
12 106
13 Purified cellulose fibers 63.8
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
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
40 520
41
42
43 521
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
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
18 135
528 degrade below 400ºC and 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
28 532 lignin.136 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
35
535 stability.
36
37
38
536 APPLICATIONS:
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
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
33 nanocomposite film. Reprinted with permission.139 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
40 chloroform from water. Reprinted with permission.142 Copyright 2014 Royal Chemical Society.
41
42 e) Alginate-oxidized nanocellulose sponge. Reprinted with permission.143 Copyright 2012
43
44 American chemical Society. f) Fabricated transparent and flexible Nano paper transistor.
45
46
47
Reprinted with permission.144 Copyright 2013 American Chemical Society. g) 3D printed small
48
49 grids and human ear from NFC and alginate. Reprinted with permission.145 Copyright 2015
50
51 American Chemical Society.
52
53
54 542
55
56
57
58
59
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
13
547 further for better understanding. Recently hydrophobic aerogels produced from rice straw
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
35
556 preparation compared to the non-biodegradable nano fillers like carbon nanotubes, nano clays
36
37 557 etc.139 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
1
2
3 566 cellulose whiskers. The authors found that the mechanical properties were increased
4
5
6 567 significantly.147
7
8
9 568
10
11
12 569 Packaging:
13
14
15
570 In the modern world, usage of packaged food is increased. Most of the food is packed in the
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
33 578 materials also reported.149Elsewhere 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
38 580 bacteria.150NC 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
51
585 which helps to hold the water hence acting as a highly viscous material. It is used in improving
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
1
2
3 588 polyurethane varnishes and paints as additives, which increased the durability of coatings of
4
5
6 589 paints.151 Some other company called Cellu Comp from United Kingdom claimed, the NC
7
8 590 extracted from carrot improved the hardness, flexibility and crack resistance of the paints.152
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
30 599 applications.153
31
32 600 Biomedicine:
33
34
35 601 NC has antiquity of application in biomedicine as excipients, in drug delivery, for
36
37
38
602 enzyme/protein immobilization, implants, skin and bone tissue repair and others. The
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
56 610 release from first layer and second layer respectively.154 Nanomaterials have wide applications as
57
58
59
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
8 613 3D bioprinting of living soft tissue with cells as shown in figure 15g.145
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
38
625 breakthroughs. In addition, they can be extracted from easily available sources and are bearable
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
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
38 635 the product based on the TAPPI NANO outlook 2015.9 Industries collaborate with other
39
40 636 universities or institutes to develop new Nano cellulosic materials. The detailed study of
41
42
43
637 industrial turnover and industrial methods is discussed in the following section.
44
45
638
46
47
48
639
49
50
51
640
52
53
54
641
55
56
57
58
59
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
26 OHI paper- JAPAN 100 NFC
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
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
14
649 biodegradable and renewable materials for the betterment of the society. This might be the main
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
30 656 ISO/TC 6/TG 1 study.157
31
32
33 657 Table 6. Industries producing nanocellulose, product type, their production capacity and method
34
35 658 of production across the world. Reproduced with permission.157 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
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
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
52 666
53
54
667
55
56
57
58
59
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
44 USDA‐Forest CNFs 1 kg/week Wood pulp
45 Service‐Forest
Products Laboratory Aqueous TEMPO oxidation and
46 suspensions mechanical treatment
47 (FPL)
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
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
11 NORWAY “Exilva MFC” planned for mid- Mechanical treatment
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
48 670
49
50
51
671
52
53
54
55
56
57
58
59
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
12 exclusive rights to
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
19 running vegetables
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
33 calcium carbonate with No fiber pretreatment;
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
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
30 target
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
1
2
3
CHINA Tianjin Haojia CNFs -- Dissolving cotton pulp
4
Cellulose Co., Bleached sulfate pulp
5 Modified CNFs
Ltd. (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
15 Indian Council CNFs 10 kg/day Cotton linters
of Agricultural
16 INDIA and CNCs Pilot plant MCC from short staple
Research -
17 cotton fibers
Central Institute
18
for Research on
19 Cotton
Sugarcane bagasse
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
35 filtration/food/industrial 10-35% Mechanical treatment
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
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
ton/day) Carboxymethylation
20
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
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
13
679 industrial wastes should be considered for the preparation of NC industrially. The properties of
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
35
688 more by the researchers and industries. The fore mentioned sources are not only easily available,
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
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
44
712 *Email: Said.Elkoun@USherbrooke.ca
45
46 713 *Email: Nagalakshmaiah.Malladi@USherbrooke.ca
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
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
13
722 from agriculture and industrial wastes and its applications.
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
36
732 Pr. Saïd Elkoun is Professor and head of the Mechanical Engineering
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
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
14
745 ACKNOWLEDGEMENTS:
15
16
17
746 The authors want to thank National Science and Engineering Research Council” (NSERC) of
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
42
757 (2) Charreau, H.; L Foresti, M.; Vázquez, A. Nanocellulose Patents Trends: A Comprehensive Review
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
53 767 Towards Sustainability and Advanced Utilization: A Review. Asian J. Plant Sci. 2016, 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
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
16 781 (13) Mariano, M.; El Kissi, N.; Dufresne, A. Cellulose Nanocrystals and Related Nanocomposites:
17 782 Review of Some Properties and Challenges. J. Polym. Sci. Part B Polym. Phys. 2014, 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
25
789 DOI: 10.1002/pen.21328.
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:
36 799 2000–2010. Prog. Polym. Sci. 2012, 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
44
806 Curaua Lignins Oxidized by Chlorine Dioxide and Reacted with Furfuryl Alcohol: Characterization
45 807 and Stability. Polym. Degrad. Stab. 2004, 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
54 815 Prod. 2016, 87, 287–296 DOI: 10.1016/j.indcrop.2016.04.060.
55
56
57
58
59
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.
8 820 Carbohydr. Polym. 2017, 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
16 827 Nanotechnol. Sci. Appl. 2015, 45 DOI: 10.2147/NSA.S64386.
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
25
835 (34) Gaffey, M. J. Spectral Reflectance Characteristics of the Meteorite Classes. J. Geophys. Res.
26 836 1976, 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
44
852 (43) Kozioł, A.; Cybulska, J.; Pieczywek, P. M.; Zdunek, A. Evaluation of Structure and Assembly of
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
55 862 Hydrosilanes. ACS Sustain. Chem. Eng. 2014, 2 (8), 1983–1991 DOI: 10.1021/sc500302j.
56
57
58
59
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
7 866 Nonrenewable Materials. J. Polym. Environ. 2002, 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
16 874 Mechanical, and Oxidative Methods. ACS Appl. Mater. Interfaces 2014, 6 (9), 6127–6138 DOI:
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
25
882 Properties, Uses, and Commercial Potential. 1983.
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
36 892 Nanowhiskers for Tissue Engineering. Nanomed. 2013, 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
44
899 (63) El-Saied, H.; Basta, A. H.; Gobran, R. H. Research Progress in Friendly Environmental Technology
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
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
6
913 4628(19970509)64:6<1185::AID-APP19>3.0.CO;2-V.
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.
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
17 923 on Synthetic Polymers. Compos. Sci. Technol. 2007, 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
25 930 (74) Cherian, B. M.; Leão, A. L.; de Souza, S. F.; Thomas, S.; Pothan, L. A.; Kottaisamy, M. Isolation of
26 931 Nanocellulose from Pineapple Leaf Fibres by Steam Explosion. Carbohydr. Polym. 2010, 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
34
938 Cellulose Whiskers from Cassava Bagasse and Their Applications as Reinforcing Agent in Natural
35 939 Rubber. Ind. Crops Prod. 2010, 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.
45 948 World J. Eng. 2012, 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
53
955 (82) Li, J.; Wei, X.; Wang, Q.; Chen, J.; Chang, G.; Kong, L.; Su, J.; Liu, Y. Homogeneous Isolation of
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
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
8 962 Nanocrystals Derived from Potato Peel Waste. Carbohydr. Polym. 2012, 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
16 969 Cellulose 2012, 19 (5), 1631–1643 DOI: 10.1007/s10570-012-9745-x.
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
25
977 Microcrystalline Cellulose from Oil Palm Biomass Residue. Carbohydr. Polym. 2013, 93 (2), 628–
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
35 986 Nanocrystals. J. Environ. Manage. 2013, 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
44
994 Grinding Process. Nord Pulp Pap Res J 2014, 29 (1), 167–175.
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
55 1004 Nanofibers. Carbohydr. Polym. 2015, 122, 60–68 DOI: 10.1016/j.carbpol.2014.12.064.
56
57
58
59
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
16 1016 Miscanthus Giganteus: A Commercially Viable Sustainable Source of Cellulose Nanocrystals.
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
25
1024 Nanofibers from Four Plant Cellulose Fibers Using a Chemical-Ultrasonic Process. Cellulose 2011,
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
44
1041 (113) Elazzouzi-Hafraoui, S.; Nishiyama, Y.; Putaux, J.-L.; Heux, L.; Dubreuil, F.; Rochas, C. The Shape
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.
55 1051 Mater. 2004, 6 (9), 754–761 DOI: 10.1002/adem.200400097.
56
57
58
59
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
16 1063 (122) Sun, Y.; Cheng, J. Hydrolysis of Lignocellulosic Materials for Ethanol Production: A Review.
17 1064 Bioresour. Technol. 2002, 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
25
1071 (125) Homogenization (Chemistry).
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
36 1081 EPFBF Nanopaper. Bioresour. Technol. 2012, 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
44
1088 (132) Nagalakshmaiah, M.; kissi, N. E.; Mortha, G.; Dufresne, A. Structural Investigation of Cellulose
45 1089 Nanocrystals Extracted from Chili Leftover and Their Reinforcement in Cariflex-IR Rubber Latex.
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
55 1098 from Pyrolysis of Cellulosic Materials. Fuel 2001, 80 (12), 1799–1807 DOI: 10.1016/S0016-
56 1099 2361(01)00063-1.
57
58
59
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
16 1111 Interfaces 2016, 8 (13), 8755–8764 DOI: 10.1021/acsami.6b01650.
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
25
1119 (144) Huang, J.; Zhu, H.; Chen, Y.; Preston, C.; Rohrbach, K.; Cumings, J.; Hu, L. Highly Transparent and
26 1120 Flexible Nanopaper Transistors. ACS Nano 2013, 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
35 1128 Materials from Latex and Cellulose Whiskers. Polym. Adv. Technol. 1995, 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
44
1136 10.1039/C5RA22748H.
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
54 1145 Codelivery. ACS Appl. Mater. Interfaces 2016, 8 (11), 6880–6889 DOI: 10.1021/acsami.6b00555.
55
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57
58
59
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
6
1148 165–188 DOI: 10.4236/jbnb.2013.42022.
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
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35 1161 applications for sustainable development.
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