Importance of Agricultural and Industrial Waste in ... - ACS Publications

Feb 3, 2018 - Besides cellulose, lignin, and hemicelluloses, some sources contain pectin, waxes, and other water-soluble components. Cellulose. Cellul...
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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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IMPORTANCE OF AGRICULTURAL AND INDUSTRIAL WASTE IN THE FIELD OF

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NANOCELLULOSE AND RECENT INDUSTRIAL DEVELOPMENTS OF WOOD

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BASED NANOCELLULOSE: A REVIEW

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Rajinipriya Malladi, Malladi Nagalakshmaiah*, Mathieu Robert and Saïd Elkoun*

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Center for Innovation in Technological Eco-design (CITE), University of Sherbrooke, Quebec, Canada.

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Abstract:

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The nano sized cellulose materials is topical in the sphere of sustainable materials lately. The two

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key groups of nanocellulose (NC) are 1) Nanofibrillated cellulose (NFC) and 2) Cellulose

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nanocrystals (CNC). They are often considered as a second-generation renewable resource,

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which also serves as a better replacement for the petroleum-based products. The major attention

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on these materials are increasing because of their low density, high mechanical, renewable and

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biodegradable properties. There are many literatures on the isolation of NFC and CNC from

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different sources like hard/soft wood and agriculture biomass. However, this is a comprehensive

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review dedicated to the extraction and properties of NFC and CNC only from the agriculture and

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industrial waste using mechanical, chemical and enzymatic methods. This article explores in

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detail about the importance of agriculture waste and the pre-treatments, methods involved in the

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production of nanocellulose, the properties of NC prepared from crop and industrial wastes. The

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potential applications of nanocellulose from different sources are discussed. The current

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extensive industrial activities in the production of nanocellulose had been presented. This review

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will likely draw attention of researchers towards crop and industrial wastes as a new source in

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the realm of nanocellulose.

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Keywords: Nanocellulose (NC), Nanofibrillated cellulose (NFC), Cellulose nanocrystals (CNC),

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Agriculture biomass and Industrial developments.

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INTRODUCTION:

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The production of cellulosic material increases tremendously to fulfil the need for renewable and

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eco-friendly sustainable materials.1 Cellulose is often considered as one of the most important

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natural resource. With the advent of nanoscience, the researchers and industries focus in the

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production of NC in huge quantities and it is evident from increasing number of publications and

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patents in this field.2The trailing purpose behind the growth of research in NC lies in their

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promising properties such as low density and high mechanical strength.3 Cellulose can be found

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in different sources like wood, natural fibers (agriculture biomass), marine animal (tunicate),

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algae and fungi.4 The composition of cellulose is highly dependent on the source.5 This review

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deals with the crop waste as a core source for the extraction of NC.

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With the ever-increasing demand for renewable resource, the crop waste is meant to be an

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appropriate material. The recovery of waste makes it possible to protect the environment and to

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benefit from low cost reinforcements. Agriculture waste biomass is significant resource for the

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reason it is environmental friendly, low cost, readily available, renewable and exhibit somehow

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acceptable mechanical properties.6 The crop waste constitutes abundant natural fibers.7 The

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agriculture waste fibers can be obtained from cotton stalk, pineapple leaf, rice straw, flax, hemp,

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soy pods, rice husk, garlic straw, potato peel, grape skin etc. Agri biomass can be used in

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multitude applications like paper, textile industry, composites, building, furniture and medical

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fields.

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The NC market is currently emphasized because of the augmented focus of the governments,

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industries, funding agencies and Universities. The bio-based economy is rapidly increasing

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resulting in the higher investments. The NC production includes high value added applications

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like composites, paper industry, packaging, paints, oil &gas, personal care, medical care etc.8

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The NC is first commercialised by celluforce Inc. in Quebec; a joint-venture between FP

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innovations and Domtar.9 The NC industries are prominent in the areas of Asia Pacific, North

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America, Europe, Latin America and Middle East and Africa including leading names like

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Paperlogic, University of Maine, Borregaard Norway, American Process, Nippon Paper Japan,

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Innventia Sweden, CTP/FCBA France, Oji Paper, Japan.

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This article aims to deliver the consolidate details on structure and multiple sources of cellulose,

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NC, their extraction from agri-based sources and the current industrial developments on NC

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production and applications. There are numerous literature which deal with various aspects of

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NC like source, production of nanofibrillated cellulose,10,11 production of nanocrystals,12–14

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extraction methods,11 pre-treatments,15 properties16 and applications.17 However, there is only

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limited review on the agriculture biomass for the extraction of NC.6,18 Since the urge of

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converting agriculture waste into wealth is increasing for the reasons of waste management,

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improve ecofriendly resource and creating new source of economy, this review paper

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concentrates on the inside story of the agriculture biomass, extraction of NC from crop waste,

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different treatments, pre-treatments involved. It also deals with the properties of isolated NC. To

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conclude, the applications and industrial evolution in the production of NC are also addressed.

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SOURCE OF CELLULOSE:

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Cellulose is the amplest resource of natural fibers. Annually, the extraction of cellulose is

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assessed to be over 7.5 x 1010 tons.12 Cellulose is extracted from various sources including wood

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(Hard or soft wood), seed (cotton), bast (Flax, hemp), cane (bamboo, bagasse), leaf (Sisal), straw

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(rice, wheat), fruit (Coir), tunicate, algae, fungi, bacteria and minerals.19 Figure 1 shows the

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hierarchical representation of the chief sources from which cellulose can be extracted.

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Figure 1. Hierarchical representation various sources of cellulose.

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The source is placed in the order of conventional source like wood and cotton, which is

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considered as the primary origin. Wood can be classified as soft/hard wood based on their

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structural aspect.20 Then comes the agriculture waste which are the unprocessed wastes that are

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coming directly from the field residues like rice straw, banana rachis, corncob etc. The crop

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waste is becoming the second highest source of cellulose. The industrial waste is the processed

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waste produced by the industries like sugarcane bagasse, tomato and garlic peels etc. which is

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another source of cellulose emerging lately. Cellulose can be obtained from some other small

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class of sources like marine animal (tunicate), algae, fungi and bacteria. The interest of this

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review lies on the second and third grid of the pyramid representation i.e. Crop and industrial

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waste for the fact that this source needs to be explored more. The basic constitution of the

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foretold fibers is cellulose, lignin and hemicelluloses. However, the chemical composition differs

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for each some of which are tabulated in table 1 on dry basis. Besides cellulose lignin and

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hemicelluloses, some sources contain pectin, waxes and other water-soluble components.

Table 1. Chemical composition of different sources on dry basis. Source

Cellulose

Hemicellulose

Lignin

(wt.%)

(wt.%)

(wt.%)

Pine (softwood)

44.0

27.0

28.0

Yellow birch

47.0

31.0

21.0

Jute

73.2

13.6

13.4

Wheat straw

48.8

35.4

17.1

Rice husk

45.0

19.0

19.5

Bagasse

55.2

16.8

25.3

Banana

63–64

10

5

71

18.6-20.6

2.2

Reference

(hardwood) 21

22

23

Flax

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Hemp

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70-74

17.9-22.4

3.7-5.7

37.38 ± 2.31

25.32 ± 2.45

9.99 ± 0.82

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Garlic straw

41

18

6.3

25

Carrot residue

81

9

2.5

26

38.31

27.62

21.10

27

41.1 ± 1.1

16.2 ± 0.6

38.9 ± 1.3

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Mulberry barks

Ground nut shells

Onion skin 92 93

CELLULOSE:

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Cellulose is the natural polysaccharide first isolated by Anselme Payen in 1838 from wood when

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treated with nitric acid.12 They exist as microfibrils in the plant cell wall of multiple sources. The

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diameter of the fibrils varies from 3-35 nm depending on the source.29 Cellulose contains linear

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polymer chain comprised of glucose monomer named β-1,4-linked anhydro-D-glucose units as

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shown in figure 2. The degree of polymerization of cellulose is up to 20000 units. For wood and

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cotton it is approximately 10000 and 15000 glucose units respectively.30

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Anhydroglucose is the monomer and cellobiase is the dimer of cellulose. Each glucopyranose

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unit contains 3 highly reactive hydroxyl groups which are responsible for the hydrophilicity,

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chirality, biodegradability etc. of cellulose. The individual cellulose chain contains reducing end

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because of the hemiacetal unit with both aliphatic and carbonyl group and the non-reducing end

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with closed end group.31 The higher mechanical properties of each microfibrils result from the

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strong hydrogen bonds.

Figure 2. a) 3D structure of cellulose.b) structure formula of cellulose. Adopted from Cave and Walker (1994).31

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The β-1,4-glycosidic bonds builds an ordered crystalline structure by Vander Waals forces and

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inter & intra molecular hydrogen bonding.32 In these regions, the cellulose chains are strongly

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arranged into crystallites. The hydrogen bond existing between cellulose chains make it highly

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stable but poorly soluble in water and other solvents. These hydrogen bonding network and the

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molecular arrangement results in polymorphs or allomorphs of cellulose. There are six

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interconvertible polymorphs of cellulose had been identified id Est cellulose I, II,IIII,IIIII,IVI and

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IV II.33 In 1984 Atalla and Vander Hart proved that the native cellulose I can be subdivided into

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Iα and Iβ.34 Cellulose II can be obtained from the chemical regeneration35 or by mercerization.36

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Cellulose III is formed when cellulose I or II is treated with ammonia or various amines37 and the

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polymorphs IVI and IVII are produced by heating cellulose IIII or IIIII respectively at 260ºC in

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glycerol.38

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The amorphous region results from the breakage and disordered hydrogen bonds.39 Figure 3

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shows the crystalline and amorphous regions of cellulose. The hydrogen bonding and orientation

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of cellulose differs extensively for the different source.

Figure 3. Crystalline and amorphous regions of cellulose. 120 121

HEMICELLULOSE:

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Plant cell wall is mainly made up of cellulose, hemicellulose and lignin as stated before.

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Hemicellulose is the second major component accounting 15-30% of the cell wall.40 They are

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entrenched around the microfibrils bundles as shown in figure 4.

Figure 4. Cellulose bundles embedded by hemicelluloses and lignin.

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Hemicellulose can be divided into four different classes based on their structure as 1) Xylans, 2)

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Mannans, 3) β-glucans and 4) Xyloglucans. Hemicelluloses are branched polysaccharides

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containing β-1→4-linked backbones of glucose, mannose or xylose in equatorial configuration at

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C1 and C4 and the structure varies with the side chain type and the distribution of these

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backbones.

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glucan (figure 5a) β 1,4-xylan (figure 5b) and β 1,4-Mannan (figure 5b).42

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The figure 5 shows the structure of some backbones of hemicellulose like β 1,4-

Figure 5. Structural backbone of hemicellulose a) β 1,4-glucan b) β 1,4-xylan c) β 1,4-Mannan. Adopted from 42 131 132

Few examples of xylans are glucoronoxylans and arabinoxylans and they can be found in straw,

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stalks, husk etc. Mannans can be classified as gluco and galactomannans which can be extracted

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form gaur, locust bean etc. Xyloglucans are used as thickening and gelling agent in foods and

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can be isolated from tamarind seeds.43 As reported in the literature, it is known that

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hemicelluloses play a key role in facilitating the fibrillation process.44,45 The reason is most

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likely because of the hydrogen bonding and negative charges on hemicelluloses. As realised

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from figure 4, hemicellulose surrounds cellulose microfibrils through numerous hydrogen

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bonding which in turn seals the gap between the microfibrils and hinders the fibrils from

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aggregation. Also, hemicelluloses contain glucuronic acid with carboxyl groups which enables

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the delamination of fibers by means of electrostatic repulsion forces. 45

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LIGNIN:

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Lignin is a heterogeneous and irregular cross-linked polymer of phenyl propane. It is amorphous

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and optically inactive material with three different monomers namely Coumaryl alcohol,

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Coniferyl alcohol and Sinapyl alcohol whose structure is shown in figure 6.46 Lignin is derived

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by the enzyme mediated polymerization. The molecular weight of isolated lignin is typically in

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the range of 1000-20,000 g/mol, though the degree of polymerisation in nature is difficult to

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arrive on the account that lignin is highly fragmented during isolation and it also contains many

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repeating substructures in a seemingly haphazard manner.47

Figure 6. Structural units of lignin. Reprinted with permission.46 Copyright 2014 American Chemical Society. 150 151

Lignin is used in multiple applications as emulsifiers, dyes, synthetic flooring, binding,

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thermosets, paints etc. The sulfur-free and water soluble lignin is used for automotive brakes,

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wood panel products, bio dispersants, polyurethane foams, and epoxy resins for printed circuit

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boards.48

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Nanocellulose:

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The plant cell wall can be classified into two namely primary and secondary. The primary cell

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wall is the external thin layer (less than 1 µm) and the secondary cell wall chiefly contains

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cellulose microfibrils.49 The Hierarchical configuration of wood to cellulose nanocrystals are

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shown in figure 7. Generally, either length or diameter of the cellulose particles are in the nano

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size (1-100nm) are called as NC. The plant cell wall consisting bundles of the cellulose fibrils

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and their diameter is in few microns. Each cellulose bundle is consisting millions of micro

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fibrils, these micro fibrils are composed with elementary fibrils or nano fibrils. The diameter of

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the nanofibrils is about 5nm, whereas in the case of the micro fibrils the diameter will vary from

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10-50nm. Every nano fibers are composed of flexible amorphous and strong crystalline parts.

Figure 7. Hierarchical structure of cellulose and its derivatives in nanoscale. 166 167

Several cellulosic derivatives are isolated from these microfibrils and depending on their

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isolation methods, source, dimensions they are called , NC, whiskers, nanofibrils.1 Depending on

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their method of preparation, NC is classified into 1) cellulose nanocrystals (CNC) and 2) nano

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fibrillated cellulose (NFC). The other type of NC called bacterial cellulose (BC) and electro spun

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cellulose nanofibers (ECNF) can also be isolated. Nevertheless, CNC and NFC are considered as

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the more common and they are produced by top-down process i.e. by disintegration of cellulose

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fibers to nanoscale particles whereas BC and ECNF are produced by bottom-up process in which

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nanofibers are formed from low molecular weight sugars by bacteria or from dissolved cellulose

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by electrospinning respectively.11 The morphological images of four different NC from corn

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husk (figure 8a), tunicate (figure 8b), bacterial cellulose (figure 8c) and electro spun cellulose

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nanofibers (figure 8d) is shown in figure 8. 50–53

Figure 8. Micrographs of NC a) NFC from corn husk. Reprinted with permission.50 Copyright 2015 Elsevier. b) CNC from tunicate. Reprinted with permission.51 Copyright 2014 American Chemical Society c) Bacterial cellulose. Reprinted with permission.52 Copyright 2006 American Chemical Society and, d) electro spun cellulose nanofibers. Reprinted with permission.53 Copyright Intech, DOI: 10.5772/8153. 178

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NANOFIBRILLATED CELLULOSE:

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The cellulose fibers are fibrillated usually by mechanical breakdown to achieve clusters of

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cellulose microfibrils due to shear forces called nanofibrillated cellulose. The nomenclature can

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be different for these nanofibrils as a) nano fibrillated cellulose (NFC) b) micro fibrillated

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cellulose (MFC) c) cellulose nanofibrils (CNF) d) cellulose filaments (CF). The diameter of NFC

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is in nanoscale i.e. less than 100 nm and the length can be of few micrometers. The structural

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morphology of NFC from corn husk is shown in figure 8a.

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The NFC was first obtained by Turbak et al., 1983 and Herrick et al., 1983 by means of a Gaulin

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laboratory homogenizer.54,

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ensuing from the surface hydroxyl groups is increased during fibrillation or delamination. Owing

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to this, NFCs are inclined to form gels showing increased viscosity. The major impairment of

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NFCs are they tend to form gels once produced, their hydrophilicity restricts the dispersion with

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few hydrophobic polymers. Importantly, the extraction process consumes high-energy. All these

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difficulties can be overcome with some pre-treatments and surface modifications. Besides the

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drawbacks, NFCs are commercially produced and used in plenitude applications including

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composites, coatings, personal care, constructions etc.8

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CELLULOSE NANOCRYSTALS:

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Cellulose nanocrystals, also termed nano whiskers, are spherical “rod” or “needle” like highly

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crystalline structures with diameter of 2-25 nm and length from 100-750 nm depending on the

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source. The morphology of CNC from tunicate is shown in figure 8b. CNCs are first obtained by

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acid hydrolysis by Ranby in 1949.56 As discussed in the structure of cellulose, it contains both

55

The specific surface area and the number of hydrogen bonds

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crystalline and amorphous regions. During the acid hydrolysis, the amorphous region is removed

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leaving behind the crystalline particles as displayed in figure 9.

Figure 9. Isolation of CNC from cellulose by sulphuric acid hydrolysis. Reprinted with permission.57 Copyright 2017 Royal Society of Chemistry. 202 203

The amorphous regions present in the cellulose chain is the first and easily accessible to the acid

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for the hydrolytic action due to kinetic force and steric hindrance however the crystalline

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regions are more unaffected by the hydrolysis.

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crystallinity will vary depends on the source. The acid hydrolysis can be achieved using

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hydrochloric acid (HCL) and sulphuric acid. However, HCL does not result in stable suspensions

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due to the absence of the surface charge. Whereas in the case of sulphuric acid hydrolysis, the

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surface of the cellulose attains the half ester sulfate groups resulting in high negative charge. 59 It

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was reported that the length and surface charge of CNC fibers depends on the hydrolysis period

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by Dong et al.60The length of CNC fibers decreased while increasing the hydrolysis time by

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increasing the surface charge.

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Another interesting aspect was studied by R.H. Marchessault et al. which showed the

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birefringent liquid crystalline phases.

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nematic phases. The authors stated that cellulose, in the form of fibrillar fragments was dispersed

61

13, 56

The size, morphology and degree of

Revol et al. in 1992 proved that CNC formed chiral

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in water and above critical concentration, the self-organization of cellulose crystallites into chiral

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nematic liquid crystalline phase (parallel alignments of the anisotropic crystallites) was observed.

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BACTERIAL CELLULOSE:

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Evident from figure 1, cellulose is not only found in plant cell walls but also can be obtained

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from bacteria and are named as bacterial cellulose (BC). The bacterial cellulose is also referred

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as microbial cellulose, bacterial NC or bio cellulose.1 BC can be synthesized from Acetobacter,

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Rhizobium, Agrobacterium, and Sarcina by aqueous culture media cultivation.63 The

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morphology of the bacterial cellulose is shown in the figure-8c.

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ELECTROSPUN CELLULOSE NANOFIBERS:

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In this method, cellulose is dissolved in a suitable solvent and a high voltage is applied through

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the solution so that the particles are charged and repulsive force is created. The network of the

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ECNF is shown in the figure 8d. At a critical voltage, the repulsive forces overcome the surface

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tension of the solution. When it is passed through air, the solvent evaporates resulting in fiber

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formation which are then collected on an electrically grounded plate.64 ECNF is used invarious

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applications.65

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IMPORTANCE OF AGRICULTURE BIOMASS:

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Agriculture sector is producing huge volume of wastes which is menace to the environment as

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they are either burnt in the fields causing air pollution or accumulated in the soil. The recovery of

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this waste makes it possible to protect the environment. But at the same time, it will also create

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new economy. Agriculture waste is the richest form of natural fiber and it is more promising and

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sustainable material. Towards the advancement of the materials, scientists and researchers need

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to elaborate new materials and new technology based on intelligent and eco-conscious materials.

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In other words, materials have greater impact on environment and thus choosing them reflects on

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the technologies they are used. On that account, materials can be an important part of solution to

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the problem that created by specific technology. Aforesaid solution could be developing a new

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material that works better based on eco-designed or bio based

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towards sustainable materials produced using crop waste is increasing among researchers.

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Compared to wood in which case cellulose is present in secondary cell wall, it is more facile to

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isolate cellulose from agriculture fibers wherein cellulose is found in primary cell wall and the

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fibrillation in the latter case is done with low energy consumption.67

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As per the OECD-FAO (Organisation for Economic Co-operation and Development and 38 the

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Food and Agriculture Organization) agriculture outlook, every year farmers are harvesting 39.35

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million tons of natural fibres from plants.68 Considering the amount of production, the waste

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outcome is also a lot out of which fibers can be obtained. Correspondingly, few millions of

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metric tons of fibers are available every year and the sum increases annually. Converting these

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waste materials into wealth is ongoing interest of the researchers. NC from plant origin alone or

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with mixture of another materials can be used in quite a lot of applications. Natural fibers serving

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as agri based raw material for the extraction of NC can be obtained from all parts of the plant

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like stem, leaves, bark, seeds. Fibers gained from the stem are called ‘bast fibers’ and few

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examples of bast fibers are flax, hemp, kenaf etc. Pineapple, banana, date palm, Sisal are

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examples of leaf fiber and cotton, kapok & coir falls under the seed fibers.

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The quality of the fibers depends on different factors like production location, climatic

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conditions, plant species as presented in figure 10.69 Consequently, it is a requisite to have better

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understanding of the properties of vegetal waste fiber.

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products.66 Hence, interest

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Figure 10. Factors that affect the quality of the fiber at various stages of production. Adopted with permission.69 Copyrights 2011 Elsevier.

261

ISOLATION OF NANOCELLULOSE FROM AGRICULTURE WASTE:

262

The chemical composition of NC consists of cellulose, lignin, hemicellulose, pectins and others

263

as discussed earlier. It is indispensable to remove lignin and other components to get pure

264

cellulose. Figure 11 shows the exact picture of diverse techniques involved in the production of

265

NC. Alkali treatment followed by delignification (bleaching) is the first process in the extraction

266

of NC from any fiber. NC can be extracted from countless agriculture biomass by means of

267

chemical, mechanical or enzymatic treatment. The isolation of cellulose nanocrystals can be

268

attained by acid hydrolysis directly after the purification of biomass. Whereas nanofibrillated

269

cellulose is produced typically by mechanical treatments like homogenization, grinding, steam

270

explosion, Cryocrushing etc. The detailed procedures of these methods are discussed in the

271

following sections.

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Figure 11. Different methods of nanocellulose production from agriculture waste. Reprinted with permission with slight modification. © 2015 Rojas J, Bedoya M, Cito Y. Published in Intech under CC BY 3.0 license. Available from: http://dx.doi.org/10.5772/61334 272 273

Since the mechanical treatment involves high energy consumption pre-treatments like chemical/

274

enzymatic are carried prior mechanical treatments. Table 2 presents the extraction of NC from

275

different crop biomass, method of purification, pre-treatments, their production methods, type of

276

NC obtained is reported.

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277 278

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Table 2. Agriculture biomass source, purification method, Pre-treatments, mechanical treatments, type of nanocellulose and references.

Biomass

Purification

Pre-treatment

technique Sugar beet

Sodium hydroxide,

pulp

sodium chlorite

homogenization

Extraction

Type of

method

nanocellulose

Blending

Cellulose

Cryocrushing,

microfibrils

Cryocrushing

Cellulose

References

67

treatments Hemp/spring

Sodium hydroxide,

flax,

hydrochloric acid

/rutabaga

treatments/kraft

-

70

nanofibers

process

Soybean

Sodium hydroxide,

Refining (PFI

pods

hydrochloric acid,

mill)

Homogenization

Nanofibers

71

Chemical and

Cellulose

72

microfibrils

chlorine dioxide treatments Banana

Sodium hydroxide,

Biological

rachis

Hydrogen peroxide,

retting /

mechanical

Potassium

mechanical

treatments

hydroxide

processing

Sodium chlorite treatments Peel of

Bleaching Toluene,

prickly pear

ethanol

-

Homogenization

Cellulose microfibrils

fruits

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Mulberry

Sodium hydroxide

Acid hydrolysis

barks

treatment

Pineapple

Sodium

leaf

hydroxideAcetic

explosion

acid, Sodium

Blending

Cellulose

24

whiskers -

Steam

Nanocellulose

74

Cellulose Nano

75

hypochlorite, Oxalic acid treatments Coconut

Sodium hydroxide

husk fiber

Acid hydrolysis

-

Acid hydrolysis

whiskers

Bleaching with Sodium chlorite and glacial acetic acid Cassava

-

-

Acid hydrolysis

bagasse Banana

Cellulose

76

whiskers

Sodium hydroxide

-

Acetic acid

Steam explosion,

Cellulose

Sodium

nanofibers

77

hypochlorite and oxalic acid treatments

Oat straw

-

Homogenisation Quarterisation

Jute fibers

-

Nanofibrillated

78

cellulose Ball milling

Nanocellulose

79

Acid hydrolysis

Cellulose

80

Mercerisation Rice husk

Sodium hydroxide

-

treatment, Bleaching

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chardonnay

Toluene, ethanol

-

Acid hydrolysis

grape skins

Cellulose

81

nanocrystals

Sugar cane

Sodium hydroxide

bagasse

treatment

Sesame husk

Sodium hydroxide,

Ionic liquid

-

Homogenization

Nanocellulose

82

Acid hydrolysis

Cellulose

83

Bleaching

nanocrystals

sodium chlorite treatments Sugar cane

Sodium hydroxide

bagasse

treatment

Potato peel

Sodium hydroxide

waste

treatment, Bleaching

Raw cotton

-

Ionic liquid

-

Homogenization

Nanocellulose

82

Acid hydrolysis

Cellulose

84

nanocrystals -

Acid hydrolysis

linter Bleached

Cellulose

85

nanowhiskers

Bleaching

-

Grinding

Eucalyptus

Nanofibrillated

86

cellulose

pulp Rice straw

Maize straw

Toluene, ethanol,

Carboxylation

sodium chlorite,

(TEMPO)

Blending

Cellulose nanocrystals

potassium hydroxide

and cellulose

treatments

nanofibers

Soxhlet extraction

Bleaching with

using hexane, ethyl

H2O2 and

alcohol and DI water

TAED solution.

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Acid hydrolysis

Cellulose whiskers

88

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Acetic acid and nitric acid treatment Oil palm

-

-

Acid hydrolysis

Microcrystalline

biomass

followed by

cellulose

residue

NH4OH

89

treatment Pomelo

Sodium hydroxide

(Citrus

treatment, Bleaching

-

Acid hydrolysis

Cellulose

90

nanocrystals

grandis) Albedo Kenaf bast

Sodium hydroxide,

fibers

Bleaching and

-

Grinding

Cellulose

91

nanofiber

anthraquinone treatment Mango seed

Sodium hydroxide

-

Acid hydrolysis

treatment, Bleaching Orange waste

Sodium hydroxide,

Cellulose

92

nanocrystals -

Sonification

Nanocellulose

93

45

sodium chlorite treatments Alfa and

Sodium chlorite,

Carboxylation

Blending

Nanofibrillated

sunflower

Acetic acid

(TEMPO)

Homogenization

cellulose

Acid hydrolysis

Cellulose

Sodium hydroxide treatments Corn cob

Sodium hydroxide

-

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Treatment,

nanocrystals

Bleaching Wheat Straw

Hydrogen peroxide treatment

Acetic

Grinding

acid/formic

Cellulose

95

nanofibrils

acid, water Agave

Sodium hydroxide,

tequilana and

Bleaching

barley

sodium chlorite and

-

Acid hydrolysis

Cellulose

96

nanocrystals

acetic acid treatments Garlic skin

Alkali treatment

-

Acid hydrolysis

Cellulose

28

nanocrystals Corn husk

Benzene, ethanol

-

Ultra-sonication

Bleaching Chilli

Sodium hydroxide,

leftover

acetic acid,

Nanofibrillated

50

cellulose -

Acid hydrolysis

Cellulose

68

nanocrystals

Bleaching Citrus waste

Sodium hydroxide

-

and Sodium chlorite Lotus leaf

Toluene, ethanol,

stalk

Bleaching

-

sodium chlorite, potassium hydroxide treatments

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Enzymatic

Cellulose

hydrolysis

nanofibers

High intensity

Nanocellulose

ultra-sonication

97

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Tomato peel

Sodium hydroxide,

-

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Acid hydrolysis

Bleaching and

Cellulose

99

nanocrystals

Sodium chlorite Flax fibers

Sodium hydroxide,

-

Ultrasonication

Cellulose

Bleaching,sodium

and acid

nanowhiskers

chlorite,

hydrolysis

100

potassiumhydroxide treatments Carrot

Sodium hydroxide

residue

Treatment,

-

Grinding

nanofibers

101

-

Acid hydrolysis

Cellulose

28

Bleaching Onion skin

Sodium hydroxide

waste

Treatment,

nanocrystals

Bleaching Groundnut

Benzene, ethanol

shells

Bleaching

Flax fibers

Sodium hydroxide

-

Acid hydrolysis

Cellulose

27

nanocrystals -

Acid hydrolysis

Treatment,

Cellulose

102

nanocrystals

Bleaching Miscanthus

Sodium chlorite,

x. Giganteus

Bleaching, Acetic

-

Acid hydrolysis

Cellulose

103

nanocrystals

acid Sodium hydroxide treatments Citrus waste

Toluene, ethanol,

-

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Acid hydrolysis

Nanocellulose

104

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Bleaching, sodium

chlorite,

280 potassium hydroxide treatments Garlic straw

Sodium hydroxide

-

Treatment, Bleaching

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Cellulose nanocrystals

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281

PURIFICATION OF BIOMASS:

282

The first interest involved in the extraction of NC is purification of biomass to remove non-

283

cellulosic (hemicellulose, lignin) to get the pure cellulose fibers. Firstly, raw materials treated

284

with alkali67,105 (NaOH or KOH), organic solvents106, Soxhlet88 or mineral acids in order to

285

remove the hemicellulose, lignin, pectin’s and waxes (This step also called as pulping).

286

Secondly, delignification often called as bleaching is usually done by chemical process. The

287

bleaching step involves single or multiple stages depending the end use applications. The most

288

frequent bleaching agents used are sodium chlorite,75 hydrogen peroxide,

289

Additional process like Kraft process also called as sulfite process is also carried in the

290

purification process.70

291

EXTRACTION OF CNC:

292

Classical extraction of cellulose nanocrystals includes 60-65 wt.% of sulfuric acid hydrolysis

293

(H2SO4) at temperature less than 50 ºC followed by purification of biomass as shown in figure

294

11. Acid hydrolysis benefits to disintegrate the fibers into nanoscale and helps in preferential

295

acid hydrolysis of the amorphous parts of cellulose leaving behind the crystalline parts of

296

cellulose.33 The hydrolysis is followed by repeated cycles of sonication and dialysis against

297

ionized water yielding the pure CNC. CNC can also be produced by the acid hydrolysis using

298

hydrochloric acid (HCL), phosphoric acid and hydrobromic acid.107–109Apart these, CNC was

299

also isolated by microbial hydrolysis.110One of the recent study showed the isolation of CNC

300

using catalytic ionic liquid hydrolysis.111The downside of producing CNC using HCL is that the

301

suspension is unstable leading to the flocculation112 wherein during sulfuric acid hydrolysis, the

302

sulfate ester (-OSO3- ) are randomly spread on the surface of the nanoparticles resulting in the

303

electrostatic layer which promotes the dispersion of CNCs in water.

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oxygen or ozone.

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304

Importantly, the acid hydrolysis conditions like hydrolysis time, concentration of the acid,

305

temperature affect the properties of CNC. The influence of temperature ranging from 45 to 72 ͦ C

306

on the sulfuric acid hydrolysis of cotton was studied by Elazzouzi-Hafraoui et al. The authors

307

reported that increase in temperature resulted in shorter crystals. Though there was no clear

308

effect on width was reported.113 These studies were carried out on the wood/cotton based NC.

309

However they can also be applicable to the crop and industrial waste based NC.

310

In literature, CNCs were obtained from agriculture waste like mulberry barks, coconut husk,

311

cassava bagasse, rice husk, onion skin waste, citrus waste etc. The dimensions and structural

312

morphology of these CNCs are tabulated in table-3 and figure 13 respectively. Of vital

313

importance in the production of CNC, the industries are trying to reuse the sulfuric acid. The cost

314

of sulfuric acid is 4-6 times more than that of the market pulp. Hence recovering the acid by

315

centrifugation and reusing the sulfuric acid can provide an extensive cost advantage.114

316

EXTRACTION OF NFC:

317

Unlike the extraction of cellulose nanocrystals which could be extracted in single step after

318

purification of the cellulose fibers. NFC is extracted in different steps like homogenization,54

319

cryocrushing,115 grinding116 , micro fluidization

320

treatment consumes high energy, chemical and enzymatic pre-treatments have been followed

321

prior. Chemical pre-treatment includes tempo-oxidation,118 quarterisation, refining etc. and in the

322

enzymatic pre-treatment, enzymes like endo and/or exoglucanase were used previously.119 In this

323

section, initially the pre-treatments are discussed in detail followed by the mechanical process

324

involved in the production of NFC.

117

, and ultra-sonication.98Since the mechanical

325

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326

PRETREATMENTS:

327

Pre-treatment is the very important step for the extraction of the NFC. Chemical or enzymatic

328

pretreatment helps to overcome the recalcitrance of plant cell wall. Recalcitrance in other words

329

is the resistance of the cell wall breakdown. The deconstruction of cellulose and non-cellulosic

330

materials like lignin and hemicellulose from the cell wall is not a very simple process because

331

the recalcitrance results from the extreme crystalline structure of cellulose surrounded with lignin

332

and hemicellulose. An ideal cleavage of biomass to extract pure cellulose must prevent the loss

333

of cellulose, be cost effective and consume less energy and produce less toxic wastes and hence

334

pre-treatments should comply all these criteria.120 Mechanical extraction of NFC consumes high

335

energy from 20,000–30,000 kWh/ton. That being said, chemical or enzyme pre-treatments bring

336

down the energy consumption 20times less, i.e. 1000 kWh/ton.121

337

CHEMICAL PRE-TREATMENT:

338

The chemical pre-treatment comprises 1. Acid hydrolysis 2. Alkaline hydrolysis 3. Oxidation

339

and 4. Organic solvents/ionic liquids. Acid hydrolysis breaks the hydronium ions in the biomass

340

and inter and intra molecular bonding between hemicelluloses and lignin leaving behind the pure

341

cellulose. Acids like sulfuric acid (H2SO4), hydrochloric acid (HCL), nitric acid (HNO3) and

342

phosphoric acid (H3PO4) are often used for the pre-treatments. Rosa et al. used H2SO4 acid

343

hydrolysis to treat coconut husk fibers, Wang et al. used HCL to treat soy pods.75,86 Strong acid

344

hydrolysis is not eco-friendly. Moreover, it is difficult to recover the acid after the hydrolysis. On

345

the other hand, the dilute acids at moderate temperature achieve better hydrolysis.122

346

The alkali treatment is mainly to remove the hemicellulose and it also helps in breaking the

347

bonds between cellulose, hemicellulose and lignin. The alkali treatment involves the

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saponification of intermolecular ester bond between lignin and hemicelluloses. Normally, alkalis

349

like NaOH, KOH, Ca (OH)2, hydrazine and ammonium hydroxide. Most of the crop waste

350

biomass like rice husk, mulberry barks, onion skin waste, and mango seed were treated with

351

sodium hydroxide to remove lignin. The alkali treatment also causes swelling of the cellulose

352

which leads to the increase in the surface area and decrease in the degree of crystallinity. In 2006

353

Saito et al. used TEMPO (2,2,6,6-tetramethylpiperidine-N-oxyl) to oxidise cellulose while

354

extracting NFC by blending process.118 Organic solvents like methanol, ethanol, acetone,

355

ethylene glycol are also used in removing lignin and hemicelluloses.

356

ENZYMATIC PRE-TREATMENT:

357

Biological enzymes catalyse the hydrolysis of cellulose fibers which makes the fibrillation much

358

easier. Pääkkö et al., 2007 used endoglucanase to hydrolyse cellulose fibers and they carried out

359

three following steps before the isolation of NFC using micro fluidizer. 1) Refining the fibers to

360

swell the cellulose making it more available for the enzymes 2) enzymatic hydrolysis for the

361

delamination of fibers and 3) Washing and yet again refining.119 Mayra Mariño et al. (2015) used

362

Xanthomonas axonopodis pv. citri (Xac 306) enzyme for the degradation of citrus waste fibers

363

to yield cellulose nanofibers.97

364

MECHANICAL TREATMENT:

365

It is worth to note that in this section authors covered the mechanical treatments used for the

366

extraction of NFC from agriculture biomass though there are other mechanical treatments. In the

367

literature, we can find that nanofibrillated cellulose have been extracted from number of agri

368

biomass like alfa and sunflower, carrot, kenaf bast fibers, jute fibers, peel of prickly pear fibers,

369

soybean pods, oats straw etc. as shown in table 5. Regardless of the source, NFC is produced

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370

chiefly using mechanical treatment. The mechanical treatment comprises 1. Homogenization, 2.

371

Micro fluidization, 3. Grinding, 4. Cryocrushing and 5. Ultra-sonication. All these treatments

372

work under high shear forces cleaving the cellulose fibers resulting in the fibrillation. Following

373

is the detailed description of these different mechanical treatments.

374

REFINING AND HOMOGENIZATION:

375

Refining in most cases is performed prior homogenization. Different refiners like PFI mills, disk

376

refiners are used to refine the pulp.71,123 In 2011, Karande et al., extracted NFC from cotton

377

fibers by using only disk refiner.124 The working principle of homogenizer is shown in figure 12

378

a.

Figure 12. Diagram for working principle of a) homogenizer adopted from 125b) micro fluidizer. Adopted with permission.126c) grinding adopted from www.masuko.com and d) Cryocrushing from 127 379

In this method, the cellulose suspension is passed through a vessel between two valve seats and

380

high pressure is applied because of which high shear forces are generated causing the fibrillation

381

of cellulose. This procedure is repeated number of times to increase the degree of fibrillation.

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382

The isolation of micro fibrillated cellulose using homogenization was first done by Turbak et al.

383

in 1985 using Gaulin homogenizer.54 Dufresne et al. (1997) produced cellulose micro fibrils

384

from sugar beet pulp using homogenization. The purified sugar beet pulp suspension was poured

385

into the vessel and high pressure (500 bars) was applied for 0.5-3 hours resulting in the

386

invidualization of micro fibrils.67 In 2007, Wang and Sain used soybean pods as a raw material to

387

produce NFC. The pre-treated soybean fibers were first beaten and refined in PFI mill at 12000

388

revolution which reduced the fiber length. The sample was then homogenized at high pressure

389

(500-1000 bars) for 20 passes to delaminate the cellulose fibers into nanofibers.71 NFC from Alfa

390

and sunflower was extracted in 2013 by Chaker et al. using high pressure homogenization. The

391

delignified pulp was pumped into GEA homogenizer processor. In this case, the fibrillation was

392

done in two steps. During the first step, 1.5 wt. % of the fiber suspension was passed through the

393

slits at 300 bars for several times to increase the viscosity of the slurry. Then the pressure was

394

increased to 600 bars for the defibrillation process.128 The main drawback of this method is

395

clogging of the system and so the fiber size should be reduced before performing high pressure

396

homogenization.10 The other downside of this treatment is the excessive energy consumption for

397

which few pre-treatments were developed as discussed in the previous section.

398

MICROFLUIDIZATION:

399

Micro fluidization is another mechanical treatment to manufacture NFC and this method was

400

first used by Zimmermann et al. at 2004.117 In this method, the cellulosic suspension is passed

401

through a Z or Y- shaped chamber as shown in figure 12b with channel sizes usually 200-400

402

µm and by applying high pressure through intensifier pump, the fibers are delaminated by the

403

resulting shear forces against the colliding suspension and the channel walls. Ferrer et al.

404

extracted NFC from empty palm fruit bunch fibers (EPFBF) using microfluidizer.129The

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405

clogging of fibers in homogenizer can be overcome in micro fluidization process because it has

406

no in-line moving parts, and it can easily be resolved by reverse flow through the chamber.130

407

GRINDING:

408

Another method to produce NFC is grinding process in which the sample slurry is passed

409

through an ultrafine grinder as in figure 12c. The principle is that the fibers are ground between a

410

static and a rotating stone (disc) rotor. The distance of the discs can be adjusted based on the type

411

of the raw material. The cell wall structure, bonds are cleaved down by the shear forces produced

412

during grinding causing the NFC production. In 2012, Wang et al. produced NFC for first time

413

from bleached eucalyptus pulp using Super Mass-Colloider (Model: MKZA6-2, Disk Model:

414

MKGA6-80#, Masuko Sangyo Co., Ltd, Japan) grinder at 1500 rpm. They used the energy input

415

from 5 and 30 kWh/kg to study the relation between consumed energy and the fibrillation by

416

means of crystallinity and degree of polymerisation.86 Karimi et al., Jossel et al., Siquiera et al.

417

extracted cellulose nanofibers from kenaf bast fibers, wheat straw and carrot residue respectively

418

using grinding process.26,91,95

419

CRYO CRUSHING:

420

In 1997, Dufresne et al. isolated NFC from sugar beet pulp using cryocrushing.67 In this

421

treatment, the cellulosic fibers are frozen in liquid nitrogen and then crushed by high shearing

422

forces which causes the release of exert pressure of ice crystals on the cell wall breakdown

423

leading to the nanofiber formation. Figure 12d shows the working principle of Cryocrushing.

424

Bhatnagar and Sain extracted NFC from hemp, flax and rutabaga in 2005 using cryocrushing.70

425 426

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427

ULTRASONICATION:

428

Ultra-sonication is another strategy of producing NFC in which the suspension is exposed to the

429

ultra-sonic waves. During this process, alternating low and high pressure waves are produced

430

creating, expanding and colliding the gas bubbles. These hydrodynamic forces are used to

431

liberate cellulose nanofibers. Junko Tsukamoto et al. isolated NFC from citrus processing waste

432

from oranges (CPWO) using ultrasonic processor, Sonics at 750 Watt, 20 kHz and 4J. The

433

residue from enzymatic hydrolysis of CPWO was used as a raw material here.93

434

STEAM EXPLOSION:

435

Steam explosion is a thermomechanical process in which the heat carried by the steam penetrates

436

sample by diffusion and the sudden release of pressure generates shear forces cleaving the

437

glyosidic and hydrogen bonds leading to the isolation of nanofibers. This method was used by

438

Cherian et al. to isolate NFC from pineapple leaf and by Deepa et al. in the production of NFC

439

from banana fibers.74,77

440

BALL MILLING:

441

In this technique, the sample is placed in a cylindrical, hollow jar partly filled with metal,

442

ceramic or zirconia ball and when the jar rotates, the collision between fibers, ball and the walls

443

of the container causes the fibrillation. Using ball milling Baheti et al. prepared NFC from jute

444

fibers.79

445

CHARACTERISATION OF NANOCELLULOSE:

446

In this section, the important characterizations of NC produced from agriculture biomass are

447

discussed. The quality assessment of produced NC is done by studying morphology, chemical

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448

composition, crystallinity and thermal properties few of them are discussed in the following

449

section.

450

MORPHOLOGY:

451

Morphology is the key parameter to check the fibrillation of the NFC. It is imperative to study

452

the morphology of the obtained NC to understand the sizes, smoothness and fibrillation. The

453

morphology in usual depends on the source and extraction methods. The size and roughness of

454

the fibers is reduced during the production process possibly because of the removal of lignin,

455

hemicellulose, lignin and other non-cellulosic materials during the alkali and bleaching stages.

456

Morphology is studied using many microscopic techniques like scanning electronic microscopy

457

(SEM), field emission scanning electron microscopy (FE-SEM), transmission electron

458

microscopy (TEM) and Atomic force microscopy (AFM). Few of the micrographs of nano

459

fibrillated cellulose and cellulose nanocrystals produced from different agriculture biomass

460

sources are shown in figure 13.

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Figure 13. Micrographs of nanocellulose produced from different agriculture biomass 461 462

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463

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Table 3. Source, diameter and reference of NC obtained from different crop waste.

464

NFC

465

Source

Diameter (nm)

References

466

Banana rachis

3–5

72

Prickly pear fruits

2–5

73

Wheat straw

10–80

115

Oil palm

5–40

89

Soy hull

20–120

131

467 468 469 470 471

CNC

472 473 474 475 476 477 478

Source

Diameter (nm)

length (nm)

References

Coconut husk

5.5 ± 1.4

58

75

Chilli leftover

4-6

90-180

132

Garlic straw

6

480

25

Groundnut shells

5-18

111

27

Mulberry bark

25-30

400-500

24

479

It is worth noting that size and morphology of NC varies much depending on the source from

480

which they are extracted. The sizes of NFC and CNC produced from various agri-biomass

481

sources are listed in the table 3.

482

Beside source, the morphology of NFC depends on the number of passes (cycle time) and pre-

483

treatments involved in the isolation. As stated earlier, the homogenization is repeated for

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484

different passes to get maximum fibrillation. On that note, Lee et al. in 2009 studied the effect of

485

cycle time (1-20 passes) of homogenization on the size of NFC obtained from commercial

486

microcrystalline cellulose. With the 1-5 passes they reported that the fibrillation was limited only

487

to the surface as shown in figure below. However, with mechanical treatment of 10-15 passes the

488

fibrils were split into smaller fibrils with increased aspect ratio. When passed the suspension

489

further for 20 passes, the fibrils were more chopped into thinner fibers. Having said that, the

490

fibers tend to aggregate due to the higher surface area and high density of hydroxyl groups.

491

Hence the authors concluded that increasing the cycle time may result in the decreased

492

mechanical strength.133

493

Zuluaga et al. (2009) investigated the effect of pre-treatments of banana rachis on the

494

morphology of NFC obtained by using TEM shown in figure 14. They pre-treated the banana

495

rachis using peroxide alkaline (PA) (figure 14a), peroxide alkaline-HCL (PA-HCL) (figure 14b),

496

5 wt.% potassium hydroxide (KOH) (figure 14c) and 18 wt. % KOH (figure 14d). The PA and 5

497

wt.% KOH treated sample showed loose networks whereas PA-HCL treatment resulted in

498

shorter fibrils and finally with 18 wt.% KOH the microfibrils were even shorter and interestingly

499

part of cellulose I was changed into cellulose II.72

500 501 502 503 504

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Table 4. Crystallinity of raw, NFC and CNC obtained from various biomass.

505

506

Figure 14. TEM images of cellulose microfibrils after a) PA b) PA–HCl c) 5 wt. % KOH and d)

507

18 wt. % (KOH-18) treatments. Reprinted with permission. 72 Copyright 2017 Elsevier.

508

The morphology of CNC depends on source, hydrolysis time, temperature, acid concentration

509

and different acids like hydrochloric acid, phosphoric acid or acetic acid. The effect of pre-

510

treatments and the hydrolysis time on the morphology of CNC obtained from coconut husk fibers

511

were inspected by Rosa et al., 2010.75

512

CRYSTALLINITY:

513

The crystallinity study of produced NC is necessary to understand the effect of production

514

methods on the crystal structure of the cellulose. The crystallinity is usually studied by X-ray

515

diffraction (XRD) technique. It is explained elsewhere that cellulose is made of highly crystalline

516

and disordered amorphous regions. It is believed that during extraction the disordered amorphous

517

regions are removed resulting in the increased crystallinity. The degree of crystallinity of NFC

518

and CNC gained from different crop waste sources is shown in the table 4.

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ACS Sustainable Chemistry & Engineering

NFC CNC Source Coconut husk fibers

Crystallinity (%)

References

RiceUntreated straw (Stem)

38.9 ± 0.3

75

Original fibres

50.9

Purified cellulose fibers

63.8

Cellulose nanofibers

63.4

106

Corn husk Original corn husk

35.9

Corn husk NFC

64.8

50

Oil palm residue OPEFB-pulp

80

OPEFB-MCC

87

89

Pineapple leaf Raw



Steam exploded

35.97

Bleached

54.18

Acid treated

73.62

74

Oat straw Starting cellulose material

70

Non-modified CNC

64

519

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CNC (1B at 150 min)

Page 40 of 70

62.2 ± 0.5

Garlic straw Raw

37.4

Bleached

47.1

CNC

68.8

25

132

Chilli leftover Alkali treated

52

Bleached fibers

68

CNC

78.5

Groundnut shell Raw

56

Purified

68

CNC

74

27

Mulberry bark Original mulberry barks

46.9

Pre-treated mulberry barks

58.8

Cellulose whiskers

73.4

520 521

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522

The crystallinity of NC is higher compared to that of starting material and this is due to the

523

removal of lignin, hemicellulose, pectin or any non-cellulosic materials. In some cases, the fibers

524

can partially contain both cellulose I and II. Normally, cellulose I can be identified at 2θ=14.9º

525

(110), 2θ=16.6º (110), 2θ=22.7º (200) and 2θ=34.4º (004).

526

THERMAL PROPERTIES:

527

The thermal property of NC is indispensable to use them in the composites. Cellulosic materials

528

degrade below 400ºC

529

composition. The degradation starts at lower temperature owing to the decomposition of

530

hemicellulose, lignin and then pyrolysis of cellulose occurs after which charring happens. The

531

thermal stability of NFC in most of the cases increases due to the removal of hemicelluloses and

532

lignin.136 In contrast, the thermal stability of CNC decreases when compared to that of raw

533

material because of the introduction of sulfate groups. The sulfate groups degrade at around

534

120ºC and they decrease the defense of cellulose pyrolysis thereby decreasing the thermal

535

stability.

536

APPLICATIONS:

537

The applications of NC from different sources are discussed in this section. NC is of growing

538

interest on the grounds of innumerous applications, for example in various realm from paper

539

industry, composites, biomedicine, textile, construction to aerospace, automotive, and sensors

540

etc.137,138. Recently few studies reported the substantial role of NC in the field of filter

541

application as shown in figure 15c.

135

and the degradation temperature depends on the structure and chemical

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Figure 15. Multitude applications of nanocellulose a) Extruded PP/CNC and M-CNC nanocomposite film. Reprinted with permission.139 Copyright 2016 American Chemical Society b) Bio based pouches from VTT technical research.140 c) Nanocellulose filter. Image obtained from nanografi.com

141

. d) Cellulose nanofibril aerogels from rice straw absorbing dyed

chloroform from water. Reprinted with permission.142 Copyright 2014 Royal Chemical Society. e) Alginate-oxidized nanocellulose sponge. Reprinted with permission.143 Copyright 2012 American chemical Society. f) Fabricated transparent and flexible Nano paper transistor. Reprinted with permission.144 Copyright 2013 American Chemical Society. g) 3D printed small grids and human ear from NFC and alginate. Reprinted with permission.145 Copyright 2015 American Chemical Society. 542

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543

Importantly, the properties like high mechanical properties and low density with high aspect ratio

544

facilitate to use NC in composite field for the fabrication of lightweight and high performance

545

materials. The high water holding capacity due to the enlarged surface area enables their use as a

546

rheology modifier mainly in paints and personal care products and this field need to be explored

547

further for better understanding. Recently hydrophobic aerogels produced from rice straw

548

(agricultural waste) was developed and results shown the great tendency of absorption of

549

hydrophobic solvents as shown in figure 15d. NC has attractive optical properties this could be

550

an added benefit in the fields of electronics, ultra-filter papers, sensors and transparent solar

551

cells. Due to their biodegradability, compatibility NC can play vital role in biomedical field for

552

the progress of drug delivery, artificial body parts and tissue engineering.

553

Composites:

554

Production of high mechanical performance composites can be achieved by the reinforcement of

555

nano fillers into polymers. In this case, NC is an appropriate candidate for composites

556

preparation compared to the non-biodegradable nano fillers like carbon nanotubes, nano clays

557

etc.139 However, it is challenging to prepare nanocomposites by using NC for the reason of poor

558

dispersion of CNC and NFC up on drying and low compatibility with hydrophobic matrices. It

559

can be overcome by introducing hydrophobic groups through surface modification and grafting.

560

Iwatake et al. has described the cellulose nanofiber reinforcement on polylactic acid (PLA). The

561

goal of this study was to prepare green composites. The nanofiber reinforcement increased the

562

Young’s modulus and tensile strength of PLA by 40% and 25% respectively.146Recently, high

563

dispersion and thermal stability was achieved for the quaternary salt modified CNC reinforced

564

with polypropylene as shown in the figure 15a.

565

reinforcement was done by Favier and group wherein poly(S-co-BuA) was reinforced by using

139

The first application of NC in composite

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566

cellulose whiskers. The authors found that the mechanical properties were increased

567

significantly.147

568 569

Packaging:

570

In the modern world, usage of packaged food is increased. Most of the food is packed in the

571

petro based polymers. Therefore, industries are very keen to develop biodegradable and

572

lightweight food-packaging materials. This kind of materials can preserve the quality in terms of

573

freshness and taste. In this aspect VTT technical research center produced bio based packaging

574

materials as shown in figure 15b. Moreover, the shelf life of the food also will increase which is

575

important for both consumers and industries.148

576

Previously, paper substrate was coated with mixture of microfibrillarted cellulose and

577

chlorhexidine digluconate (anti-bacterial molecule) and quality of the food packed with these

578

materials also reported.149Elsewhere reported the antimicrobial activity of the nisin grafted CNF

579

has shown promising anti-bacterial activity against Bacillus subtilis and Staphylococcus aureus

580

bacteria.150NC materials increases the fiber-fiber bond strength and increases the reinforcement

581

effect on paper materials with only less amount of cellulose pulp as a filler resulting in the light

582

weight packaging.

583

Paints and coatings:

584

NC is an ideal material to use in the paint and coating industry. Thanks to their high surface area

585

which helps to hold the water hence acting as a highly viscous material. It is used in improving

586

the durability of paints and protects paints and varnishes from wear and tear caused by UV rays.

587

They can alter the viscosity of paints and coatings. The VTT group, Finland used NC in

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588

polyurethane varnishes and paints as additives, which increased the durability of coatings of

589

paints.151 Some other company called Cellu Comp from United Kingdom claimed, the NC

590

extracted from carrot improved the hardness, flexibility and crack resistance of the paints.152

591

Optical materials:

592

Nanofibrillated cellulose possess great optical properties considering the size of the NFC is less

593

than the wavelength of the visible light. Hence the paper prepared with nanofibrils are

594

transparent.153 This can be added benefit to the different applications like electronics, sensors and

595

solar panels. Adequate research results have been reported in the literature. Jia Huang and team

596

reported the flexible field effect transistors printing on the nano paper for the green electronic

597

transistor applications as shown in figure 15f.144 The other research group studied the deposition

598

of tin-doped indium oxide along with silver nano wires and carbon nanotubes for solar cell

599

applications.153

600

Biomedicine:

601

NC has antiquity of application in biomedicine as excipients, in drug delivery, for

602

enzyme/protein immobilization, implants, skin and bone tissue repair and others. The

603

competence of NC in drug delivery was studied by Letchford et al.

604

nanocrystalline cellulose could bind the significant amount of ionizable water soluble antibiotics

605

tetracycline and doxorubicin by surface modification using cationic surfactant called CTAB

606

(cetyl trimethylammonium bromide). In other study reported by Alain dufresne and his group the

607

cross-linking between the alginate and oxidised nano fibrillated cellulose hydrogels for the drug

608

delivery system was produced as shown in figure 15e.143 Same group also reported the double

609

membrane hydrogels using cationic cellulose nanocrystals and alginate for quick and slow drug

610

release from first layer and second layer respectively.154 Nanomaterials have wide applications as

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134

. This study proved that

ACS Sustainable Chemistry & Engineering 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

611

hydrogels in tissue engineering. In 2015, Markstedt et al. reported the novel method to produce

612

3D bioprinting with living cells. They combined nanofibrillated cellulose with alginate for the

613

3D bioprinting of living soft tissue with cells as shown in figure 15g.145

614

NANOCELLULOSE TOWARDS INDUSTRIALIZATION:

615

The scientific abilities of the NC were progressed from last six decades. The attractive properties

616

of the tiny fibers and particles play vital role for the creation of the new bio economy. Few

617

decades ago, microcrystalline cellulose (MCC) emerged as new material, which is widely used in

618

pharma, composites and chemical fields. Subsequently, NC is emerging as a key material in

619

industrialization.155 According to the global market outlook for NC, by 2022, the annual turnover

620

can reach 808.29 million dollars. The significant mechanical, optical and rheological properties

621

of these materials attracted the both researchers and industries. The journey of the NC from last

622

seven decades is shown in figure 16 along with the major research findings.

623

The enticements for the NC industries are because it is a new source with wide range of

624

applications that need to be established. Hence producing new products resulting in new business

625

breakthroughs. In addition, they can be extracted from easily available sources and are bearable

626

and renewable. The first pilot plant to produce NC was started in 2011 by Innventia at

627

Sweden.156The industrialization of NC can be parted into three main segments viz. products,

628

applications and areas where there are produced. The products of NC are cellulose nanocrystals,

629

nanofibrillated cellulose, bacterial cellulose and electro spun cellulose nanofibers. Applications

630

of NC includes paper industry, composites, personal care, biomedical, electronics, paints etc.

631

Figure 16 shows the pioneering work during the journey of NC towards industrialization.

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ACS Sustainable Chemistry & Engineering

Figure 16. Past, present and future research and industrial trends of nanocellulose 632 633

The pronounced market of NC is seen in areas of North America, Europe, middle East. Table 5

634

indicates the company producing NC across the world with the quantity produced and the type of

635

the product based on the TAPPI NANO outlook 2015.9 Industries collaborate with other

636

universities or institutes to develop new Nano cellulosic materials. The detailed study of

637

industrial turnover and industrial methods is discussed in the following section.

638 639 640 641

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Page 48 of 70

Table 5. Company producing nanocellulose, product type and the production capacity/day in kilograms. Production unit

Production capacity/day (Kg)

Product type

CelluForce-CANADA

1000

CNC

Paper logic -USA

2000

NFC and CNC

University of Maine-USA

1000

NFC and CNC (dry &wet)

Borregaard-NORWAY

1000

NFC

American process-USA

500 to 1000

NFC, CNC

Nippon paper-JAPAN

150-500

Tempo- CNC, NFC and CNC

Innventia-SWEDEN

100

NFC

CTP/ FCBA - FRANCE

100

Enzi. NFC, T-CNF

OHI paper- JAPAN

100

NFC

Stora Enso-FINLAND

unknown

NFC

UPM- FINLAND

unknown

NFC

SAPPI- NETHERLANDS

unknown

NFC

Lulea university- SWEDEN

unknown

NFC

Holmen - SWEDEN

100

CNC

Alberta innovates - CANADA

20

CNC

India council for Ag. research

10

CNC

Melodea - Israel

unknown

CNC

FP-Innovations - CANADA

unknown

CNC, NFC

Blue goose refineries-CANADA

10

CNC

642 643 644

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645

INDUSTRIAL TURNOVER AND METHODS:

646

Every material invention starts at research table and it will take decades to commercialize.

647

Similarly, commercial NC production was started in 2012, nearly six decades after first

648

invention. From thereon, focus on the biomaterials increased due to the awareness of the

649

biodegradable and renewable materials for the betterment of the society. This might be the main

650

reason behind the production activities of the NC. All over the world more than 40 companies

651

was established with their allied organizations to produce the NC. However, the potential

652

application was not yet established. Industries are currently under research to find the key

653

advancements in the fields of the concretes, paints, composites and packaging. Authors

654

attempted to shortlist all the production sites of NC, nature of material manufactured, their

655

production capacity and methods of the preparation in table 6 based on the TAPPI NANO, 2015

656

ISO/TC 6/TG 1 study.157

657

Table 6. Industries producing nanocellulose, product type, their production capacity and method

658

of production across the world. Reproduced with permission.157 TAPPI NANO, 2015 ISO/TC

659

6/TG 1 study. Cellulose Nanocrystals (CNCs) - Production activities

660 Country

CANADA

Company

Product/ Trade name

Production Capacity

Source/Method

CelluForce*

NCCTM

1 ton/day

Bleached kraft pulp Sulfuric acid hydrolysis

Alberta Innovates (AITF)

CNCs

20 kg/day

MCC, bleached kraft pulps (softwood and hardwood), dissolving pulp Sulfuric acid hydrolysis

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Page 50 of 70

Blue Goose Biorefineries Inc.

CNCs

10 kg/day

Lignocellulosic feedstocks including wood, grasses and cereal straws Oxidative, nanocatalytic process

FP Innovations

CNCs

2 kg/day

Bleached chemical pulp and others Sulfuric acid hydrolysis

American Process Inc.**

Nanocellulose BioPlusTM CNCs Lignin-coated hydrophobic CNCs

0.5 ton/day (est.)

Wood chips, Agricultural residues Bamboo, grasses USA Sulfur dioxide and ethanol pretreatment (Patented AVAP® technology)

USDA‐Forest Service‐Forest Products Laboratory (FPL)

Aqueous suspensions Freeze‐dried CNCs

50 kg/week

Wood pulp, Sulfuric acid hydrolysis

SWEDEN

MoRe Research backed by Holmen Pulp and Paper and SP Technical Research Institute of Sweden

Nanocrystalline cellulose

0.1 ton/day pilot plant in place during first half of 2016

Paper industry sludge Controlled sulfuric acid hydrolysis + washing, sonication Based on technology by Melodea

ISRAEL

Melodea Ltd. backed by Holmen Pulp and Paper, Sweden

Nanocrystalline cellulose (NCC) NCC foam

--

Paper industry sludge Bleached pulp Flax, Hemp Hydrolysis + washing, sonication

USA

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ACS Sustainable Chemistry & Engineering

IRAN

CHINA

INDIA

Nano Novin Polymer Co

Bacterial nanocellulose

--

Bacterial cellulose Production of cellulose nanofibers using bottom-up approach of bacterial synthesis Provide nanocellulose and other bio-based nanopolymers using top-down approaches

Tianjin Haojia Cellulose Co., Ltd.

CNCs Suspension Spray-dried Freeze-dried Chemically modified?

--

Dissolving pulp Cotton Bleached kraft pulp (softwood, hardwood) Mechanical shearing + combined enzymatic and acidic hydrolysis

Indian Council of Agricultural Research - Central Institute for Research on Cotton Technology (ICAR-CIRCOT)

CNCs and CNFs

10 kg/day

Cotton linters MCC from short staple cotton fibers Sugarcane bagasse, other agro-biomass Novel microbial, enzymatic and chemo-mechanical processes, e.g. in membrane reactor for continuous hydrolysis and removal of nanocellulose without substrate inhibition

661 662 663 664 665 666 667

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Nanofibrillated cellulose (NFCs) - Production activities

668 669

Country

Company

Product/ Trade name

Kruger Bioproducts Inc.** FILOCELL

Cellulose filaments

Production Capacity

5 tons/day

Source/Method

Bleached kraft pulp or TMP Mechanical treatment

CANADA Performance BioFilaments Inc.**

Cellulose filaments

Bleached kraft pulp or TMP --

Wet fluff form or rolls of dried film

GreenCore Composites Inc.**

NCellTM

--

Natural fiberreinforced thermoplastics

Mechanical treatment

Wood or agricultural fibers “In-situ generation of lignocellulosic microfibers” PP or PE matrix reinforced with up to 40% natural cellulosic microfibers

USA

American Process Inc.

Nanocellulose BioPlusTM

(AVAPCO)**

CNFs

0.5 ton/day (est.)

Agricultural residues SO2/ethanol pulping

Lignin-coated hydrophobic CNFs USDA‐Forest Service‐Forest Products Laboratory (FPL)

CNFs

UMaine

CNFs

Wood chips

Mechanical treatment

1 kg/week

Aqueous suspensions Freeze‐dried

Wood pulp TEMPO oxidation and mechanical treatment

1 ton/week

Aqueous suspensions

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Wood pulp Mass colloider grinder

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paperlogic

CNFs

--

Planned for first half of 2015 Borregaard NORWAY

Norske Skog Saugbrugs

SWEDEN

Innventia AB

Wood pulp Mechanical treatment

CMFs

~3 ton/day

“Specialty cellulose”

“Exilva MFC”

planned for mid2016

Mechanical treatment

CMFs/

Pilot plant

nanocellulose

planned as of Dec 2013

Thermomechanical pulp

CMFs

High pressure treatment

100 kg/day

Wood fibers

pilot plant

Chemical and/or enzyme pre-treatment, Mechanical treatment (homogenization)

Mobile demo plant July 2014, planned with BillerudKorsnäs

FINLAND

UPM-Kymmene Ltd.*

BiofibrilsTM

Pilot-scale

Wood fibers

demo plant

Mechanical treatment

“For trials at UPM mills” VTT*

CNFs

Pilot scale

collaboration with Aalto U, UPM

Roll-to-roll film

Stora Enso Ltd.

CMFs

Pilot plant

Wood fibers

“Microcellulose”

started up end 2011

Mechanical treatment

Birch fibril pulp Mechanical treatment

670 671

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UK

Zelfo Technology GmbH

MFC

--

Page 54 of 70

Cellulose fibres, fibrebased waste (recycled) CORE technology enables modification of cellulose fibres using minimum energy BASF SE owns exclusive rights to industrialise Zelfo MFC fibre technology within pulp, paper and board industries

CelluComp

CNFs

11 partners in 5 countries,

Curran®

supported by Strathclyde U and Reading U, coordinated by Institute of Nanotechnology UK Imerys

Small plant running

Waste streams of root vegetables “Proprietary technology”

Paste/slurry Powder Thin sheets Composites

FibreLean MFC combination of kaolin or calcium carbonate with MFCs

1000 to > 10,000 tons/year

Range of (wood) pulp species No fiber pretreatment; co-grinding mineral with fiber On trial by Imerys customers in a wide range of papers

FRANCE

CTP/FCBA

CMFs/CNFs

InTechFibres

~ 0.1 ton/day capacity 100 g to 80 kg CMF/CNF

partnership (to summer 2014)

Lignocellulosics TEMPO-catalyzed oxidation Meca-enzymatic pretreatments Other pre-treatments Ariete NS3075H 1000 L/h, 55 kW motor, 1500 bars maxi Semi-industrial production For research

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applications: Panther homogenizer 50 L/h and lab microfluidizer

SWITZERLAND

GERMANY

NETHERLANDS/UK

IRAN

InoFib

CMFs

LGP2 start-up

Modified CMFs

Swiss Federal Laboratories for Materials Science and Technology Empa

CNFs

J. Rettenmaier & Söhne GmbH

CMFs

Sappi

CNFs

in partnership with Edinburgh Napier University, on Brightlands Chemelot Campus in Sittard-Geleen, the Netherlands

dry powder readily redispersed in water

Nano Novin Polymer Co

Industry

unavailable

Cellulosic fibres Mechanical treatment

15 kg/day

Wood and other lignocellulosic fiber sources Enzymatic pre-treatment Microfluidizer

--

--

8 tons/year target

Wood fibres

(maybe)

(pilot plant) planned for early 2016

--

“New low-cost process” CNFs with unique morphology, specifically modified for either hydrophobic or hydrophilic applications

Bacterial cellulose Production of cellulose nanofibers using bottom-up approach of bacterial synthesis Provide nanocellulose and other bio-based nanopolymers using topdown approaches

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CHINA

Tianjin Haojia Cellulose Co., Ltd.

CNFs

--

Modified CNFs TEMPO-oxidized, cationized, carboxymethylated, polymer grafted

Page 56 of 70

Dissolving cotton pulp Bleached sulfate pulp (soft- and hardwood) High pressure homogenizer -orSuper micro-grinder

INDIA

Indian Council of Agricultural Research Central Institute for Research on Cotton Technology

CNFs

10 kg/day

Cotton linters

and CNCs

Pilot plant

MCC from short staple cotton fibers Sugarcane bagasse Other agro-biomass

(ICARCIRCOT)

JAPAN

Novel microbial, enzymatic and chemomechanical processes, e.g. in membrane reactor for continuous hydrolysis and simultaneous removal of nano-cellulose without substrate inhibition

Daicel**

Nano CelishTM

--

Purified pulp

filtration/food/industrial grades

10-35% solids

Mechanical treatment

Dai-ichi Kogyo Seiyaku Co., Ltd.

“Cellulose single nanofiber”:

50 ton/year

NO INFO

2% solids

TEMPO oxidation

Daio Paper

CNFs

--

NO INFO

RheocrystaTM

Mechanical treatment, etc.

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ACS Sustainable Chemistry & Engineering

Sugino Machine

Chuetsu Pulp & Paper

BiNFi-s

--

NO INFO

Biomass nanofiber

2, 5, 10% solids

Ultra-high pressure water jet

CNFs

--

Bleached kraft pulp:

CNF/plastic composites

Bamboo, Softwood/Hardwood Aqueous counter collision

Nippon Paper Industries*

CNFs CellenpiaTM

> 30 ton/year (> 0.1 ton/day)

Wood pulp TEMPO oxidation Carboxymethylation Mechanical treatment

Oji Holdings

CNFs

--

Chemical modification Mechanical treatment

Asahi Kasei**

PreciséTM

--

--

--

Wood pulp

(non-woven containing CNFs)

Seiko PMC

CNF nanocomposites Mentioned in slide from TAPPI Nano conference, holds patent with DIC Products

Mechanical treatment + Hydrophobization

DIC Corporation

CNF/plastic nanocomposites

--

--

Tokushu Tokai Paper

Absorbent products

--

No information on company website

(SAP and CNF)

672 673

Though the nanocellulose could be commercially available, the preparation methods of

674

nanocellulose involves multiple steps and demands many harsh chemicals. The recovery

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675

methods should also be developed. These short comings should be overcome and single step

676

preparation methods should be developed by the researchers. In recent times, the researchers also

677

concentrate on the recovery of lignin and hemicelluloses that are removed during the purification

678

process for their further use in different applications. The new sources like agriculture and

679

industrial wastes should be considered for the preparation of NC industrially. The properties of

680

the NC from these sources are also promising when compared to that of NC from wood sources.

681

Since the crop and industrial wastes are abundant everywhere in the world, they can be used in

682

number of applications worldwide.

683

CONCLUSION:

684

This review has presented the detailed study on the preparation and properties of the

685

nanocellulose obtained from the crop and industrial wastes, application of NC from various

686

sources and the most recent industrial trend of wood based NC. This review emphasizes the use

687

of agriculture and industrial wastes in the field of nanotechnology and it should be explored

688

more by the researchers and industries. The fore mentioned sources are not only easily available,

689

cost effective and diverse in properties but also, they can produce the value-added nanomaterials

690

which will create new economy and acts as most suitable raw material for the NC production.

691

While the applications of NC have been explored in different fields as composites, films,

692

hydrogels and aerogels, many new age applications in the form of smart materials, stiffer carbon

693

fibers, printing ink and electronic devices should be explored. With the ever-increasing

694

environment concerns and moving towards green materials, the researchers should think about

695

outside the box applications to move the cellulose nanomaterials forward considering the

696

alternative sustainable raw materials like agriculture and industrial wastes.

697

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ACS Sustainable Chemistry & Engineering

698 699 700 701 702 703 704 705 706 707 708 709 710

Author information:

711

Corresponding Authors

712

*Email: [email protected]

713

*Email: [email protected]

714

Address: 730 Rue Bernard, Granby, Quebec, J2J 0H6, Canada.

715

Note: The authors declare no competing financial interest.

716

Biographies: 717

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718

Malladi Rajinipriya is a PhD student, under Prof. Mathieu Robert and Prof. Said Elkoun at

719

University of Sherbrooke, Canada. She is a master graduate from University Joseph Fourier in

720

Nano chemistry and nanomaterials. She worked as a Research chemist in analytical department

721

at Gland Pharma Ltd, Hyderabad, India. She is currently working on extraction of nanocellulose

722

from agriculture and industrial wastes and its applications.

723 724 725

Dr. Malladi Nagalakshmaiah currently postdoctoral researcher at University of

726

Sherbrooke, Canada. He received his PhD in 2016 from university of Grenoble

727

Alpes, France. His PhD research was on the melt processing of cellulose

728

nanocrystals: thermal, mechanical and rheological properties of nanocomposites.

729

His research interests are Biorefinery, Biomaterials, Nanocellulose, Surface modification,

730

Polymer nano composites. 731

Prof. Saïd Elkoun

732

Pr. Saïd Elkoun is Professor and head of the Mechanical Engineering

733

Department at the Faculty of Engineering of Université de Sherbrooke, Canada

734

(UdeS). Pr Elkoun is also co-founder and scientific co-director of the Center for

735

Innovation in Technological Eco-design (CITE). His expertise is on polymer crystallization,

736

processing-microstructure-property relationships of polymers, biopolymers and nanocomposites.

737 738

Dr. Mathieu Robert is Professor at the Faculty of Engineering of Université de

739

Sherbrooke, Canada (UdeS). Pr Robert is also Chair holder of the Canada

740

research chair on polymer Eco composites and scientific co-director of the

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ACS Sustainable Chemistry & Engineering

741

Center for Innovation in Technological Eco-design (CITE). He is a material scientist with an

742

expertise in the elaboration, characterization and durability study of bio-based composite

743

materials. His current research interests deal with the extraction, pre-treatment, functionalization

744

and characterization of bio-sourced reinforcements from agriculture wastes.

745

ACKNOWLEDGEMENTS:

746

The authors want to thank National Science and Engineering Research Council” (NSERC) of

747

Canada, the “Centre québecois des matériaux fonctionnels” (CQMF) and the “Consortium de

748

Recherché ET Innovations en Bioprocédés Industriels du Québec” (CRIBIQ) of Fonds de

749

recherche du Québec – Nature ET technologies (FRQNT).

750 751 752 753

REFERENCES:

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(1)

(2)

(3) (4) (5) (6)

(7)

Klemm, D.; Kramer, F.; Moritz, S.; Lindström, T.; Ankerfors, M.; Gray, D.; Dorris, A. Nanocelluloses: A New Family of Nature-Based Materials. Angew. Chem. Int. Ed. 2011, 50 (24), 5438–5466 DOI: 10.1002/anie.201001273. Charreau, H.; L Foresti, M.; Vázquez, A. Nanocellulose Patents Trends: A Comprehensive Review on Patents on Cellulose Nanocrystals, Microfibrillated and Bacterial Cellulose. Recent Pat. Nanotechnol. 2013, 7 (1), 56–80. Yano, H.; Nakahara, S. Bio-Composites Produced from Plant Microfiber Bundles with a Nanometer Unit Web-like Network. J. Mater. Sci. 2004, 39 (5), 1635–1638. de Souza Lima, M. M.; Borsali, R. Rodlike Cellulose Microcrystals: Structure, Properties, and Applications. Macromol. Rapid Commun. 2004, 25 (7), 771–787 DOI: 10.1002/marc.200300268. Chen, H. Chemical Composition and Structure of Natural Lignocellulose. In Biotechnology of lignocellulose; Springer, 2014; pp 25–71. Dungani, R.; Karina, M.; . S.; Sulaeman, A.; Hermawan, D.; Hadiyane, A. Agricultural Waste Fibers Towards Sustainability and Advanced Utilization: A Review. Asian J. Plant Sci. 2016, 15 (1), 42– 55 DOI: 10.3923/ajps.2016.42.55. Doree, C. Methods in Cellulose Chemistry. 1947.

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(8)

(9) (10)

(11) (12) (13)

(14)

(15)

(16)

(17) (18)

(19)

(20) (21)

(22)

(23) (24) (25)

Abitbol, T.; Rivkin, A.; Cao, Y.; Nevo, Y.; Abraham, E.; Ben-Shalom, T.; Lapidot, S.; Shoseyov, O. Nanocellulose, a Tiny Fiber with Huge Applications. Curr. Opin. Biotechnol. 2016, 39, 76–88 DOI: 10.1016/j.copbio.2016.01.002. Jack Miller. NANOCELLULOSE STATE OF THE INDUSTRY. Tappi Nano.org December 2015. Abdul Khalil, H. P. S.; Davoudpour, Y.; Islam, M. N.; Mustapha, A.; Sudesh, K.; Dungani, R.; Jawaid, M. Production and Modification of Nanofibrillated Cellulose Using Various Mechanical Processes: A Review. Carbohydr. Polym. 2014, 99, 649–665 DOI: 10.1016/j.carbpol.2013.08.069. Nechyporchuk, O.; Belgacem, M. N.; Bras, J. Production of Cellulose Nanofibrils: A Review of Recent Advances. Ind. Crops Prod. 2016, 93, 2–25 DOI: 10.1016/j.indcrop.2016.02.016. Habibi, Y.; Lucia, L. A.; Rojas, O. J. Cellulose Nanocrystals: Chemistry, Self-Assembly, and Applications. Chem. Rev. 2010, 110 (6), 3479–3500 DOI: 10.1021/cr900339w. Mariano, M.; El Kissi, N.; Dufresne, A. Cellulose Nanocrystals and Related Nanocomposites: Review of Some Properties and Challenges. J. Polym. Sci. Part B Polym. Phys. 2014, 52 (12), 791– 806 DOI: 10.1002/polb.23490. Trache, D.; Hussin, M. H.; Haafiz, M. K. M.; Thakur, V. K. Recent Progress in Cellulose Nanocrystals: Sources and Production. Nanoscale 2017, 9 (5), 1763–1786 DOI: 10.1039/C6NR09494E. Kalia, S.; Kaith, B. S.; Kaur, I. Pretreatments of Natural Fibers and Their Application as Reinforcing Material in Polymer Composites-A Review. Polym. Eng. Sci. 2009, 49 (7), 1253–1272 DOI: 10.1002/pen.21328. Moon, R. J.; Martini, A.; Nairn, J.; Simonsen, J.; Youngblood, J. Cellulose Nanomaterials Review: Structure, Properties and Nanocomposites. Chem. Soc. Rev. 2011, 40 (7), 3941 DOI: 10.1039/c0cs00108b. Mohammadinejad, R.; Karimi, S.; Iravani, S.; Varma, R. S. Plant-Derived Nanostructures: Types and Applications. Green Chem 2016, 18 (1), 20–52 DOI: 10.1039/C5GC01403D. García, A.; Gandini, A.; Labidi, J.; Belgacem, N.; Bras, J. Industrial and Crop Wastes: A New Source for Nanocellulose Biorefinery. Ind. Crops Prod. 2016, 93, 26–38 DOI: 10.1016/j.indcrop.2016.06.004. Faruk, O.; Bledzki, A. K.; Fink, H.-P.; Sain, M. Biocomposites Reinforced with Natural Fibers: 2000–2010. Prog. Polym. Sci. 2012, 37 (11), 1552–1596 DOI: 10.1016/j.progpolymsci.2012.04.003. Madison, W. Density, Fiber Length, and Yields of Pulp for Various Species of Wood. 1953. Martí-Ferrer, F.; Vilaplana, F.; Ribes-Greus, A.; Benedito-Borrás, A.; Sanz-Box, C. Flour Rice Husk as Filler in Block Copolymer Polypropylene: Effect of Different Coupling Agents. J. Appl. Polym. Sci. 2006, 99 (4), 1823–1831 DOI: 10.1002/app.22717. Hoareau, W.; Trindade, W. G.; Siegmund, B.; Castellan, A.; Frollini, E. Sugar Cane Bagasse and Curaua Lignins Oxidized by Chlorine Dioxide and Reacted with Furfuryl Alcohol: Characterization and Stability. Polym. Degrad. Stab. 2004, 86 (3), 567–576 DOI: 10.1016/j.polymdegradstab.2004.07.005. Mohanty, A. K.; Misra, M.; Drzal, L. T. Natural Fibers, Biopolymers, and Biocomposites; CRC press, 2005. Li, R.; Fei, J.; Cai, Y.; Li, Y.; Feng, J.; Yao, J. Cellulose Whiskers Extracted from Mulberry: A Novel Biomass Production. Carbohydr. Polym. 2009, 76 (1), 94–99 DOI: 10.1016/j.carbpol.2008.09.034. Kallel, F.; Bettaieb, F.; Khiari, R.; García, A.; Bras, J.; Chaabouni, S. E. Isolation and Structural Characterization of Cellulose Nanocrystals Extracted from Garlic Straw Residues. Ind. Crops Prod. 2016, 87, 287–296 DOI: 10.1016/j.indcrop.2016.04.060.

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(27) (28)

(29) (30) (31) (32)

(33) (34) (35) (36) (37) (38) (39)

(40) (41) (42) (43)

(44)

(45)

(46)

Siqueira, G.; Oksman, K.; Tadokoro, S. K.; Mathew, A. P. Re-Dispersible Carrot Nanofibers with High Mechanical Properties and Reinforcing Capacity for Use in Composite Materials. Compos. Sci. Technol. 2016, 123, 49–56 DOI: 10.1016/j.compscitech.2015.12.001. Bano, S.; Negi, Y. S. Studies on Cellulose Nanocrystals Isolated from Groundnut Shells. Carbohydr. Polym. 2017, 157, 1041–1049 DOI: 10.1016/j.carbpol.2016.10.069. Rhim, J.-W.; Reddy, J. P.; Luo, X. Isolation of Cellulose Nanocrystals from Onion Skin and Their Utilization for the Preparation of Agar-Based Bio-Nanocomposites Films. Cellulose 2015, 22 (1), 407–420 DOI: 10.1007/s10570-014-0517-7. Klemm, D.; Heublein, B.; Fink, H.-P.; Bohn, A. Cellulose: Fascinating Biopolymer and Sustainable Raw Material. Angew. Chem. Int. Ed. 2005, 44 (22), 3358–3393 DOI: 10.1002/anie.200460587. George, J.; S N, S. Cellulose Nanocrystals: Synthesis, Functional Properties, and Applications. Nanotechnol. Sci. Appl. 2015, 45 DOI: 10.2147/NSA.S64386. Cave, I.; Walker, J. Stiffness of Wood in Fast-Grown Plantation Softwoods: The Influence of Microfibril Angle. For. Prod. J. 1994, 44 (5), 43. Yokouchi, M.; Sakakibara, Y.; Chatani, Y.; Tadokoro, H.; Tanaka, T.; Yoda, K. Structures of Two Crystalline Forms of Poly (Butylene Terephthalate) and Reversible Transition between Them by Mechanical Deformation. Macromolecules 1976, 9 (2), 266–273. Habibi, Y.; Lucia, L. A.; Rojas, O. J. Cellulose Nanocrystals: Chemistry, Self-Assembly, and Applications. Chem. Rev. 2010, 110 (6), 3479–3500 DOI: 10.1021/cr900339w. Gaffey, M. J. Spectral Reflectance Characteristics of the Meteorite Classes. J. Geophys. Res. 1976, 81 (5), 905–920. HATTORI. New Solvents for Cellulose. II. Ethylenediamine/Thiocyanate Salt System. 2003. Kuga, S.; Takagi, S.; Brown, R. M. Native Folded-Chain Cellulose II. Polymer 1993, 34 (15), 3293– 3297 DOI: 10.1016/0032-3861(93)90404-X. Marrinan, H. J.; Mann, J. Infrared Spectra of the Crystalline Modifications of Cellulose. J. Polym. Sci. 1956, 21 (98), 301–311. Gardiner, E. S.; Sarko, A. Packing Analysis of Carbohydrates and Polysaccharides. 16. The Crystal Structures of Celluloses IVI and IVII. Can. J. Chem. 1985, 63 (1), 173–180. Estela, R.; Luis, J. Hydrolysis of Biomass Mediated by Cellulases for the Production of Sugars. In Sustainable Degradation of Lignocellulosic Biomass - Techniques, Applications and Commercialization; Chandel, A., Ed.; InTech, 2013. Scheller, H. V.; Ulvskov, P. Hemicelluloses. Annu. Rev. Plant Biol. 2010, 61 (1), 263–289 DOI: 10.1146/annurev-arplant-042809-112315. Ebringerová, A.; Hromádková, Z.; Heinze, T. Hemicellulose. In Polysaccharides I; Heinze, T., Ed.; Springer-Verlag: Berlin/Heidelberg, 2005; Vol. 186, pp 1–67. Eero Kontturi. Hemicellulose: Structure, Characterization, Dissolution, Modification, 2015. Kozioł, A.; Cybulska, J.; Pieczywek, P. M.; Zdunek, A. Evaluation of Structure and Assembly of Xyloglucan from Tamarind Seed (Tamarindus Indica L.) with Atomic Force Microscopy. Food Biophys. 2015, 10 (4), 396–402 DOI: 10.1007/s11483-015-9395-2. Arola, S.; Malho, J.; Laaksonen, P.; Lille, M.; Linder, M. B. The Role of Hemicellulose in Nanofibrillated Cellulose Networks. Soft Matter 2013, 9 (4), 1319–1326 DOI: 10.1039/C2SM26932E. Chaker, A.; Alila, S.; Mutjé, P.; Vilar, M. R.; Boufi, S. Key Role of the Hemicellulose Content and the Cell Morphology on the Nanofibrillation Effectiveness of Cellulose Pulps. Cellulose 2013, 20 (6), 2863–2875 DOI: 10.1007/s10570-013-0036-y. Zhang, J.; Chen, Y.; Brook, M. A. Reductive Degradation of Lignin and Model Compounds by Hydrosilanes. ACS Sustain. Chem. Eng. 2014, 2 (8), 1983–1991 DOI: 10.1021/sc500302j.

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(47) (48) (49) (50)

(51)

(52)

(53) (54) (55) (56) (57)

(58) (59)

(60) (61) (62) (63)

(64) (65)

(66)

Doherty, W. O. S.; Mousavioun, P.; Fellows, C. M. Value-Adding to Cellulosic Ethanol: Lignin Polymers. Ind. Crops Prod. 2011, 33 (2), 259–276 DOI: 10.1016/j.indcrop.2010.10.022. Lora, J. H.; Glasser, W. G. Recent Industrial Applications of Lignin: A Sustainable Alternative to Nonrenewable Materials. J. Polym. Environ. 2002, 10 (1), 39–48. E Sjostrom. Wood Chemistry: Fundamentals and Applications. 1981. Xiao, S.; Gao, R.; Gao, L.; Li, J. Poly(vinyl Alcohol) Films Reinforced with Nanofibrillated Cellulose (NFC) Isolated from Corn Husk by High Intensity Ultrasonication. Carbohydr. Polym. 2016, 136, 1027–1034 DOI: 10.1016/j.carbpol.2015.09.115. Sacui, I. A.; Nieuwendaal, R. C.; Burnett, D. J.; Stranick, S. J.; Jorfi, M.; Weder, C.; Foster, E. J.; Olsson, R. T.; Gilman, J. W. Comparison of the Properties of Cellulose Nanocrystals and Cellulose Nanofibrils Isolated from Bacteria, Tunicate, and Wood Processed Using Acid, Enzymatic, Mechanical, and Oxidative Methods. ACS Appl. Mater. Interfaces 2014, 6 (9), 6127–6138 DOI: 10.1021/am500359f. Yoon, S. H.; Jin, H.-J.; Kook, M.-C.; Pyun, Y. R. Electrically Conductive Bacterial Cellulose by Incorporation of Carbon Nanotubes. Biomacromolecules 2006, 7 (4), 1280–1284 DOI: 10.1021/bm050597g. Lim, Y.-M.; Gwon, H.-J.; Jeun, J. P.; Nho, Y.-C. Preparation of Cellulose-Based Nanofibers Using Electrospinning. In Nanofibers; InTech, 2010. Turbak, A. .; Snyder, F.W.; Sandberg, K.R. Microfibrillated Cellulose, a New Cellulose Product: Properties, Uses, and Commercial Potential. 1983. Herrick, F. W.; Casebier, R. L.; Hamilton, J. K.; Sandberg, K. R. Microfibrillated Cellulose: Morphology and Accessibility; ITT Rayonier Inc., Shelton, WA, 1983; Vol. 37. Ranby. Aqeous Colliodal Solutions of Cellulose Micelles. 1949. Ehmann, H. M. A.; Mohan, T.; Koshanskaya, M.; Scheicher, S.; Breitwieser, D.; Ribitsch, V.; StanaKleinschek, K.; Spirk, S. Design of Anticoagulant Surfaces Based on Cellulose Nanocrystals. Chem Commun 2014, 50 (86), 13070–13072 DOI: 10.1039/C4CC05254D. Nickerson, R. F.; Habrle, J. A. Cellulose Intercrystalline Structure. Ind. Eng. Chem. 1947, 39 (11), 1507–1512. Dugan, J. M.; Gough, J. E.; Eichhorn, S. J. Bacterial Cellulose Scaffolds and Cellulose Nanowhiskers for Tissue Engineering. Nanomed. 2013, 8 (2), 287–298 DOI: 10.2217/nnm.12.211. Dong, X. M.; Revol, J.-F.; Gray, D. G. Effect of Microcrystallite Preparation Conditions on the Formation of Colloid Crystals of Cellulose. Cellulose 1998, 5 (1), 19–32. Marchessault et al. Liquid Crystal Systems from Fibrillar Polysaccharides. 1959. Revol, J.-F.; Bradford, H.; Giasson, J.; Marchessault, R.; Gray, D. Helicoidal Self-Ordering of Cellulose Microfibrils in Aqueous Suspension. Int. J. Biol. Macromol. 1992, 14 (3), 170–172. El-Saied, H.; Basta, A. H.; Gobran, R. H. Research Progress in Friendly Environmental Technology for the Production of Cellulose Products (Bacterial Cellulose and Its Application). Polym.-Plast. Technol. Eng. 2004, 43 (3), 797–820 DOI: 10.1081/PPT-120038065. Ramakrishna, S.; Fujihara, K.; Teo, W.-E.; Yong, T.; Ma, Z.; Ramaseshan, R. Electrospun Nanofibers: Solving Global Issues. Mater. Today 2006, 9 (3), 40–50. Konwarh, R.; Karak, N.; Misra, M. Electrospun Cellulose Acetate Nanofibers: The Present Status and Gamut of Biotechnological Applications. Biotechnol. Adv. 2013, 31 (4), 421–437 DOI: 10.1016/j.biotechadv.2013.01.002. Graedel, T. E.; Allwood, J.; Birat, J.-P.; Buchert, M.; Hagelüken, C.; Reck, B. K.; Sibley, S. F.; Sonnemann, G.; United Nations Environment Programme; Working Group on the Global Metal Flows. Recycling Rates of Metals: A Status Report; United Nations Environment Programme: Nairobi, Kenya, 2011.

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(81)

(82)

Dufresne, A.; Cavaill�, J.-Y.; Vignon, M. R. Mechanical Behavior of Sheets Prepared from Sugar Beet Cellulose Microfibrils. J. Appl. Polym. Sci. 1997, 64 (6), 1185–1194 DOI: 10.1002/(SICI)10974628(19970509)64:63.0.CO;2-V. Nagalakshmaiah, M.; kissi, N. E.; Mortha, G.; Dufresne, A. Structural Investigation of Cellulose Nanocrystals Extracted from Chili Leftover and Their Reinforcement in Cariflex-IR Rubber Latex. Carbohydr. Polym. 2016, 136, 945–954 DOI: 10.1016/j.carbpol.2015.09.096. Dittenber, D. B.; GangaRao, H. V. S. Critical Review of Recent Publications on Use of Natural Composites in Infrastructure. Compos. Part Appl. Sci. Manuf. 2012, 43 (8), 1419–1429 DOI: 10.1016/j.compositesa.2011.11.019. Bhatnagar, A. Processing of Cellulose Nanofiber-Reinforced Composites. J. Reinf. Plast. Compos. 2005, 24 (12), 1259–1268 DOI: 10.1177/0731684405049864. Wang, B.; Sain, M. Isolation of Nanofibers from Soybean Source and Their Reinforcing Capability on Synthetic Polymers. Compos. Sci. Technol. 2007, 67 (11–12), 2521–2527 DOI: 10.1016/j.compscitech.2006.12.015. Zuluaga, R.; Putaux, J. L.; Cruz, J.; Vélez, J.; Mondragon, I.; Gañán, P. Cellulose Microfibrils from Banana Rachis: Effect of Alkaline Treatments on Structural and Morphological Features. Carbohydr. Polym. 2009, 76 (1), 51–59 DOI: 10.1016/j.carbpol.2008.09.024. Habibi, Y.; Mahrouz, M.; Vignon, M. R. Microfibrillated Cellulose from the Peel of Prickly Pear Fruits. Food Chem. 2009, 115 (2), 423–429 DOI: 10.1016/j.foodchem.2008.12.034. Cherian, B. M.; Leão, A. L.; de Souza, S. F.; Thomas, S.; Pothan, L. A.; Kottaisamy, M. Isolation of Nanocellulose from Pineapple Leaf Fibres by Steam Explosion. Carbohydr. Polym. 2010, 81 (3), 720–725 DOI: 10.1016/j.carbpol.2010.03.046. Rosa, M. F.; Medeiros, E. S.; Malmonge, J. A.; Gregorski, K. S.; Wood, D. F.; Mattoso, L. H. C.; Glenn, G.; Orts, W. J.; Imam, S. H. Cellulose Nanowhiskers from Coconut Husk Fibers: Effect of Preparation Conditions on Their Thermal and Morphological Behavior. Carbohydr. Polym. 2010, 81 (1), 83–92 DOI: 10.1016/j.carbpol.2010.01.059. Pasquini, D.; Teixeira, E. de M.; Curvelo, A. A. da S.; Belgacem, M. N.; Dufresne, A. Extraction of Cellulose Whiskers from Cassava Bagasse and Their Applications as Reinforcing Agent in Natural Rubber. Ind. Crops Prod. 2010, 32 (3), 486–490 DOI: 10.1016/j.indcrop.2010.06.022. Deepa, B.; Abraham, E.; Cherian, B. M.; Bismarck, A.; Blaker, J. J.; Pothan, L. A.; Leao, A. L.; de Souza, S. F.; Kottaisamy, M. Structure, Morphology and Thermal Characteristics of Banana Nano Fibers Obtained by Steam Explosion. Bioresour. Technol. 2011, 102 (2), 1988–1997 DOI: 10.1016/j.biortech.2010.09.030. Xiao, S.; Gao, R.; Gao, L.; Li, J. Poly(vinyl Alcohol) Films Reinforced with Nanofibrillated Cellulose (NFC) Isolated from Corn Husk by High Intensity Ultrasonication. Carbohydr. Polym. 2016, 136, 1027–1034 DOI: 10.1016/j.carbpol.2015.09.115. Baheti, V.; Abbasi, R.; Militky, J. Ball Milling of Jute Fibre Wastes to Prepare Nanocellulose. World J. Eng. 2012, 9 (1), 45–50. Johar, N.; Ahmad, I.; Dufresne, A. Extraction, Preparation and Characterization of Cellulose Fibres and Nanocrystals from Rice Husk. Ind. Crops Prod. 2012, 37 (1), 93–99 DOI: 10.1016/j.indcrop.2011.12.016. Lu, P.; Hsieh, Y.-L. Cellulose Isolation and Core–shell Nanostructures of Cellulose Nanocrystals from Chardonnay Grape Skins. Carbohydr. Polym. 2012, 87 (4), 2546–2553 DOI: 10.1016/j.carbpol.2011.11.023. Li, J.; Wei, X.; Wang, Q.; Chen, J.; Chang, G.; Kong, L.; Su, J.; Liu, Y. Homogeneous Isolation of Nanocellulose from Sugarcane Bagasse by High Pressure Homogenization. Carbohydr. Polym. 2012, 90 (4), 1609–1613 DOI: 10.1016/j.carbpol.2012.07.038.

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(97)

(98) (99)

Purkait, B. S.; Ray, D.; Sengupta, S.; Kar, T.; Mohanty, A.; Misra, M. Isolation of Cellulose Nanoparticles from Sesame Husk. Ind. Eng. Chem. Res. 2011, 50 (2), 871–876 DOI: 10.1021/ie101797d. Chen, D.; Lawton, D.; Thompson, M. R.; Liu, Q. Biocomposites Reinforced with Cellulose Nanocrystals Derived from Potato Peel Waste. Carbohydr. Polym. 2012, 90 (1), 709–716 DOI: 10.1016/j.carbpol.2012.06.002. Morais, J. P. S.; Rosa, M. de F.; de Souza Filho, M. de sá M.; Nascimento, L. D.; do Nascimento, D. M.; Cassales, A. R. Extraction and Characterization of Nanocellulose Structures from Raw Cotton Linter. Carbohydr. Polym. 2013, 91 (1), 229–235 DOI: 10.1016/j.carbpol.2012.08.010. Wang, Q. Q.; Zhu, J. Y.; Gleisner, R.; Kuster, T. A.; Baxa, U.; McNeil, S. E. Morphological Development of Cellulose Fibrils of a Bleached Eucalyptus Pulp by Mechanical Fibrillation. Cellulose 2012, 19 (5), 1631–1643 DOI: 10.1007/s10570-012-9745-x. Jiang, F.; Hsieh, Y.-L. Chemically and Mechanically Isolated Nanocellulose and Their SelfAssembled Structures. Carbohydr. Polym. 2013, 95 (1), 32–40 DOI: 10.1016/j.carbpol.2013.02.022. Rehman, N.; de Miranda, M. I. G.; Rosa, S. M. L.; Pimentel, D. M.; Nachtigall, S. M. B.; Bica, C. I. D. Cellulose and Nanocellulose from Maize Straw: An Insight on the Crystal Properties. J. Polym. Environ. 2013 DOI: 10.1007/s10924-013-0624-9. Mohamad Haafiz, M. K.; Eichhorn, S. J.; Hassan, A.; Jawaid, M. Isolation and Characterization of Microcrystalline Cellulose from Oil Palm Biomass Residue. Carbohydr. Polym. 2013, 93 (2), 628– 634 DOI: 10.1016/j.carbpol.2013.01.035. Mat Zain, N. F. Preparation and Characterization of Cellulose and Nanocellulose From Pomelo (Citrus Grandis) Albedo. J. Nutr. Food Sci. 2014, 05 (01) DOI: 10.4172/2155-9600.1000334. Karimi, S.; Tahir, P. M.; Karimi, A.; Dufresne, A.; Abdulkhani, A. Kenaf Bast Cellulosic Fibers Hierarchy: A Comprehensive Approach from Micro to Nano. Carbohydr. Polym. 2014, 101, 878– 885 DOI: 10.1016/j.carbpol.2013.09.106. Henrique, M. A.; Silvério, H. A.; Flauzino Neto, W. P.; Pasquini, D. Valorization of an AgroIndustrial Waste, Mango Seed, by the Extraction and Characterization of Its Cellulose Nanocrystals. J. Environ. Manage. 2013, 121, 202–209 DOI: 10.1016/j.jenvman.2013.02.054. Tsukamoto, J.; Durán, N.; Tasic, L. Nanocellulose and Bioethanol Production from Orange Waste Using Isolated Microorganisms. J. Braz. Chem. Soc. 2013 DOI: 10.5935/0103-5053.20130195. Silvério, H. A.; Flauzino Neto, W. P.; Pasquini, D. Effect of Incorporating Cellulose Nanocrystals from Corncob on the Tensile, Thermal and Barrier Properties of Poly(Vinyl Alcohol) Nanocomposites. J. Nanomater. 2013, 2013, 1–9 DOI: 10.1155/2013/289641. Josset, S.; Orsolini, P.; Siqueira, G.; Tejado, A.; Tingaut, P.; Zimmermann, T. Energy Consumption of the Nanofibrillation of Bleached Pulp, Wheat Straw and Recycled Newspaper through a Grinding Process. Nord Pulp Pap Res J 2014, 29 (1), 167–175. Espino, E.; Cakir, M.; Domenek, S.; Román-Gutiérrez, A. D.; Belgacem, N.; Bras, J. Isolation and Characterization of Cellulose Nanocrystals from Industrial by-Products of Agave Tequilana and Barley. Ind. Crops Prod. 2014, 62, 552–559 DOI: 10.1016/j.indcrop.2014.09.017. Mariño, M.; Lopes da Silva, L.; Durán, N.; Tasic, L. Enhanced Materials from Nature: Nanocellulose from Citrus Waste. Molecules 2015, 20 (4), 5908–5923 DOI: 10.3390/molecules20045908. Chen, Y.; Wu, Q.; Huang, B.; Huang, M.; Ai, X. Isolation and Characteristics of Cellulose and Nanocellulose from Lotus Leaf Stalk Agro-Wastes. BioResources 2014, 10 (1), 684–696. Jiang, F.; Hsieh, Y.-L. Cellulose Nanocrystal Isolation from Tomato Peels and Assembled Nanofibers. Carbohydr. Polym. 2015, 122, 60–68 DOI: 10.1016/j.carbpol.2014.12.064.

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ACS Sustainable Chemistry & Engineering

(100)

(101)

(102)

(103)

(104)

(105) (106)

(107)

(108) (109)

(110)

(111)

(112) (113)

(114) (115)

(116) (117)

Mtibe, A.; Mandlevu, Y.; Linganiso, L. Z.; Anandjiwala, R. D. Extraction of Cellulose Nanowhiskers from Flax Fibres and Their Reinforcing Effect on Poly (Furfuryl) Alcohol. J. Biobased Mater. Bioenergy 2015, 9 (3), 309–317. Siqueira, G.; Tapin-Lingua, S.; Bras, J.; da Silva Perez, D.; Dufresne, A. Morphological Investigation of Nanoparticles Obtained from Combined Mechanical Shearing, and Enzymatic and Acid Hydrolysis of Sisal Fibers. Cellulose 2010, 17 (6), 1147–1158 DOI: 10.1007/s10570-0109449-z. Barbosa, A.; Robles, E.; Ribeiro, J.; Lund, R.; Carreño, N.; Labidi, J. Cellulose Nanocrystal Membranes as Excipients for Drug Delivery Systems. Materials 2016, 9 (12), 1002 DOI: 10.3390/ma9121002. Cudjoe, E.; Hunsen, M.; Xue, Z.; Way, A. E.; Barrios, E.; Olson, R. A.; Hore, M. J. A.; Rowan, S. J. Miscanthus Giganteus: A Commercially Viable Sustainable Source of Cellulose Nanocrystals. Carbohydr. Polym. 2017, 155, 230–241 DOI: 10.1016/j.carbpol.2016.08.049. Naz, S.; Ahmad, N.; Akhtar, J.; Ahmad, N. M.; Ali, A.; Zia, M. Management of Citrus Waste by Switching in the Production of Nanocellulose. IET Nanobiotechnol. 2016, 10 (6), 395–399 DOI: 10.1049/iet-nbt.2015.0116. Ludueña, L.; Fasce, D.; Alvarez, V. A. Nanocellulose from Ricehusk Following Alkaline Treatment to Remove Silica. 2011. Chen, W.; Yu, H.; Liu, Y.; Hai, Y.; Zhang, M.; Chen, P. Isolation and Characterization of Cellulose Nanofibers from Four Plant Cellulose Fibers Using a Chemical-Ultrasonic Process. Cellulose 2011, 18 (2), 433–442 DOI: 10.1007/s10570-011-9497-z. Yu, H.; Qin, Z.; Liang, B.; Liu, N.; Zhou, Z.; Chen, L. Facile Extraction of Thermally Stable Cellulose Nanocrystals with a High Yield of 93% through Hydrochloric Acid Hydrolysis under Hydrothermal Conditions. J. Mater. Chem. A 2013, 1 (12), 3938 DOI: 10.1039/c3ta01150j. Koshizawa, T. Degradation of Wood Cellulose and Cotton Linters in Phosphoric Acid. 1960. Sadeghifar, H.; Filpponen, I.; Clarke, S. P.; Brougham, D. F.; Argyropoulos, D. S. Production of Cellulose Nanocrystals Using Hydrobromic Acid and Click Reactions on Their Surface. J. Mater. Sci. 2011, 46 (22), 7344–7355 DOI: 10.1007/s10853-011-5696-0. Satyamurthy, P.; Jain, P.; Balasubramanya, R. H.; Vigneshwaran, N. Preparation and Characterization of Cellulose Nanowhiskers from Cotton Fibres by Controlled Microbial Hydrolysis. Carbohydr. Polym. 2011, 83 (1), 122–129 DOI: 10.1016/j.carbpol.2010.07.029. Iskak, N. A. M.; Julkapli, N. M.; Hamid, S. B. A. Understanding the Effect of Synthesis Parameters on the Catalytic Ionic Liquid Hydrolysis Process of Cellulose Nanocrystals. Cellulose 2017, 24 (6), 2469–2481 DOI: 10.1007/s10570-017-1273-2. Araki, J.; Wada, M.; Kuga, S.; Okano, T. Influence of Surface Charge on Viscosity Behavior of Cellulose Microcrystal Suspension. J. Wood Sci. 1999, 45 (3), 258–261. Elazzouzi-Hafraoui, S.; Nishiyama, Y.; Putaux, J.-L.; Heux, L.; Dubreuil, F.; Rochas, C. The Shape and Size Distribution of Crystalline Nanoparticles Prepared by Acid Hydrolysis of Native Cellulose. Biomacromolecules 2007, 9 (1), 57–65. Kargarzadeh, H.; Ahmad, I.; Thomas, S.; Dufresne, A. Handbook of Nanocellulose and Cellulose Nanocomposites, 2 Volume Set; John Wiley & Sons, 2017. Alemdar, A.; Sain, M. Isolation and Characterization of Nanofibers from Agricultural Residues – Wheat Straw and Soy Hulls. Bioresour. Technol. 2008, 99 (6), 1664–1671 DOI: 10.1016/j.biortech.2007.04.029. Taniguchi, T.; Okamura, K. New Films Produced from Microfibrillated Natural Fibres. 1998. Zimmermann, T.; Pöhler, E.; Geiger, T. Cellulose Fibrils for Polymer Reinforcement. Adv. Eng. Mater. 2004, 6 (9), 754–761 DOI: 10.1002/adem.200400097.

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(118)

(119)

(120) (121) (122) (123)

(124) (125) (126)

(127) (128)

(129)

(130)

(131)

(132)

(133)

(134)

(135)

Saito, T.; Isogai, A. Introduction of Aldehyde Groups on Surfaces of Native Cellulose Fibers by TEMPO-Mediated Oxidation. Colloids Surf. Physicochem. Eng. Asp. 2006, 289 (1–3), 219–225 DOI: 10.1016/j.colsurfa.2006.04.038. Pääkkö, M.; Vapaavuori, J.; Silvennoinen, R.; Kosonen, H.; Ankerfors, M.; Lindström, T.; Berglund, L. A.; Ikkala, O. Long and Entangled Native Cellulose I Nanofibers Allow Flexible Aerogels and Hierarchically Porous Templates for Functionalities. Soft Matter 2008, 4 (12), 2492 DOI: 10.1039/b810371b. Lee, H. V.; Hamid, S. B. A.; Zain, S. K. Conversion of Lignocellulosic Biomass to Nanocellulose: Structure and Chemical Process. Sci. World J. 2014, 2014, e631013 DOI: 10.1155/2014/631013. Siró, I.; Plackett, D. Microfibrillated Cellulose and New Nanocomposite Materials: A Review. Cellulose 2010, 17 (3), 459–494 DOI: 10.1007/s10570-010-9405-y. Sun, Y.; Cheng, J. Hydrolysis of Lignocellulosic Materials for Ethanol Production: A Review. Bioresour. Technol. 2002, 83 (1), 1–11. Nakagaito, A. N.; Yano, H. The Effect of Morphological Changes from Pulp Fiber towards NanoScale Fibrillated Cellulose on the Mechanical Properties of High-Strength Plant Fiber Based Composites. Appl. Phys. Mater. Sci. Process. 2004, 78 (4), 547–552 DOI: 10.1007/s00339-0032453-5. Karande, V. S.; Bharimalla, A. K.; Hadge, G. B.; Mhaske, S. T.; Vigneshwaran, N. Nanofibrillation of Cotton Fibers by Disc Refiner and Its Characterization. 2011. Homogenization (Chemistry). Piorkowski, D. T.; McClements, D. J. Beverage Emulsions: Recent Developments in Formulation, Production, and Applications. Food Hydrocoll. 2014, 42, 5–41 DOI: 10.1016/j.foodhyd.2013.07.009. D Yashwanth Reddy. Cryogenicgrindingrenew-130914065822-phpapp01.pptx. Chaker, A.; Alila, S.; Mutjé, P.; Vilar, M. R.; Boufi, S. Key Role of the Hemicellulose Content and the Cell Morphology on the Nanofibrillation Effectiveness of Cellulose Pulps. Cellulose 2013, 20 (6), 2863–2875 DOI: 10.1007/s10570-013-0036-y. Ferrer, A.; Filpponen, I.; Rodríguez, A.; Laine, J.; Rojas, O. J. Valorization of Residual Empty Palm Fruit Bunch Fibers (EPFBF) by Microfluidization: Production of Nanofibrillated Cellulose and EPFBF Nanopaper. Bioresour. Technol. 2012, 125, 249–255 DOI: 10.1016/j.biortech.2012.08.108. Spence, K. L.; Venditti, R. A.; Rojas, O. J.; Habibi, Y.; Pawlak, J. J. A Comparative Study of Energy Consumption and Physical Properties of Microfibrillated Cellulose Produced by Different Processing Methods. Cellulose 2011, 18 (4), 1097–1111 DOI: 10.1007/s10570-011-9533-z. Alemdar, A.; Sain, M. Isolation and Characterization of Nanofibers from Agricultural Residues – Wheat Straw and Soy Hulls. Bioresour. Technol. 2008, 99 (6), 1664–1671 DOI: 10.1016/j.biortech.2007.04.029. Nagalakshmaiah, M.; kissi, N. E.; Mortha, G.; Dufresne, A. Structural Investigation of Cellulose Nanocrystals Extracted from Chili Leftover and Their Reinforcement in Cariflex-IR Rubber Latex. Carbohydr. Polym. 2016, 136, 945–954 DOI: 10.1016/j.carbpol.2015.09.096. Lee, S.-Y.; Chun, S.-J.; Kang, I.-A.; Park, J.-Y. Preparation of Cellulose Nanofibrils by High-Pressure Homogenizer and Cellulose-Based Composite Films. J. Ind. Eng. Chem. 2009, 15 (1), 50–55 DOI: 10.1016/j.jiec.2008.07.008. Letchford; Jackson; Wasserman, B.; Ye; Hamad, W.; Burt, H. The Use of Nanocrystalline Cellulose for the Binding and Controlled Release of Drugs. Int. J. Nanomedicine 2011, 321 DOI: 10.2147/IJN.S16749. Hajaligol, M.; Waymack, B.; Kellogg, D. Low Temperature Formation of Aromatic Hydrocarbon from Pyrolysis of Cellulosic Materials. Fuel 2001, 80 (12), 1799–1807 DOI: 10.1016/S00162361(01)00063-1.

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(136)

(137) (138)

(139)

(140) (141) (142) (143)

(144) (145)

(146) (147) (148) (149)

(150)

(151) (152) (153)

(154)

Jonoobi, M.; Oladi, R.; Davoudpour, Y.; Oksman, K.; Dufresne, A.; Hamzeh, Y.; Davoodi, R. Different Preparation Methods and Properties of Nanostructured Cellulose from Various Natural Resources and Residues: A Review. Cellulose 2015, 22 (2), 935–969 DOI: 10.1007/s10570-0150551-0. Qiu, X.; Hu, S. “Smart” Materials Based on Cellulose: A Review of the Preparations, Properties, and Applications. Materials 2013, 6 (3), 738–781 DOI: 10.3390/ma6030738. Kim, J.-H.; Shim, B. S.; Kim, H. S.; Lee, Y.-J.; Min, S.-K.; Jang, D.; Abas, Z.; Kim, J. Review of Nanocellulose for Sustainable Future Materials. Int. J. Precis. Eng. Manuf.-Green Technol. 2015, 2 (2), 197–213 DOI: 10.1007/s40684-015-0024-9. Nagalakshmaiah, M.; El Kissi, N.; Dufresne, A. Ionic Compatibilization of Cellulose Nanocrystals with Quaternary Ammonium Salt and Their Melt Extrusion with Polypropylene. ACS Appl. Mater. Interfaces 2016, 8 (13), 8755–8764 DOI: 10.1021/acsami.6b01650. VTT to Reduce Food Loss with Stand-up Pouches. Incredible Uses of Nanocellulose. Jiang, F.; Hsieh, Y.-L. Amphiphilic Superabsorbent Cellulose Nanofibril Aerogels. J Mater Chem A 2014, 2 (18), 6337–6342 DOI: 10.1039/C4TA00743C. Lin, N.; Bruzzese, C.; Dufresne, A. TEMPO-Oxidized Nanocellulose Participating as Crosslinking Aid for Alginate-Based Sponges. ACS Appl. Mater. Interfaces 2012, 4 (9), 4948–4959 DOI: 10.1021/am301325r. Huang, J.; Zhu, H.; Chen, Y.; Preston, C.; Rohrbach, K.; Cumings, J.; Hu, L. Highly Transparent and Flexible Nanopaper Transistors. ACS Nano 2013, 7 (3), 2106–2113 DOI: 10.1021/nn304407r. Markstedt, K.; Mantas, A.; Tournier, I.; Martínez Ávila, H.; Hägg, D.; Gatenholm, P. 3D Bioprinting Human Chondrocytes with Nanocellulose–Alginate Bioink for Cartilage Tissue Engineering Applications. Biomacromolecules 2015, 16 (5), 1489–1496 DOI: 10.1021/acs.biomac.5b00188. Iwatake, A.; Nogi, M.; Yano, H. Cellulose Nanofiber-Reinforced Polylactic Acid. Compos. Sci. Technol. 2008, 68 (9), 2103–2106 DOI: 10.1016/j.compscitech.2008.03.006. Favier, V.; Canova, G. R.; Cavaillé, J. Y.; Chanzy, H.; Dufresne, A.; Gauthier, C. Nanocomposite Materials from Latex and Cellulose Whiskers. Polym. Adv. Technol. 1995, 6 (5), 351–355. Johansson, C.; Julien, B.; Mondragon, I. Renewable Fibers and Bio-Based Materials for Packaging Applications - A Review of Recent Developments. 2012. Lavoine, N.; Desloges, I.; Manship, B.; Bras, J. Antibacterial Paperboard Packaging Using Microfibrillated Cellulose. J. Food Sci. Technol. 2015, 52 (9), 5590–5600 DOI: 10.1007/s13197014-1675-1. Saini, S.; Sillard, C.; Naceur Belgacem, M.; Bras, J. Nisin Anchored Cellulose Nanofibers for Long Term Antimicrobial Active Food Packaging. RSC Adv 2016, 6 (15), 12422–12430 DOI: 10.1039/C5RA22748H. VTT; Technical Research Centre of Finland, Espoo, Finland,. VTT, Innovation and Competitiveness from Nanocellulose. 2011. Markham, D. Cellucomp, Cellulose Nano-Fiber from Carrots Is Twice as Strong as Carbon Fiber. Hu, L.; Zheng, G.; Yao, J.; Liu, N.; Weil, B.; Eskilsson, M.; Karabulut, E.; Ruan, Z.; Fan, S.; Bloking, J. T.; others. Transparent and Conductive Paper from Nanocellulose Fibers. Energy Environ. Sci. 2013, 6 (2), 513–518. Lin, N.; Gèze, A.; Wouessidjewe, D.; Huang, J.; Dufresne, A. Biocompatible Double-Membrane Hydrogels from Cationic Cellulose Nanocrystals and Anionic Alginate as Complexing Drugs Codelivery. ACS Appl. Mater. Interfaces 2016, 8 (11), 6880–6889 DOI: 10.1021/acsami.6b00555.

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Rebouillat, S.; Pla, F. State of the Art Manufacturing and Engineering of Nanocellulose: A Review of Available Data and Industrial Applications. J. Biomater. Nanobiotechnology 2013, 04 (02), 165–188 DOI: 10.4236/jbnb.2013.42022. paperage.com. World’s First Pilot Plant for Production of Nanocellulose Inaugurated. 2011. TAPPI NANO, I. 6/TG 1 – C. N. Summary of International Activities on Cellulosic Nanomaterials. July 2015.

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