Open access peer-reviewed chapter

Production, Processes and Modification of Nanocrystalline Cellulose from Agro-Waste: A Review

Written By

R.A. Ilyas, S.M. Sapuan, R. Ibrahim, M.S.N. Atikah, A. Atiqah, M.N.M. Ansari and M.N.F. Norrrahim

Submitted: 25 February 2019 Reviewed: 22 May 2019 Published: 12 September 2019

DOI: 10.5772/intechopen.87001

From the Edited Volume

Nanocrystalline Materials

Edited by Behrooz Movahedi

Chapter metrics overview

1,658 Chapter Downloads

View Full Metrics

Abstract

Nanocrystalline cellulose is a renewable nanomaterial that has gained huge attention for its use in various applications from advanced biomedical material to food packaging material due to its exceptional physical and biological properties, such as high crystallinity degree, large specific surface area, high aspect ratio, high thermal resistance, good mechanical properties, abundance of surface hydroxyl groups, low toxicity, biodegradability, and biocompatibility. However, they still have drawbacks: (1) sources of raw materials and its utilization in the production of nanocomposites and (2) high chemical and energy consumption regarding the isolation of macro-sized fibers to nano-sized fibers. The incorporation of hydrophilic nanocrystalline cellulose within hydrophobic polymer limits the dispersion of nano-sized fibers, thus resulting in low mechanical properties of nanocomposites. Hence, surface modification on nano-sized fiber could be a solution to this problem. This review focuses on the advanced developments in pretreatment, nanocrystalline production and modifications, and its application in food packaging, biomedical materials, pharmaceutical, substitution biomaterials, drug excipient, drug delivery automotive, and nanopaper applications.

Keywords

  • nanocrystalline cellulose
  • nanocomposites
  • surface modification
  • hydrolysis
  • agro-waste

1. Introduction

During the past decades, huge efforts have been made to improve new chemicals and/or materials and replace broadly used petroleum-based products by utilizing biomass renewable feedstock [1, 2, 3]. Biocompatible composites and biodegradable plastics produced from biorenewable resources are regarded as promising biomaterials that could replace petrochemical-based polymers and hence reduce global dependence on nonrenewable sources (i.e., fossil fuels: coal, petroleum, and natural gas) and provide simplified recycling or end-of-life disposal [4, 5, 6, 7, 8, 9, 10].

Agro-based industry’s function is to increase the value of raw agricultural products through downstream processing so that products are marketable, consumable, and used to generate income and provide profit to the producer [11]. However, there is waste generated through the process of downstream and upstream of agro-industry. The composition of industrial wastes varies depending on the types of industry as different countries apply various categories for industrial waste which contribute adversely to air, soil, and water quality. This is due to some of the industrial wastes which are neither toxic nor hazardous. For example, organic wastes, such as corncob, sugarcane bagasse, sugar palm (fiber, frond, bunch, trunk), areca nut husk fiber, wheat straw fiber, soy hull fiber, pineapple leaf fiber, oil palm (mesocarp fiber, empty fruit bunch, frond), rubber wood thinning, curaua fiber, banana fiber, water hyacinth fiber, wheat straw, sugar beet fiber, etc. that are produced by agro-based industries are not hazardous in nature and thus have potential for other uses [12, 13, 14]. Figure 1 shows the by-products of agro-industry that are used for sources of lignocellulose biomass.

Figure 1.

By-products of agro-industry that are used for sources of lignocellulose biomass.

Biomass renewable feedstocks are of great interest due to the possibility of nontoxicity, renewability, and biodegradability as well as sustainability [12, 13, 14, 15, 16, 17]. Lignocellulosic can be classified as lower-value biomass (LVB). Lower-value biomass (LVB) in forest or agriculture industry constitutes noncommercial material traditionally left on site following harvesting of crops. However, emerging markets for energy, chemicals, and bioproducts have increased incentives to harvest and utilize this material in some cases [20, 21, 22, 23, 24, 25]. Lignocellulosic biomass suppliers do not use any kind of wood indiscriminately due to economic and environmental reasons; they usually used mobilized woody biomass sourced from by-products of forest operations, agriculture, and crops’ waste as well as the wood industry waste such as sawmills. Lignocellulosic biomass sector has been developed to work in synergy with other agro-based industry and wood-based industries to give value to non-mobilized and/or low-value biomass such as trunk, fiber, sugar cane bagasse, manure bedding, plant stalks, vines, hulls, leaves, vegetable matter, sawdust, mill residues, thinnings, low-quality wood, tops, and limbs. Biomass generators do not use high-quality timber or main agricultural products, as using lumber or major crops would make the price of biomass wholly uncompetitive for end consumers. Figure 2 shows the by-products of forest operation that are used for sources of lignocellulose biomass. Natural fibers or lignocellulosic fibers can be classified into two main groups that are wood and non-wood bio-fibers (Figure 3). This review will be focusing on production, processes, modification, and application of nanocrystalline cellulose from agro-waste.

Figure 2.

By-products of forest operation that are used for sources of lignocellulose biomass. Adapted from Ref. [23]. http://www.europeanbioenergyday.eu/solid-bioenergy-in-questions-an-asset-to-eu-forests/.

Figure 3.

Schematic representation of lignocellulosic agro-waste and by-product of forest classification. Adapted from Ref. [7].

Advertisement

2. Lignocellulosic biomass from agro-waste fiber and forest by-products

Lignocellulosic biomass comprises of three major chemical components that are cellulose, lignin, and hemicellulose [18, 19, 20, 21]. The chemical compositions of agro-waste fibers are different depending on the type of fiber as summarized in Table 1. Besides that, it can be concluded in Table 1 that the highest cellulose contents are pineapple leaf fibers (81.27%), followed by kenaf core powder (80.26%). Besides that, from Table 1 also we can summarize that the chemical composition of natural fibers is 30–80% cellulose, 7–40% hemicellulose, and 3–33% lignin. Cellulose, hemicellulose, and lignin have their own properties and functionality. Table 2 shows the functional properties of the cellulose, hemicellulose, and lignin. The physical, thermal, and mechanical properties of the natural fibers are diverse between each other as they are mostly depending on cellulose crystallinity. Intra- and intermolecular hydrogen bonding among the cellulose chains affects the packing compactness of cellulose crystallinity. Table 1 shows the chemical composition of natural fibers and their crystallinity. From the abovementioned lignocellulosic, particularly, the hemicellulose and cellulose have promising features such as existing refining agro-forest or agro-waste factories. For centuries, cellulose has been utilized in the form of non-wood plant fibers and wood as building materials, clothing, textile, and paper.

Fibers Holocellulose (wt%) Lignin (wt%) Ash (wt%) Extractives (wt%) Crystallinity (%) Ref.
Cellulose (wt%) Hemicellulose (wt%)
Sugar palm fiber 43.88 7.24 33.24 1.01 2.73 55.8 [6]
Sugar palm frond 66.49 14.73 18.89 3.05 2.46 [28]
Sugar palm bunch 61.76 10.02 23.48 3.38 2.24 [28]
Sugar palm trunk 40.56 21.46 46.44 2.38 6.30 [28]
Wheat straw fiber 43.2 ± 0.15 34.1 ± 1.2 22.0 ± 3.1 57.5 [29]
Soy hull fiber 56.4 ± 0.92 12.5 ± 0.72 18.0 ± 2.5 59.8 [29]
Areca nut husk fiber 34.18 20.83 31.60 2.34 37 [14]
Helicteres isora plant 71 ± 2.6 3.1 ± 0.5 21 ± 0.9 38 [30]
Pineapple leaf fiber 81.27 ± 2.45 12.31 ± 1.35 3.46 ± 0.58 35.97 [31]
Ramie fiber 69.83 9.63 3.98 55.48 [32]
Oil palm mesocarp fiber (OPMF) 28.2 ± 0.8 32.7 ± 4.8 32.4 ± 4.0 6.5 ± 0.1 34.3 [33]
Oil palm empty fruit bunch (OPEFB) 37.1 ± 4.4 39.9 ± 0.75 18.6 ± 1.3 3.1 ± 3.4 45.0 [33]
Oil palm frond (OPF) 45.0 ± 0.6 32.0 ± 1.4 16.9 ± 0.4 2.3 ± 1.0 54.5 [33]
Oil palm empty fruit bunch (OPEFB) fiber 40 ± 2 23 ± 2 21 ± 1 2.0 ± 0.2 40 [34]
Rubber wood 45 ± 3 20 ± 2 29 ± 2 2.5 ± 0.5 46 [34]
Curaua fiber 70.2 ± 0.7 18.3 ± 0.8 9.3 ± 0.9 64 [35]
Banana fiber 7.5 74.9 7.9 0.01 9.6 15.0 [36]
Sugarcane bagasse 43.6 27.7 27.7 76 [37]
Kenaf bast 63.5 ± 0.5 17.6 ± 1.4 12.7 ± 1.5 2.2 ± 0.8 4.0 ± 1.0 48.2 [38]
Phoenix dactylifera palm leaflet 33.5 26.0 27.0 6.5 50 [39]
Phoenix dactylifera palm rachis 44.0 28.0 14.0 2.5 55 [39]
Kenaf core powder 80.26 23.58 48.1 [40]
Water hyacinth fiber 42.8 20.6 4.1 59.56 [41]
Wheat straw 43.2 ± 0.15 34.1 ± 1.2 22.0 ± 3.1 57.5 [42]
Sugar beet fiber 44.95 ± 0.09 25.40 ± 2.06 11.23 ± 1.66 17.67 ± 1.54 35.67 [43]
Mengkuang leaves 37.3 ± 0.6 34.4 ± 0.2 24 ± 0.8 2.5 ± 0.02 55.1 [44]

Table 1.

Chemical composition of agro-waste fibers and forest by-products from different plants and different parts.

Cellulose Hemicellulose Lignin
Structure
  • Cellulose is assembled together with pectin fibers, which function to bind the cellulose together to produce tighter cell walls in natural fibers, accounting for their strength providing resistance to lysing in the presence of water

  • Hemicelluloses consist of long chain—7000–15,000 glucose molecules per polymer

  • Hemicellulose is a cell wall polysaccharide that has the capacity to bind strongly to cellulose microfibrils by hydrogen bonds

  • Hemicelluloses consist of short chains—500–3000 glucose molecules per polymer

  • Lignin is a cross-linked polymer with molecular masses in excess of 10,000 u

Function
  • Connecting cells to form tissue

  • Provide structural support

  • Provides a strong resistance to stress

  • Prevents the cell from bursting in hypotonic solution

  • Responsible for the moisture absorption, biodegradation

  • Microfibrils are cross-linked together by hemicellulose homopolymers

  • Responsible for UV degradation

  • Lignin assists and strengthens the attachment of hemicelluloses to microfibrils

  • Lignin plays a crucial part in conducting water in plant stems

Properties
  • Thermal stability (occurred from 315 to ∼400°C)

  • Thermal stability occurred from 220 to ∼315°C

  • Thermal stability occurred from 165 to ∼900°C

Table 2.

Functions and properties of cellulose, hemicellulose, and lignin. Adapted from Refs. [6, 7, 27].

Advertisement

3. Nanocrystalline cellulose

Nanocrystalline cellulose (NCC) has several notable optical, chemical, and electrical properties due to their needlelike shape, high surface area, high aspect ratio (length/diameter), high crystallinity, nanoscale size, high strength and stiffness, low density, and highly negative charge which lead to unique behavior in solutions. The high chemical reactivity of the surface makes NCC customizable for various applications, besides their heat stability which allows high-temperature applications. Moreover, they also have huge surface OH groups which provide active sites for hydrogen bonding through the interlocking with nonpolar matrix [4, 7, 10, 45, 46]. Nanocrystalline cellulose can be isolated from cellulose as shown in Figure 4. The nanocellulose can be obtained through two approaches: top-down by the disintegration of plant fiber or bottom-up by biosynthesis [46]. For bottom-up biosynthesis approach, fermentation of low-molecular-weight sugars occurred by using bacteria from Acetobacter species. Meanwhile, for the top-down approach, the production of nanocrystalline cellulose is chemically induced via removing amorphous region. The chemical or mechanical treatments or a combination of both treatments involves enzymatic treatment, grinding, high-pressurized homogenization, acid hydrolysis, TEMPO-mediated oxidation, microfluidization, cryocrushing, and high-intensity ultrasonification. Table 3 shows the hydrolysis approaches from various sources of agro-waste and forest by-product for NCC isolation.

Figure 4.

Schematic representation of lignocellulosic agro-waste and by-product of forest classification. Adapted from Ref. [47].

Source Process References
Acacia mangium H2SO4 hydrolysis [56]
Algae H2SO4 hydrolysis [57]
Areca nut husk fiber HCl hydrolysis [14]
Bacterial cellulose H2SO4 hydrolysis [58]
Bamboo H2SO4 hydrolysis [59]
Bamboo (Pseudosasa amabilis) H2SO4 hydrolysis [60]
Banana fiber H2C2O4 hydrolysis [31]
Banana pseudo-stem TEMPO-mediated oxidation, formic acid hydrolysis [61]
Cassava bagasse H2SO4 hydrolysis [62]
Coconut husk H2SO4 hydrolysis [63]
Colored cotton H2SO4 hydrolysis [64]
Corncob H2SO4 hydrolysis [13]
Cotton (cotton wool) H2SO4 hydrolysis [65]
Cotton linters HCl hydrolysis [66]
Cotton Whatman filter paper H2SO4 hydrolysis [67]
Cotton (Gossypium hirsutum) linters H2SO4 hydrolysis [68]
Cotton stalk TEMPO-mediated oxidation and H2SO4 hydrolysis [69]
Cotton fiber H2SO4 hydrolysis [70]
Curaua fiber H2SO4, H2SO4/HCl, HCl hydrolysis [35]
Eucalyptus kraft pulp H2SO4 hydrolysis [71]
Grass fibers H2SO4 hydrolysis [72]
Grass fibers (Imperata brasiliensis) H2SO4 hydrolysis [73]
Groundnut shells H2SO4 hydrolysis [74]
Hibiscus sabdariffa fibers Steam explosion H2SO4 hydrolysis [75]
Humulus japonicus stem H2SO4 hydrolysis with high-temperature pretreatment [76]
Industrial bioresidue H2SO4 hydrolysis [77]
Industrial bioresidue (sludge) H2SO4 hydrolysis [78]
Kraft pulp H2SO4 hydrolysis [79]
Kenaf core wood H2SO4 hydrolysis [40]
MCC H2SO4 hydrolysis [55]
Mengkuang leaves H2SO4 hydrolysis [44]
Mulberry H2SO4 hydrolysis [80]
Oil palm trunk H2SO4 hydrolysis [81]
Oil palm empty fruit bunch (OPEFB) H2SO4 hydrolysis [82]
Phormium tenax (harakeke) fiber H2SO4 hydrolysis [83]
Potato peel waste H2SO4 hydrolysis [84]
Flax fiber H2SO4 hydrolysis [83]
Ramie KOH hydrolysis [85]
Ramie H2SO4 hydrolysis [86]
Ramie H2SO4 hydrolysis [87]
Rice husk H2SO4 hydrolysis [63]
Rice straw H2SO4 hydrolysis [88]
Sesame husk H2SO4 hydrolysis [89]
Sisal fiber H2SO4 hydrolysis [90]
Soy hulls H2SO4 hydrolysis [91]
Sugar palm fiber H2SO4 hydrolysis [6]
Sugar palm frond H2SO4 hydrolysis [92]
Sugarcane bagasse H2SO4 hydrolysis [37]
Sago seed shells H2SO4 hydrolysis [93]
Tunicate H2SO4 hydrolysis [94]
Water hyacinth fiber HCl hydrolysis [48]
Wood pulp TEMPO oxidation followed by HCl hydrolysis [95]
Wheat straw H2SO4 hydrolysis [96]
Valonia ventricosa HCl hydrolysis [97]

Table 3.

Available process of extraction approaches from different sources for NCC isolation.

Advertisement

4. Processes of nanocrystalline cellulose

Recently, researchers are exploring the potential utilization of agriculture or forest wastes as NCCs’ sources. As a consequence, the various local sources are used to investigate the potential of NCC in certain technologies. The isolation of NCC needs intensive hydrolysis chemical treatment. However, according to the degree of processing and raw material, physical, chemical, enzymatic, and ionic pretreatments are performed before nanocrystalline cellulose synthesis. Figure 5 shows the sources, pretreatments, synthesis, and application of nanocrystalline cellulose. It is good to know that appropriate pretreatments of cellulosic fibers promote the accessibility of hydroxyl group, alter crystallinity, increase the inner surface, and break cellulose hydrogen bonds and hence improved the reactivity of the fibers [6, 7, 10]. Several approaches to diminish cellulosic fibers into nanofibers can be divided into several techniques such as acid hydrolysis, alkali treatment, mechanical treatments, and combination of mechanical and chemical treatments. Common methods for isolate NCC are hydrolysis methods which are a chemical method. Figure 6 shows the typical process for the production of nanocrystalline cellulose. Hydrolysis process includes inserting raw plant fibers into a strong acidic environment with the help of mechanical agitation. Concentrated acid and shear forces on solution generate shear rates in the stream and decrease the size of fibers to the nanoscale. Sulfuric acid (H2SO4) is commonly used in the isolation process of NCC besides other chemicals such as HCL [48], HBr [49], and H3PO4 [50]. Hydrolysis process using sulfuric acid solution resulted in a high number of negatively charged sulfate groups on the surface of NCC. This process limits the agglomeration and flocculation of NCC in an aqueous medium [51]. The drawback from this process is that the NCC displays moderate thermostability. Hence to overcome this drawback, the NCC will either undergo dialysis process using distilled water to fully dispose free acid molecules or use sodium hydroxide (NaOH), which functions to neutralize nanoparticles [52]. Figure 7 displays three steps in the mechanism of acid hydrolysis [53]:

  1. Development of conjugated acid by reactions between oxygen protons and glycoside acid

  2. Breaking down of C-O bonds and segregation of conjugated acid into cyclic carbonium ions

  3. Release of the proton and free sugar after the addition of water

Figure 5.

Sources, pretreatments, synthesis, and application of nanocrystalline cellulose. Adapted from Refs. [6, 7, 10].

Figure 6.

Typical process for the production of nanocrystalline cellulose. Adapted from Refs. [4, 5, 8].

Figure 7.

Mechanism of hydrolysis of acid [53].

There are numerous studies that have been conducted on the effects of concentration of acid, acid-to-fiber ratio, and temperature and time of the hydrolysis process on the dimensions and morphological properties of yielded nanocrystalline cellulose. According to Azizi et al. [29], there is a strong relationship between the hydrolysis time and acid-to-fiber ratio to the length and dimensions of nanocrystalline cellulose, which by increasing the hydrolysis time and acid-to-fiber ratio would reduce the dimension and length of nanocrystalline cellulose.

Besides that, there are large numbers of published studies [51, 54] that describe the dimension, size, and shape of NCC that were affected by the conditions of hydrolysis process (purity of the material, temperature, time, and ultrasound treatment) and a variety of cellulosic fiber sources. Bondeson et al. [55] conducted an experiment on the isolation of NCC and found that the optimized condition is at a concentration of 63.5% H2SO4, which yielded 38 wt.% of NCCs with a width of 10 nm. Another experiment that is conducted by Ilyas et al. [6] found that the optimum yield for isolating sugar palm nanocrystalline cellulose is at a concentration of 60 wt% H2SO4 and duration hydrolysis of 45 min, with length and diameters of 130 ± 30 and 9 ± 1.96 nm, respectively. Table 3 shows the preparation of NCC using various acid hydrolysis processes from different cellulosic sources. Typical procedures for NCC extraction are composed of several steps: strong acid hydrolysis, dilution, dialysis, sonification, and drying of NCC.

Advertisement

5. Limitation and modification of nanocrystalline cellulose

There are several limitations when using natural fibers as reinforcement filler in the polymer matrix such as single-particle dispersion, barrier properties, permeability properties, and poor interfacial adhesion (Figure 8). Nanocrystalline cellulose has a strong propensity of self-association due to the interaction of abundance OH groups within its surface, which causes agglomeration and limits its potential applications. Besides, hydrophilic properties of nanocrystalline cellulose make it difficult to disperse homogenously within any medium and matrix. Therefore, in order to overcome the incompatible nature, poor interfacial adhesion, and difficult dispersion of nanocrystalline cellulose in a polymer matrix, surface modification of fibers or modification of matrix is introduced. Nanocellulose displays a high surface area valued more than 100 m2/g. This gives advantages to nanocellulose for surface modification in order to introduce any desired surface functionality. However, according to Postek et al. [98], the surface chemistry of nanocellulose is primarily controlled by the process of isolation that used to prepare these nanocelluloses from raw cellulose substrate. Figure 9 shows the most common surface chemical modifications of nanocrystalline cellulose. Surface modification of NCC can be categorized into three typical groups, namely, (1) polymer grafting based on “grafting onto” strategy with different coupling agents (as indicated with blue arrows in Figure 9), (2) substitution of hydroxyl group with small molecules (as indicated with red arrows in Figure 9), and (3) polymer grafting based on the “grafting from” approach with a radical polymerization involving single-electron transfer-living radical polymerization (SET-LP), ring opening polymerization (ROP), and atom transfer radical polymerization (ATRP) (as indicated with yellow arrows in Figure 9). The enhancement of NCC-polymer matrix interaction is predicted to improve the stress transfer from the matrix to the dispersed phase and hence enhances the capability of load bearing material. Besides, the chemical modification of NCC can be dispersed in the low polarity of organic solvent and mixed with a polymer matrix solution or directly introduced into the polymer melt after drying. Nevertheless, two effects ascend from this process: (1) allow the improvement of dispersion of modified NCC in the polymer matrix and (2) limit the interaction between NNC and matrix through hydrogen bonding which is the basis of the outstanding mechanical properties of nanocellulose-based nanocomposites.

Figure 8.

Limitation of nanocellulose. Adapted from Refs. [6, 7, 10].

Figure 9.

Schematic diagram illustrating nanocellulose surface functionalization modification. PEG, poly(ethylene glycol); PEO, poly(ethylene oxide); PLA, poly(lactic acid); PAA, poly(acrylic acid); PNiPAAm, poly(N-isopropylacrylamide); PDMAEMA, poly(N,N-dimethylaminoethyl methacrylate). Adapted from Ref. [99].

Advertisement

6. Applications of nanocrystalline cellulose from agro-waste fiber and forest by-products

The incorporation of nanocrystalline cellulose in biopolymers for the nanocomposite production provides huge advantages with superior performance which would extend their applications in various applications. This is due to their outstanding thermal and mechanical properties. NCC also can reduce the water vapor permeability of the composites due to its high gas permeability [26]. Besides that, NCC can be used to stabilize the encapsulated bioactive compounds in biopolymers for allowing better control in food applications which can improve the food quality, extend the shelf-life of food, and serve as active substance carriers such as antifungal, antioxidant compounds, antimicrobial, and insecticide.

The utilization of natural cellulose-based materials continues today as verified by the various industry players from forest product to make pulp and paper to the advanced technology used in biomedical applications. These uses have been reported extensively as summarized in Table 4. NCC can be used as a drug delivery excipient; Burt et al. [100] investigated the capability of pure NCC to bind water-soluble antibiotics (tetracycline and doxorubicin) and the potential of cationic NCC to bind non-ionized hydrophobic anticancer agents (docetaxel, paclitaxel, and etoposide). Moreover, besides direct use as drug delivery excipient, NCC can also be used as co-stabilizer to improve the physicochemical and flow properties of polymeric excipients. Acrylic beads prepared via emulsion polymerization using NCC as co-stabilizer were proven to be a suitable excipient.

Polymer component Manufacturing technique Applications References
Cellulose esterified with lauroyl chloride Solution casting and thermopressing Interface melting [101]
Ethyl acrylate; methyl-methacrylate Solution mixing Drug carrier [100]
Ethylene-co-vinyl acetate rubber Solution mixing and vulcanization Transparent, rubbery materials [102]
Maleic-anhydride grafted PLA Electrospinning Bone tissue engineering [103]
Methylcellulose Hydrogel by aqueous dispersion Thermoreversible and tunable nanocellulose-based hydrogels [104]
PC Masterbatch melt extrusion process Optical devices [105]
PC-based polyurethane blend Solution casting Smart actuators and sensors [106]
Plasticized PLA Twin-screw extruder Film blowing, packaging [107]
Plasticized starch Solution casting Transparent materials [108]
PU Solution casting High temperature biomedical devices [109]
PVA Solution casting Stretchable photonic devices [110]
PVA Solution casting Wound diagnosis/biosensor scaffolds [111]
PVA Solution casting Conductive materials [112]
Starch Blending, solution casting Air permeable, resistant, surface-sized paper, food packaging [113, 114]
Starch Solution casting Food packaging [60]
Cassava starch Solution casting Food packaging [62]
Sugar palm starch Solution casting Food packaging [115]
Wheat starch Solution casting Food packaging [87]
Tuber native potato Solution casting Packaging [116]
Cereal corn Solution casting Packaging [116]
Legume pea Solution casting Packaging [116]
Waterborne acrylate Solution mixing Corrosion protection [79]
Wheat straw hemicelluloses Solution casting Packaging [96]
PVA Solution casting Food packaging [83]
Chitosan Solution casting Food coating/packaging [70]

Table 4.

Polymer component reinforced NCCs and its manufacturing technique and applications.

Table 5 shows several nanocelluloses, NFCs, and NCCs that have been used as reinforcement fillers in polymer matrices. The polymer matrices used are from both synthetic and natural polymers. Table 6 shows examples of NCCs used as fillers in polymeric matrices.

Source Filler Polymer matrix Ref.
Sugar palm NCC Sugar palm starch [117]
Sugar palm NFC Sugar palm starch [115]
Acacia mangium NCC PVA [56]
Bacteria NCC CAB (0–10 wt% filler) [58]
Cotton NCC PVA (0–12 wt% filler) [118]
Flax NFC/ NCC PVA (10 wt% filler), waterborne polyurethanes (0–30 wt% filler) [119, 120]
Hemp NFC PVA (10 wt% filler) [120]
Kraft pulp NCC Waterborne acrylate [79]
MCC NCC PLA (5 wt% filler) [121]
Potato pulp NFC Starch/glycerol (0–40 wt% filler) [122]
Ramie NFC Unsaturated polyester resin [85]
Ramie NCC Starch/glycerol (0–40 wt% filler) [87]
Rutabaga NFC PVA (10 wt% filler) [120]
Soy hulls NFC No attempts were made with composites [29]
Sugar beet NFC/ NCC Styrene/butyl acrylate (6 wt% filler) [123]
Tunicate NCC Styrene/butyl acrylate (6 wt% filler), starch/sorbitol (25 wt% filler), waterborne epoxy (0.5–5 wt% filler) [94, 124, 125, 126]
Water hyacinth fiber NCC Yam bean starch [48]
Water hyacinth fiber NFC Yam bean starch [127]
Wheat straw NFC No attempts were made with composites [29]
Wheat straw NCC Wheat straw hemicelluloses [96]
Wood pulp NFC/ NCC PVA (10 wt% filler), PLA (5 wt% filler) [120, 128]
Cassava bagasse NCC Cassava starch [62]
Ramie NCC Wheat starch [87]
Phormium tenax (harakeke) fiber NCC PVA [83]
Flax fiber NCC PVA [83]
Potato peel fiber NCC Starch [84]

Table 5.

Different nanocellulose sources of reinforcement fillers in polymer matrices.

Polymer References
Cellulose acetate butyrate [58, 129]
Cellulose [130]
Chitosan [131, 132, 133]
Poly(acrylic) acid, PAA [134]
Poly-(allylmethylamine hydrochloride), PAH [135]
Poly-(dimethyldiallylammonium chloride), PDDA [136]
Poly(ethylene-co-vinyl acetate), EVA [137]
Poly(hydroxyalkanoate), PHA [133, 138]
Poly(hydroxyoctanoate), PHO [139]
Poly(lactic acid), PLA [118, 121, 140, 141, 142, 143, 144]
Poly(methyl-methacrylate), PMMA [145, 146]
Poly(oxyethylene), PEO [147, 148]
Poly(styrene-co-butyl acrylate) [94, 149, 150]
Poly(vinyl alcohol) (PVA) [56, 83, 151]
Poly(vinyl alcohol), PVOH [67, 152, 153, 154]
Polycaprolactone, PCL [155, 156, 157]
Polypropylene, PP [158, 159]
Polystyrene [160]
Polysulfone [161]
Polyurethane, PU [162, 163, 164]
Polyvinyl chloride, PVC [165, 166, 167]
Regenerated cellulose [168, 169]
Soy protein [170]
Starch-based polymers [60, 62, 84, 152, 171, 172, 173]
Waterborne acrylate [79]
Xylan [174, 175, 176]
Hemicellulose [96]

Table 6.

NCC used as filler in polymeric matrices.

Advertisement

7. Conclusion

Agro-waste is an unavoidable by-product that arises from various agricultural and agro-forest activities’ operation. However, different kinds of agro-product industries, change of lifestyle, and population growth are assumed to be within the main factors that increase the rate of waste generation globally and locally. Therefore, proper waste management selections are very important based on the types of wastes and cost-effective factors in order to reduce the damage to the ecosystem. One of the alternatives to reduce agro-waste disposal is converting it to high-end value products such as nanocrystalline cellulose. In the present work, an overview of the production, processes, modification, and application of nanocrystalline cellulose from different agricultural wastes was proposed and leads to the following main concluding remarks: (1) it is important to select the proper raw material of agro-waste fiber, due to a broad variety of structure and chemical composition and its pretreatment process before the extraction process of nanocellulose begin; (2) the surface charge and morphology of nanocrystalline cellulose are affected by the production conditions such as hydrolysis time, temperature, and the acid-to-fiber ratio; and (3) nanocrystalline cellulose can be used in various applications including in hydrophobic polymer after some modification is made. The utilization of several lignocellulosic wastes from agricultural and forest by-product activities becomes the best proposal regarding cost/energy savings and economic development. The agricultural residue is available worldwide, abundant, cheap, and an unexploited source of cellulose that could be used as large-scale production of nanocellulose products.

Advertisement

Acknowledgments

The authors would like to thank Universiti Putra Malaysia for the financial support through the Graduate Research Fellowship (GRF) scholarship, Universiti Putra Malaysia Grant scheme Hi-CoE (6369107), FRGS/1/2017/TK05/UPM/01/1 (5540048) and iRMC UNITEN (RJO10436494). The authors are grateful to Dr. Muhammed Lamin Sanyang for guidance throughout the experiment. The authors also thank Dr. Rushdan Ibrahim for his advice and fruitful discussion.

References

  1. 1. Hazrati KZ, Sapuan SM, Ilyas RA. Biobased food packaging using natural fibre: A review. In: Prosiding Seminar Enau Kebangsaan 2019, Bahau, Negeri Sembilan, Malaysia: Institute of Tropical Forest and Forest Products. Universiti Putra Malaysia: INTROP; 2019. pp. 140-142
  2. 2. Abral H, Basri A, Muhammad F, Fernando Y, Hafizulhaq F, Mahardika M, et al. A simple method for improving the properties of the sago starch films prepared by using ultrasonication treatment. Food Hydrocolloids. 2019;93:276-283. DOI: 10.1016/j.foodhyd.2019.02.012
  3. 3. Huzaifah MRM, Sapuan SM, Leman Z, Ishak MR, Ilyas RA. Effect of soil burial on water absorption of sugar palm fibre reinforced vinyl ester composites. In: 6th Postgraduate Seminar on Natural Fiber Reinforced Polymer Composites 2018. Selangor: Serdang; 2018. pp. 52-54
  4. 4. Brinchi L, Cotana F, Fortunati E, Kenny JM. Production of nanocrystalline cellulose from lignocellulosic biomass: Technology and applications. Carbohydrate Polymers. 2013;94:154-169. DOI: 10.1016/j.carbpol.2013.01.033
  5. 5. Norizan MN, Abdan K, Ilyas RA. Effect of water absorption on treated sugar palm yarn fibre/glass fibre hybrid composites. In: Prosiding Seminar Enau Kebangsaan 2019, Bahau, Negeri Sembilan, Malaysia: Institute of Tropical Forest and Forest Products. Universiti Putra Malaysia: INTROP; 2019. pp. 78-81
  6. 6. Ilyas RA, Sapuan SM, Ishak MR. Isolation and characterization of nanocrystalline cellulose from sugar palm fibres (Arenga pinnata). Carbohydrate Polymers. 2018;181:1038-1051. DOI: 10.1016/j.carbpol.2017.11.045
  7. 7. Ilyas RA, Sapuan SM, Ishak MR, Zainudin ES, Atikah MSN. Characterization of sugar palm nanocellulose and its potential for reinforcement with a starch-based composite. In: Sugar Palm Biofibers, Biopolymers, and Biocomposites. 1st ed. Boca Raton, FL: CRC Press/Taylor & Francis Group; 2018. pp. 189-220. DOI: 10.1201/9780429443923-10
  8. 8. Sanyang ML, Ilyas RA, Sapuan SM, Jumaidin R. Sugar palm starch-based composites for packaging applications. In: Bionanocomposites for Packaging Applications. Cham: Springer International Publishing; 2018. pp. 125-147. DOI: 10.1007/978-3-319-67319-6_7
  9. 9. Azammi AMN, Sapuan SM, Sultan MTH, Ishak MR, Radzi AM, Ilyas RA. Structure analysis for natural fiber composite for automotive component: A review. In: Prosiding Seminar Enau Kebangsaan 2019, Bahau, Negeri Sembilan, Malaysia: Institute of Tropical Forest and Forest Products. Universiti Putra Malaysia: INTROP; 2019. pp. 44-47
  10. 10. Ilyas RA, Sapuan SM, Sanyang ML, Ishak MR, Zainudin ES. Nanocrystalline cellulose as reinforcement for polymeric matrix nanocomposites and its potential applications: A review. Current Analytical Chemistry. 2018;14:203-225. DOI: 10.2174/1573411013666171003155624
  11. 11. Mazani N, Sapuan SM, Sanyang ML, Atiqah A, Ilyas RA. Design and fabrication of a shoe shelf from kenaf fiber reinforced unsaturated polyester composites. In: Lignocellulose for Future Bioeconomy. Elsevier; 2019. pp. 315-332. DOI: 10.1016/B978-0-12-816354-2.00017-7
  12. 12. Ilyas RA, Sapuan SM, Ibrahim R, Abral H, Ishak MR, Zainudin ES, et al. Sugar palm (Arenga pinnata (Wurmb.) Merr) cellulosic fibre hierarchy: A comprehensive approach from macro to nano scale. Journal of Materials Research and Technology. 2019. DOI: 10.1016/j.jmrt.2019.04.011
  13. 13. Liu C, Li B, Du H, Lv D, Zhang Y, Yu G, et al. Properties of nanocellulose isolated from corncob residue using sulfuric acid, formic acid, oxidative and mechanical methods. Carbohydrate Polymers. 2016;151:716-724. DOI: 10.1016/j.carbpol.2016.06.025
  14. 14. Julie Chandra CS, George N, Narayanankutty SK. Isolation and characterization of cellulose nanofibrils from arecanut husk fibre. Carbohydrate Polymers. 2016;142:158-166. DOI: 10.1016/j.carbpol.2016.01.015
  15. 15. Ilyas RA, Sapuan SM, Ishak MR, Zainudin ES. Sugar palm nanocrystalline cellulose reinforced sugar palm starch composite: Degradation and water-barrier properties. IOP Conference Series: Materials Science and Engineering. 2018;368. DOI: 10.1088/1757-899X/368/1/012006
  16. 16. Sapuan SM, Ishak MR, Leman Z, Ilyas RA, Huzaifah MRM. Development of products from sugar palm trees (Arenga pinnata Wurb. Merr): A community project. INTROPica. 2017:12-13
  17. 17. Jumaidin R, Sapuan SM, Ilyas RA. Physio-mechanical properties of thermoplastic starch composites: A review. In: Prosiding Seminar Enau Kebangsaan 2019, Bahau, Negeri Sembilan, Malaysia: Institute of Tropical Forest and Forest Products. Universiti Putra Malaysia: INTROP; 2019. pp. 104-108
  18. 18. Hazrol MD, Sapuan SM, Ilyas RA. Electrical and surface resistivity of polymer composites: A review. In: 6th Postgraduate Seminar on Natural Fiber Reinforced Polymer Composites 2018; Serdang, Selangor. 2018. pp. 44-47
  19. 19. Nazrin A, Sapuan SM, Ilyas RA. Thermoplastic starch blended poly(lactic) acid for food packaging application: Mechanical properties. In: 6th Postgraduate Seminar on Natural Fiber Reinforced Polymer Composites 2018, Serdang. 2018. pp. 79-84
  20. 20. Sapuan SM, Ilyas RA. Sugar palm: Fibers, biopolymers and biocomposites. INTROPica. 2017:5-7
  21. 21. Halimatul MJ, Sapuan SM, Jawaid M, Ishak MR, Ilyas RA. Effect of sago starch and plasticizer content on the properties of thermoplastic films: Mechanical testing and cyclic soaking-drying. Polimery. 2019;64:422-431. DOI: 10.14314/polimery.2019.6.5
  22. 22. Ilyas RA, Sapuan SM, Norizan MN, Atikah MSN, Huzaifah MRM, Radzi AM, et al. Potential of natural fibre composites for transport industry: A review. In: Prosiding Seminar Enau Kebangsaan 2019, Bahau, Negeri Sembilan, Malaysia: Institute of Tropical Forest and Forest Products. Universiti Putra Malaysia: INTROP; 2019. pp. 2-11
  23. 23. Solid Bioenergy—An Asset to EU Forests? European Bioenergy Day 2018. n.d. Available from: http://www.europeanbioenergyday.eu/solid-bioenergy-in-questions-an-asset-to-eu-forests/ [Accessed: April 29, 2019]
  24. 24. Ilyas RA, Sapuan SM, Ishak MR, Zainudin ES, Atikah MSN. Nanocellulose reinforced starch polymer composites: A review of preparation, properties and application. In: Proceeding: 5th International Conference on Applied Sciences and Engineering (ICASEA, 2018), Copthorne Hotel; Cameron Highlands, Malaysia. 2018. pp. 325-341
  25. 25. Ilyas RA, Sapuan SM, Ishak MR, Zainudin ES. Sugar palm nanofibrillated cellulose (Arenga pinnata (Wurmb.) Merr): Effect of cycles on their yield, physic-chemical, morphological and thermal behavior. International Journal of Biological Macromolecules. 2019;123:379-388. DOI: 10.1016/j.ijbiomac.2018.11.124
  26. 26. Ilyas RA, Sapuan SM, Ishak MR, Zainudin ES, Atikah MSN, Huzaifah MRM. Water barrier properties of biodegradable films reinforced with nanocellulose for food packaging application: A review. In: 6th Postgraduate Seminar on Natural Fiber Reinforced Polymer Composites 2018; Serdang, Selangor. 2018. pp. 55-59
  27. 27. Ilyas RA, Sapuan SM, Ishak MR, Zainudin ES. Effect of delignification on the physical, thermal, chemical, and structural properties of sugar palm fibre. BioResources. 2017;12:8734-8754. DOI: 10.15376/biores.12.4.8734-8754
  28. 28. Sanyang ML, Sapuan SM, Jawaid M, Ishak MR, Sahari J. Recent developments in sugar palm (Arenga pinnata) based biocomposites and their potential industrial applications: A review. Renewable and Sustainable Energy Reviews. 2016;54:533-549. DOI: 10.1016/j.rser.2015.10.037
  29. 29. Alemdar A, Sain M. Isolation and characterization of nanofibers from agricultural residues—Wheat straw and soy hulls. Bioresource Technology. 2008;99:1664-1671. DOI: 10.1016/j.biortech.2007.04.029
  30. 30. Chirayil CJ, Joy J, Mathew L, Mozetic M, Koetz J, Thomas S. Isolation and characterization of cellulose nanofibrils from Helicteres isora plant. Industrial Crops and Products. 2014;59:27-34. DOI: 10.1016/j.indcrop.2014.04.020
  31. 31. Cherian BM, Leão AL, de Souza SF, Thomas S, Pothan LA, Kottaisamy M. Isolation of nanocellulose from pineapple leaf fibres by steam explosion. Carbohydrate Polymers. 2010;81:720-725. DOI: 10.1016/j.carbpol.2010.03.046
  32. 32. Syafri E, Kasim A, Abral H, Asben A. Cellulose nanofibers isolation and characterization from ramie using a chemical-ultrasonic treatment. Journal of Natural Fibers. 2018;00:1-11. DOI: 10.1080/15440478.2018.1455073
  33. 33. Megashah LN, Ariffin H, Zakaria MR, Hassan MA. Properties of cellulose extract from different types of oil palm biomass. IOP Conference Series: Materials Science and Engineering. 2018;368. DOI: 10.1088/1757-899X/368/1/012049
  34. 34. Jonoobi M, Khazaeian A, Tahir PM, Azry SS, Oksman K. Characteristics of cellulose nanofibers isolated from rubberwood and empty fruit bunches of oil palm using chemo-mechanical process. Cellulose. 2011;18:1085-1095. DOI: 10.1007/s10570-011-9546-7
  35. 35. Corrêa AC, de Morais Teixeira E, Pessan LA, Mattoso LHC. Cellulose nanofibers from curaua fibers. Cellulose. 2010;17:1183-1192. DOI: 10.1007/s10570-010-9453-3
  36. 36. Tibolla H, Pelissari FM, Menegalli FC. Cellulose nanofibers produced from banana peel by chemical and enzymatic treatment. LWT—Food Science and Technology. 2014;59:1311-1318. DOI: 10.1016/j.lwt.2014.04.011
  37. 37. De ME, Jessika T, Bruna K, Teodoro R, Carolina A, Manoel J, et al. Sugarcane bagasse whiskers: Extraction and characterizations. Industrial Crops and Products. 2011;33:66. DOI: 10.1016/j.indcrop.2010.08.009
  38. 38. Jonoobi M, Harun J, Shakeri A, Misra M, Oksmand K. Chemical composition, crystallinity, and thermal degradation of bleached and unbleached kenaf bast (Hibiscus cannabinus) pulp and nanofibers. BioResources. 2009;4:626-639. DOI: 10.15376/biores.4.2.626-639
  39. 39. Bendahou A, Habibi Y, Kaddami H, Dufresne A. Physico-chemical characterization of palm from Phoenix dactylifera-L, preparation of cellulose whiskers and natural rubber-based nanocomposites. Journal of Biobased Materials and Bioenergy. 2009;3:81-90. DOI: 10.1166/jbmb.2009.1011
  40. 40. Chan CH, Chia CH, Zakaria S, Ahmad I, Dufresne A. Production and characterisation of cellulose and nano-crystalline cellulose from kenaf core wood. BioResources. 2013;8:785-794. DOI: 10.15376/biores.8.1.785-794
  41. 41. Abral H, Dalimunthe MH, Hartono J, Efendi RP, Asrofi M, Sugiarti E, et al. Characterization of tapioca starch biopolymer composites reinforced with micro scale water hyacinth fibers. Starch/Staerke. 2018;70:1-8. DOI: 10.1002/star.201700287
  42. 42. Alemdar A, Sain M. Biocomposites from wheat straw nanofibers: Morphology, thermal and mechanical properties. Composites Science and Technology. 2008;68:557-565. DOI: 10.1016/j.compscitech.2007.05.044
  43. 43. Li M, Wang LJ, Li D, Cheng YL, Adhikari B. Preparation and characterization of cellulose nanofibers from de-pectinated sugar beet pulp. Carbohydrate Polymers. 2014;102:136-143. DOI: 10.1016/j.carbpol.2013.11.021
  44. 44. Sheltami RM, Abdullah I, Ahmad I, Dufresne A, Kargarzadeh H. Extraction of cellulose nanocrystals from mengkuang leaves (Pandanus tectorius). Carbohydrate Polymers. 2012;88:772-779. DOI: 10.1016/j.carbpol.2012.01.062
  45. 45. Ilyas RA, Sapuan SM, Sanyang ML, Ishak MR. Nanocrystalline cellulose reinforced starch-based nanocomposite: A review. In: 5th Postgraduate Seminar on Natural Fiber Composites, Serdang, Selangor: Universiti Putra Malaysia. 2016. pp. 82-87
  46. 46. Bagheri S, Julkapli NM, Mansouri N. Nanocrystalline cellulose: Green, multifunctional and sustainable nanomaterials. In: Handbook of Composites from Renewable Materials. Vol. 1–8. 2017. pp. 523-555. DOI: 10.1002/9781119441632.ch142
  47. 47. CelluForce. Cellulose Nanocrystals 2016. Available from: https://www.celluforce.com/en/products/cellulose-nanocrystals/ [Accessed: May 1, 2019]
  48. 48. Asrofi M, Abral H, Kasim A, Pratoto A, Mahardika M, Hafizulhaq F. Characterization of the sonicated yam bean starch bionanocomposites reinforced by nanocellulose water hyacinth fiber (Whf): The effect of various fiber loading. Journal of Engineering Science and Technology. 2018;13:2700-2715
  49. 49. Lee S-Y, Mohan DJ, Kang I-A, Doh G-H, Lee S, Han SO. Nanocellulose reinforced PVA composite films: Effects of acid treatment and filler loading. Fibers and Polymers. 2009;10:77-82. DOI: 10.1007/s12221-009-0077-x
  50. 50. Camarero Espinosa S, Kuhnt T, Foster EJ, Weder C. Isolation of thermally stable cellulose nanocrystals by phosphoric acid hydrolysis. Biomacromolecules. 2013;14:1223-1230. DOI: 10.1021/bm400219u
  51. 51. Beck-Candanedo S, Roman M, Gray DG. Effect of reaction conditions on the properties and behavior of wood cellulose nanocrystal suspensions. Biomacromolecules. 2005;6:1048-1054
  52. 52. Roman M, Winter WT. Effect of sulfate groups from sulfuric acid hydrolysis on the thermal degradation behavior of bacterial cellulose. Biomacromolecules. 2004;5:1671-1677. DOI: 10.1021/bm034519+
  53. 53. Xiang Q, Lee YY, Pettersson PO, Torget RW. Heterogeneous aspects of acid hydrolysis of α-cellulose. In: Biotechnology for Fuels and Chemicals. Totowa, NJ: Humana Press; 2003. pp. 505-514. DOI: 10.1007/978-1-4612-0057-4_42
  54. 54. Azizi Samir MAS, Alloin F, Dufresne A. Review of recent research into cellulosic whiskers, their properties and their application in nanocomposite field. Biomacromolecules. 2005;6:612-626. DOI: 10.1021/bm0493685
  55. 55. Bondeson D, Mathew A, Oksman K. Optimization of the isolation of nanocrystals from microcrystalline cellulose by acid hydrolysis. Cellulose. 2006;13:171-180. DOI: 10.1007/s10570-006-9061-4
  56. 56. Jasmani L, Adnan S. Preparation and characterization of nanocrystalline cellulose from Acacia mangium and its reinforcement potential. Carbohydrate Polymers. 2017;161:166-171. DOI: 10.1016/j.carbpol.2016.12.061
  57. 57. Imai T, Putaux J, Sugiyama J. Geometric phase analysis of lattice images from algal cellulose microfibrils. Polymer. 2003;44:1871-1879. DOI: 10.1016/S0032-3861(02)00861-3
  58. 58. Grunert M, Winter WT. Nanocomposites of cellulose acetate butyrate reinforced with cellulose nanocrystals. Journal of Polymers and the Environment. 2002;10:27-30
  59. 59. Brito BSL, Pereira FV, Putaux J-L, Jean B. Preparation, morphology and structure of cellulose nanocrystals from bamboo fibers. Cellulose. 2012;19:1527-1536. DOI: 10.1007/s10570-012-9738-9
  60. 60. Liu D, Zhong T, Chang PR, Li K, Wu Q. Starch composites reinforced by bamboo cellulosic crystals. Bioresource Technology. 2010;101:2529-2536. DOI: 10.1016/j.biortech.2009.11.058
  61. 61. Faradilla RHF, Lee G, Arns JY, Roberts J, Martens P, Stenzel MH, et al. Characteristics of a free-standing film from banana pseudostem nanocellulose generated from TEMPO-mediated oxidation. Carbohydrate Polymers. 2017;174:1156-1163. DOI: 10.1016/j.carbpol.2017.07.025
  62. 62. Teixeira E d M, Pasquini D, Curvelo AASS, Corradini E, Belgacem MN, Dufresne A. Cassava bagasse cellulose nanofibrils reinforced thermoplastic cassava starch. Carbohydrate Polymers. 2009;78:422-431. DOI: 10.1016/j.carbpol.2009.04.034
  63. 63. Rosa MFM, Medeiros ES, Malmonge JAJ, Gregorski KS, Wood DF, Mattoso LHC, et al. Cellulose nanowhiskers from coconut husk fibers: Effect of preparation conditions on their thermal and morphological behavior. Carbohydrate Polymers. 2010;81:83-92. DOI: 10.1016/j.carbpol.2010.01.059
  64. 64. de Morais Teixeira E, Corrêa AC, Manzoli A, de Lima Leite F, de Ribeiro Oliveira C, Mattoso LHC. Cellulose nanofibers from white and naturally colored cotton fibers. Cellulose. 2010;17:595-606. DOI: 10.1007/s10570-010-9403-0
  65. 65. Morandi G, Heath L, Thielemans W. Cellulose nano-crystals grafted with polystyrene chains through surface-initiated atom transfer radical polymerization (SI-ATRP). Langmuir. 2009;25:8280-8286
  66. 66. Braun B, Dorgan JR, Chandler JP. Cellulosic nanowhiskers. Theory and application of light scattering from polydisperse spheroids in the Rayleigh−Gans−Debye regime. Biomacromolecules. 2008;9:1255-1263. DOI: 10.1021/bm7013137
  67. 67. Paralikar SA, Simonsen J, Lombardi J. Poly(vinyl alcohol)/cellulose nanocrystal barrier membranes. Journal of Membrane Science. 2008;320:248-258. DOI: 10.1016/j.memsci.2008.04.009
  68. 68. Morais JPS, Rosa MDF, De Souza Filho MM, Nascimento LD, Do Nascimento DM, Cassales AR. Extraction and characterization of nanocellulose structures from raw cotton linter. Carbohydrate Polymers. 2013;91:229-235. DOI: 10.1016/j.carbpol.2012.08.010.
  69. 69. Soni B, Hassan EB, Mahmoud B. Chemical isolation and characterization of different cellulose nanofibers from cotton stalks. Carbohydrate Polymers. 2015;134:581-589. DOI: 10.1016/j.carbpol.2015.08.031
  70. 70. Pereda M, Dufresne A, Aranguren MI, Marcovich NE. Polyelectrolyte films based on chitosan/olive oil and reinforced with cellulose nanocrystals. Carbohydrate Polymers. 2014;101:1018-1026. DOI: 10.1016/j.carbpol.2013.10.046
  71. 71. Tonoli GHDHD, Teixeira EMM, Corrêa ACC, Marconcini JMM, Caixeta LAA, Pereira-Da-Silva MAA, et al. Cellulose micro/nanofibres from eucalyptus kraft pulp: Preparation and properties. Carbohydrate Polymers. 2012;89:80-88. DOI: 10.1016/j.carbpol.2012.02.052
  72. 72. Pandey JK, Kim C, Chu W, Lee CS, Jang D-Y, Ahn S. Evaluation of morphological architecture of cellulose chains in grass during conversion from macro to nano dimensions. E-Polymers. 2009;9:1-15. DOI: 10.1515/epoly.2009.9.1.1221
  73. 73. Benini KCCC, Voorwald HJC, Cioffi MOH, Rezende MC, Arantes V. Preparation of nanocellulose from Imperata brasiliensis grass using Taguchi method. Carbohydrate Polymers. 2018;192:337-346. DOI: 10.1016/j.carbpol.2018.03.055
  74. 74. Bano S, Negi YS. Studies on cellulose nanocrystals isolated from groundnut shells. Carbohydrate Polymers. 2017;157:1041-1049. DOI: 10.1016/j.carbpol.2016.10.069
  75. 75. Sonia A, Priya Dasan K. Chemical, morphology and thermal evaluation of cellulose microfibers obtained from Hibiscus sabdariffa. Carbohydrate Polymers. 2013;92:668-674. DOI: 10.1016/j.carbpol.2012.09.015
  76. 76. Jiang Y, Zhou J, Zhang Q, Zhao G, Heng L, Chen D, et al. Preparation of cellulose nanocrystals from Humulus japonicus stem and the influence of high temperature pretreatment. Carbohydrate Polymers. 2017;164:284-293. DOI: 10.1016/j.carbpol.2017.02.021
  77. 77. Oksman K, Etang JA, Mathew AP, Jonoobi M. Cellulose nanowhiskers separated from a bio-residue from wood bioethanol production. Biomass and Bioenergy. 2010;35:146-152. DOI: 10.1016/j.biombioe.2010.08.021
  78. 78. Herrera MA, Mathew AP, Oksman K. Comparison of cellulose nanowhiskers extracted from industrial bio-residue and commercial microcrystalline cellulose. Materials Letters. 2012;71:28-31. DOI: 10.1016/j.matlet.2011.12.011
  79. 79. He Y, Boluk Y, Pan J, Ahniyaz A, Deltin T, Claesson PM. Corrosion protective properties of cellulose nanocrystals reinforced waterborne acrylate-based composite coating. Corrosion Science. 2019. DOI: 10.1016/j.corsci.2019.04.038
  80. 80. Li R, Fei J, Cai Y, Li Y, Feng J, Yao J. Cellulose whiskers extracted from mulberry: A novel biomass production. Carbohydrate Polymers. 2009;76:94-99. DOI: 10.1016/j.carbpol.2008.09.034
  81. 81. Lamaming J, Hashim R, Sulaiman O, Leh CP, Sugimoto T, Nordin NA. Cellulose nanocrystals isolated from oil palm trunk. Carbohydrate Polymers. 2015;127:202-208. DOI: 10.1016/j.carbpol.2015.03.043
  82. 82. Haafiz MKM, Hassan A, Zakaria Z, Inuwa IM. Isolation and characterization of cellulose nanowhiskers from oil palm biomass microcrystalline cellulose. Carbohydrate Polymers. 2014;103:119-125. DOI: 10.1016/j.carbpol.2013.11.055
  83. 83. Fortunati E, Puglia D, Luzi F, Santulli C, Kenny JM, Torre L. Binary PVA bio-nanocomposites containing cellulose nanocrystals extracted from different natural sources: Part I. Carbohydrate Polymers. 2013;97:825-836. DOI: 10.1016/j.carbpol.2013.03.075
  84. 84. Chen D, Lawton D, Thompson MR, Liu Q. Biocomposites reinforced with cellulose nanocrystals derived from potato peel waste. Carbohydrate Polymers. 2012;90:709-716. DOI: 10.1016/j.carbpol.2012.06.002
  85. 85. Wahono S, Irwan A, Syafri E, Asrofi M. Preparation and characterization of ramie cellulose nanofibers/CaCO3 unsaturated polyester resin composites. ARPN Journal of Engineering and Applied Sciences. 2018;13:746-751. DOI: 10.1039/c7nr02736b
  86. 86. Habibi Y, Vignon MR. Optimization of cellouronic acid synthesis by TEMPO-mediated oxidation of cellulose III from sugar beet pulp. Cellulose. 2008;15:177-185. DOI: 10.1007/s10570-007-9179-z
  87. 87. Lu Y, Weng L, Cao X. Morphological, thermal and mechanical properties of ramie crystallites—Reinforced plasticized starch biocomposites. Carbohydrate Polymers. 2006;63:198-204. DOI: 10.1016/j.carbpol.2005.08.027
  88. 88. Lu P, Hsieh Y. Preparation and characterization of cellulose nanocrystals from rice straw. Carbohydrate Polymers. 2012;87:564-573. DOI: 10.1016/j.carbpol.2011.08.022
  89. 89. Purkait BS, Ray D, Sengupta S, Kar T, Mohanty A, Misra M. Isolation of cellulose nanoparticles from sesame husk. Industrial & Engineering Chemistry Research. 2011;50:871-876. DOI: 10.1021/ie101797d
  90. 90. Morán JI, Alvarez VA, Cyras VP, Vázquez A. Extraction of cellulose and preparation of nanocellulose from sisal fibers. Cellulose. 2008;15:149-159. DOI: 10.1007/s10570-007-9145-9
  91. 91. Flauzino Neto WP, Silvério HA, Dantas NO, Pasquini D. Extraction and characterization of cellulose nanocrystals from agro-industrial residue—Soy hulls. Industrial Crops and Products. 2013;42:480-488. DOI: 10.1016/j.indcrop.2012.06.041
  92. 92. Sumaiyah L, Wirjosentono B, Karsono, Nasution MP. Preparation and characterization of nanocrystalline cellulose from sugar palm bunch. Interantional Journal of PharmTech Research. 2014;6:814-820
  93. 93. Naduparambath S, Jinitha TV, Shaniba V, Sreejith MP, Balan AK, Purushothaman E. Isolation and characterisation of cellulose nanocrystals from sago seed shells. Carbohydrate Polymers. 2018;180:13-20. DOI: 10.1016/j.carbpol.2017.09.088.
  94. 94. Favier V, Chanzy H, Cavaille JY. Polymer nanocomposites reinforced by cellulose whiskers. Macromolecules. 1995;28:6365-6367. DOI: 10.1021/ma00122a053
  95. 95. Salajková M, Berglund LA, Zhou Q. Hydrophobic cellulose nanocrystals modified with quaternary ammonium salts. Journal of Materials Chemistry. 2012;22:19798. DOI: 10.1039/c2jm34355j
  96. 96. Pereira PHF, Waldron KW, Wilson DR, Cunha AP, de Brito ES, Rodrigues THS, et al. Wheat straw hemicelluloses added with cellulose nanocrystals and citric acid. Effect on film physical properties. Carbohydrate Polymers. 2017;164:317-324. DOI: 10.1016/j.carbpol.2017.02.019
  97. 97. Revol JF. On the cross-sectional shape of cellulose crystallites in Valonia ventricosa. Carbohydrate Polymers. 1982;2:123-134. DOI: 10.1016/0144-8617(82)90058-3
  98. 98. Postek MT, Moon RJ, Rudie AW, Bilodeau MA. Production and Applications of Cellulose Nanomaterials. Peachtree Corners: Tappi Press; 2013
  99. 99. Dufresne A. Nanocellulose: A new ageless bionanomaterial. Materials Today. 2013;16:220-227. DOI: 10.1016/j.mattod.2013.06.004
  100. 100. Letchford J, Wasserman B, Ye HW, Burt H. The use of nanocrystalline cellulose for the binding and controlled release of drugs. International Journal of Nanomedicine. 2011:321. DOI: 10.2147/IJN.S16749
  101. 101. Timhadjelt L, Serier A, Belgacem MN, Bras J. Elaboration of cellulose based nanobiocomposite: Effect of cellulose nanocrystals surface treatment and interface “melting.”. Industrial Crops and Products. 2015;72:7-15. DOI: 10.1016/j.indcrop.2015.02.040
  102. 102. Ma P, Jiang L, Hoch M, Dong W, Chen M. Reinforcement of transparent ethylene-co-vinyl acetate rubber by nanocrystalline cellulose. European Polymer Journal. 2015;66:47-56. DOI: 10.1016/j.eurpolymj.2015.01.037
  103. 103. Zhou C, Shi Q, Guo W, Terrell L, Qureshi AT, Hayes DJ, et al. Electrospun bio-Nanocomposite scaffolds for bone tissue engineering by cellulose Nanocrystals reinforcing maleic anhydride grafted PLA. ACS Applied Materials & Interfaces. 2013;5:3847-3854. DOI: 10.1021/am4005072
  104. 104. McKee JR, Hietala S, Seitsonen J, Laine J, Kontturi E, Ikkala O. Thermoresponsive nanocellulose hydrogels with tunable mechanical properties. ACS Macro Letters. 2014;3:266-270. DOI: 10.1021/mz400596g
  105. 105. Mariano M, El Kissi N, Dufresne A. Melt processing of cellulose nanocrystal reinforced polycarbonate from a masterbatch process. European Polymer Journal. 2015;69:208-223. DOI: 10.1016/j.eurpolymj.2015.06.007
  106. 106. Li Y, Chen H, Liu D, Wang W, Liu Y, Zhou S. pH-responsive shape memory poly(ethylene glycol)–poly(ε-caprolactone)-based polyurethane/cellulose nanocrystals nanocomposite. ACS Applied Materials & Interfaces. 2015;7:12988-12999. DOI: 10.1021/acsami.5b02940
  107. 107. Herrera N, Salaberria AM, Mathew AP, Oksman K. Plasticized polylactic acid nanocomposite films with cellulose and chitin nanocrystals prepared using extrusion and compression molding with two cooling rates: Effects on mechanical, thermal and optical properties. Composites Part A: Applied Science and Manufacturing. 2016;83:89-97. DOI: 10.1016/j.compositesa.2015.05.024
  108. 108. Nasseri R, Mohammadi N. Starch-based nanocomposites: A comparative performance study of cellulose whiskers and starch nanoparticles. Carbohydrate Polymers. 2014;106:432-439. DOI: 10.1016/j.carbpol.2014.01.029
  109. 109. Liu JC, Martin DJ, Moon RJ, Youngblood JP. Enhanced thermal stability of biomedical thermoplastic polyurethane with the addition of cellulose nanocrystals. Journal of Applied Polymer Science. 2015;132:1-8. DOI: 10.1002/app.41970
  110. 110. Wang B, Walther A. Self-assembled, iridescent, crustacean-mimetic nanocomposites with tailored periodicity and layered cuticular structure. ACS Nano. 2015;9:10637-10646. DOI: 10.1021/acsnano.5b05074
  111. 111. Schyrr B, Pasche S, Voirin G, Weder C, Simon YC, Foster EJ. Biosensors based on porous cellulose nanocrystal–poly(vinyl alcohol) scaffolds. ACS Applied Materials & Interfaces. 2014;6:12674-12683. DOI: 10.1021/am502670u
  112. 112. Montes S, Carrasco PM, Ruiz V, Cabañero G, Grande HJ, Labidi J, et al. Synergistic reinforcement of poly(vinyl alcohol) nanocomposites with cellulose nanocrystal-stabilized graphene. Composites Science and Technology. 2015;117:26-31. DOI: 10.1016/j.compscitech.2015.05.018
  113. 113. Yang S, Tang Y, Wang J, Kong F, Zhang J. Surface treatment of cellulosic paper with starch-based composites reinforced with nanocrystalline cellulose. Industrial & Engineering Chemistry Research. 2014;53:13980-13988. DOI: 10.1021/ie502125s
  114. 114. Slavutsky AM, Bertuzzi MA. Water barrier properties of starch films reinforced with cellulose nanocrystals obtained from sugarcane bagasse. Carbohydrate Polymers. 2014;110:53-61. DOI: 10.1016/j.carbpol.2014.03.049
  115. 115. Ilyas RA, Sapuan SM, Ishak MR, Zainudin ES. Water transport properties of bio-nanocomposites reinforced by sugar palm (Arenga pinnata) nanofibrillated cellulose. Journal of Advanced Research in Fluid Mechanics and Thermal Sciences Journal. 2018;51:234-246
  116. 116. Montero B, Rico M, Rodríguez-Llamazares S, Barral L, Bouza R. Effect of nanocellulose as a filler on biodegradable thermoplastic starch films from tuber, cereal and legume. Carbohydrate Polymers. 2017;157:1094-1104. DOI: 10.1016/j.carbpol.2016.10.073
  117. 117. Ilyas RA, Sapuan SM, Ishak MR, Zainudin ES. Development and characterization of sugar palm nanocrystalline cellulose reinforced sugar palm starch bionanocomposites. Carbohydrate Polymers. 2018;202:186-202. DOI: 10.1016/j.carbpol.2018.09.002
  118. 118. Roohani M, Habibi Y, Belgacem NM, Ebrahim G, Karimi AN, Dufresne A. Cellulose whiskers reinforced polyvinyl alcohol copolymers nanocomposites. European Polymer Journal. 2008;44:2489-2498. DOI: 10.1016/j.eurpolymj.2008.05.024
  119. 119. Cao X, Xu C, Wang Y, Liu Y, Liu Y, Chen Y. New nanocomposite materials reinforced with cellulose nanocrystals in nitrile rubber. Polymer Testing. 2013;32:819-826. DOI: 10.1016/j.polymertesting.2013.04.005
  120. 120. Bhatnagar A. Processing of cellulose nanofiber-reinforced composites. Journal of Reinforced Plastics and Composites. 2005;24:1259-1268. DOI: 10.1177/0731684405049864
  121. 121. Kvien I, Tanem BS, Oksman K. Characterization of cellulose whiskers and their nanocomposites by atomic force and electron microscopy. Biomacromolecules. 2005;6:3160-3165. DOI: 10.1021/bm050479t
  122. 122. Dufresne A, Vignon MR. Improvement of starch film performances using cellulose microfibrils. Macromolecules. 1998;31:2693-2696. DOI: 10.1021/ma971532b
  123. 123. Samir A, Alloin F, Paillet M, Dufresne A. Tangling effect in fibrillated cellulose reinforced nanocomposites. Macromolecules. 2004;37:4313-4316
  124. 124. Mathew AP, Dufresne A. Morphological investigation of nanocomposites from sorbitol plasticized starch and tunicin whiskers. Biomacromolecules. 2002;3:609-617. DOI: 10.1021/bm0101769
  125. 125. Ruiz MM, Cavaille JY, Dufresne A, Graillat C, Gerard J-F. New waterborne epoxy coatings based on cellulose nanofillers. Macromolecular Symposia. 2001;169:211-222. DOI: 10.1002/1521-3900(200105)169:1<211::AID-MASY211>3.0.CO;2-H
  126. 126. Favier V, Canova GR, Cavaillé JY, Chanzy H, Dufresne A, Gauthier C. Nanocomposite materials from latex and cellulose whiskers. Polymers for Advanced Technologies. 1995;6:351-355. DOI: 10.1002/pat.1995.220060514
  127. 127. Asrofi M, Abral H, Kasim A, Pratoto A, Mahardika M, Hafizulhaq F. Mechanical properties of a water hyacinth nanofiber cellulose reinforced thermoplastic starch bionanocomposite: Effect of ultrasonic vibration during processing. Fibers. 2018;6:40. DOI: 10.3390/fib6020040
  128. 128. Bondeson D, Oksman K. Polylactic acid/cellulose whisker nanocomposites modified by polyvinyl alcohol. Composites Part A: Applied Science and Manufacturing. 2007;38:2486-2492. DOI: 10.1016/j.compositesa.2007.08.001
  129. 129. Petersson L, Mathew AP, Oksman K. Dispersion and properties of cellulose nanowhiskers and layered silicates in cellulose acetate butyrate nanocomposites. Journal of Applied Polymer Science. 2009;112:2001-2009. DOI: 10.1002/app.29661
  130. 130. Magalhaes E, Luiz W, Cao X, Ramires MA, Lucia LA. Novel all-cellulose composite displaying aligned cellulose nanofibers reinforced with cellulose nanocrystals. Tappi Journal. 2011;10:19-25
  131. 131. Li Q, Zhou J, Zhang L. Structure and properties of the nanocomposite films of chitosan reinforced with cellulose whiskers. Journal of Polymer Science Part B: Polymer Physics. 2009;47:1069-1077. DOI: 10.1002/polb.21711
  132. 132. Azeredo HMC, Mattoso LHC, Avena-Bustillos RJ, Filho GC, Munford ML, Wood D, et al. Nanocellulose reinforced chitosan composite films as affected by nanofiller loading and plasticizer content. Journal of Food Science. 2010;75:1-7. DOI: 10.1111/j.1750-3841.2009.01386.x
  133. 133. de Mesquita JP, Donnici CL, Pereira FV. Biobased nanocomposites from layer-by-layer assembly of cellulose nanowhiskers with chitosan. Biomacromolecules. 2010;11:473-480. DOI: 10.1021/bm9011985
  134. 134. Lu P, Hsieh Y-L. Cellulose nanocrystal-filled poly(acrylic acid) nanocomposite fibrous membranes. Nanotechnology. 2009;20:415604. DOI: 10.1088/0957-4484/20/41/415604
  135. 135. Jean B, Dubreuil F, Heux L, Cousin F. Structural details of cellulose nanocrystals/polyelectrolytes multilayers probed by neutron reflectivity and AFM. Langmuir. 2008;24:3452-3458. DOI: 10.1021/la703045f
  136. 136. Podsiadlo P, Choi S-Y, Shim B, Lee J, Cuddihy M, Kotov NA. Molecularly engineered nanocomposites: Layer-by-layer assembly of cellulose nanocrystals. Biomacromolecules. 2005;6:2914-2918. DOI: 10.1021/bm050333u
  137. 137. Chauve G, Heux L, Arouini R, Mazeau K. Cellulose poly(ethylene-co-vinyl acetate) nanocomposites studied by molecular modeling and mechanical spectroscopy. Biomacromolecules. 2005;6:2025-2031. DOI: 10.1021/bm0501205
  138. 138. Dufresne A, Kellerhals MB, Witholt B. Transcrystallization in mcl-PHAs/cellulose whiskers composites. Macromolecules. 1999;32:7396-7401. DOI: 10.1021/ma990564r
  139. 139. Dubief D, Samain E, Dufresne A. Polysaccharide microcrystals reinforced amorphous poly(β-hydroxyoctanoate) nanocomposite materials. Macromolecules. 1999;32:5765-5771. DOI: 10.1021/ma990274a
  140. 140. Pandey JK, Kim CS, Chu WS, Choi WY, Ahn SH, Lee CS. Preparation and structural evaluation of nano reinforced composites from cellulose whiskers of grass and biodegradable polymer matrix. Journal of Composite Materials. 2012;46:653-663. DOI: 10.1177/0021998312438174
  141. 141. Fortunati E, Armentano I, Zhou Q, Iannoni A, Saino E, Visai L, et al. Multifunctional bionanocomposite films of poly(lactic acid), cellulose nanocrystals and silver nanoparticles. Carbohydrate Polymers. 2012;87:1596-1605. DOI: 10.1016/j.carbpol.2011.09.066
  142. 142. Hamad WY, Chuanwei M. Nanocomposite biomaterials of nanocrystalline cellulose (NCC) and polylactic acid (PLA). U.S. Patent 8,829,110; 2014
  143. 143. Xiang C, Joo YL, Frey MW. Nanocomposite fibers electrospun from poly(lactic acid)/cellulose nanocrystals. Journal of Biobased Materials and Bioenergy. 2009;3:147-155. DOI: 10.1166/jbmb.2009.1016
  144. 144. Salmieri S, Islam F, Khan RA, Hossain FM, Ibrahim HMM, Miao C, et al. Antimicrobial nanocomposite films made of poly(lactic acid)-cellulose nanocrystals (PLA-CNC) in food applications: Part A—Effect of nisin release on the inactivation of Listeria monocytogenes in ham. Cellulose. 2014;21:1837-1850. DOI: 10.1007/s10570-014-0230-6
  145. 145. Dong H, Strawhecker KE, Snyder JF, Orlicki JA, Reiner RS, Rudie AW. Cellulose nanocrystals as a reinforcing material for electrospun poly(methyl methacrylate) fibers: Formation, properties and nanomechanical characterization. Carbohydrate Polymers. 2012;87:2488-2495. DOI: 10.1016/j.carbpol.2011.11.015
  146. 146. Liu H, Liu D, Yao F, Wu Q. Fabrication and properties of transparent polymethylmethacrylate/cellulose nanocrystals composites. Bioresource Technology. 2010;101:5685-5692. DOI: 10.1016/j.biortech.2010.02.045
  147. 147. Horvath AE, Lindström T, Laine J. On the indirect polyelectrolyte titration of cellulosic fibers. Conditions for charge stoichiometry and comparison with ESCA. Langmuir. 2006;22:824-830. DOI: 10.1021/la052217i
  148. 148. Zhou C, Chu R, Wu R, Wu Q. Electrospun polyethylene oxide/cellulose nanocrystal composite nanofibrous mats with homogeneous and heterogeneous microstructures. Biomacromolecules. 2011;12:2617-2625. DOI: 10.1021/bm200401p
  149. 149. Helbert W, Cavaille JY, Dufresne A, Fourier UJ. Thermoplastic nanocomposites filled with wheat straw cellulose whisker. Part 1: Processing and mechanical behavior. Polymer Composites. 1996;17:604-611. DOI: 10.1002/pc.10650
  150. 150. Oksman K, Mathew AP, Bondeson D, Kvien I. Manufacturing process of cellulose whiskers/polylactic acid nanocomposites. Composites Science and Technology. 2006;66:2776-2784. DOI: 10.1016/j.compscitech.2006.03.002
  151. 151. Fortunati E, Puglia D, Monti M, Santulli C, Maniruzzaman M, Kenny JM. Cellulose nanocrystals extracted from okra fibers in PVA nanocomposites. Journal of Applied Polymer Science. 2013;128:3220-3230. DOI: 10.1002/app.38524
  152. 152. Alain D, Danièle D, Michel RV. Cellulose microfibrils from potato tuber cells: Processing and characterization of starch-cellulose microfibril composites. Journal of Applied Polymer Science. 2000;76:2080-2092. DOI: 10.1002/(SICI)1097-4628(20000628)76:143.0.CO;2-U
  153. 153. Peresin MS, Habibi Y, Vesterinen A, Rojas OJ, Pawlak JJ, Seppa JV. Effect of moisture on electrospun nanofiber composites of poly(vinyl alcohol) and cellulose nanocrystals. Biomacromolecules. 2010;11:2471-2477
  154. 154. Li W, Yue J, Liu S. Preparation of nanocrystalline cellulose via ultrasound and its reinforcement capability for poly(vinyl alcohol) composites. Ultrasonics Sonochemistry. 2012;19:479-485. DOI: 10.1016/j.ultsonch.2011.11.007
  155. 155. Zoppe JO, Peresin MS, Habibi Y, Venditti RA, Rojas OJ. Reinforcing poly(ε-caprolactone) nanofibers with cellulose nanocrystals. ACS Applied Materials & Interfaces. 2009;1:1996-2004. DOI: 10.1021/am9003705
  156. 156. Habibi Y, Goffin A-L, Schiltz N, Duquesne E, Dubois P, Dufresne A. Bionanocomposites based on poly(ε-caprolactone)-grafted cellulose nanocrystals by ring-opening polymerization. Journal of Materials Chemistry. 2008;18:5002. DOI: 10.1039/b809212e
  157. 157. Habibi Y, Dufresne A. Highly filled bionanocomposites from functionalized polysaccharide nanocrystals. Biomacromolecules. 2008;9:1974-1980. DOI: 10.1021/bm8001717
  158. 158. Ljungberg N, Bonini C, Bortolussi F, Boisson C, Heux L, Cavaillé. New nanocomposite materials reinforced with cellulose whiskers in atactic polypropylene: Effect of surface and dispersion characteristics. Biomacromolecules. 2005;6:2732-2739. DOI: 10.1021/bm050222v
  159. 159. Ljungberg N, Cavaillé JY, Heux L. Nanocomposites of isotactic polypropylene reinforced with rod-like cellulose whiskers. Polymer. 2006;47:6285-6292. DOI: 10.1016/j.polymer.2006.07.013
  160. 160. Rojas OJ, Montero GA, Habibi Y. Electrospun nanocomposites from polystyrene loaded with cellulose nanowhiskers. Journal of Applied Polymer Science. 2009;113:927-935. DOI: 10.1002/app.30011
  161. 161. Li S, Gao Y, Bai H, Zhang L, Qu P, Bai L. Preparation and characteristics of polysulfone dialysis composite membranes modified with nanocrystalline cellulose. BioResources. 2011;6:1670-1680
  162. 162. Auad ML, Richardson T, Hicks M, Mosiewicki MA, Aranguren MI, Marcovich NE. Shape memory segmented polyurethanes: Dependence of behavior on nanocellulose addition and testing conditions. Polymer International. 2012;61:321-327. DOI: 10.1002/pi.3193
  163. 163. Marcovich NE, Auad ML, Bellesi NE, Nutt SR, Aranguren MI. Cellulose micro/nanocrystals reinforced polyurethane. Journal of Materials Research. 2006;21:870-881. DOI: 10.1557/jmr.2006.0105
  164. 164. Pei A, Malho J-M, Ruokolainen J, Zhou Q, Berglund LA. Strong nanocomposite reinforcement effects in polyurethane elastomer with low volume fraction of cellulose nanocrystals. Macromolecules. 2011;44:4422-4427. DOI: 10.1021/ma200318k
  165. 165. Chazeau L, Cavaille JY, Canova G, Dendievel R, Boutherin B. Viscoelastic properties of plasticized PVC reinforced with cellulose whiskers. Journal of Applied Polymer Science. 1999;71:1797-1808. DOI: 10.1002/(SICI)1097-4628(19990314)71:11<1797:AID-APP9>3.0.CO;2-E
  166. 166. Chazeau L, Cavaillé J, Terech P. Mechanical behaviour above Tg of a plasticised PVC reinforced with cellulose whiskers; a SANS structural study. Polymer. 1999;40:5333-5344. DOI: 10.1016/S0032-3861(98)00748-4
  167. 167. Chazeau L, Cavaillé JY, Perez J. Plasticized PVC reinforced with cellulose whiskers. II. Plastic behavior. Journal of Polymer Science. Part B: Polymer Physics. 2000;38:383-392. DOI: 10.1002/(SICI)1099-0488(20000201)38:3<383::AID-POLB5>3.0.CO;2-Q
  168. 168. Qi H, Cai J, Zhang L, Kuga S. Properties of films composed of cellulose nanowhiskers and a cellulose matrix regenerated from alkali/urea solution. Biomacromolecules. 2009;10:1597-1602. DOI: 10.1021/bm9001975
  169. 169. Ma H, Zhou B, Li HS, Li YQ, Ou SY. Green composite films composed of nanocrystalline cellulose and a cellulose matrix regenerated from functionalized ionic liquid solution. Carbohydrate Polymers. 2011;84:383-389. DOI: 10.1016/j.carbpol.2010.11.050
  170. 170. Wang Y, Cao X, Zhang L. Effects of cellulose whiskers on properties of soy protein thermoplastics. Macromolecular Bioscience. 2006;6:524-531. DOI: 10.1002/mabi.200600034
  171. 171. Cao X, Chen Y, Chang PR, Stumborg M, Huneault MA. Green composites reinforced with hemp nanocrystals in plasticized starch. Journal of Applied Polymer Science. 2008;109:3804-3810. DOI: 10.1002/app.28418
  172. 172. Cao X, Chen Y, Chang PR, Muir AD, Falk G. Starch-based nanocomposites reinforced with flax cellulose nanocrystals. Express Polymer Letters. 2008;2:502-510. DOI: 10.3144/expresspolymlett.2008.60
  173. 173. Lu Y, Weng L, Cao X. Biocomposites of plasticized starch reinforced with cellulose crystallites from cottonseed linter. Macromolecular Bioscience. 2005;5:1101-1107. DOI: 10.1002/mabi.200500094
  174. 174. Saxena A, Ragauskas AJ. Water transmission barrier properties of biodegradable films based on cellulosic whiskers and xylan. Carbohydrate Polymers. 2009;78:357-360. DOI: 10.1016/j.carbpol.2009.03.039
  175. 175. Saxena A, Elder TJ, Kenvin J, Ragauskas AJ. High oxygen nanocomposite barrier films based on xylan and nanocrystalline cellulose. Nano-Micro Letters. 2010;2:235-241. DOI: 10.3786/nml.v2i4.p235-241
  176. 176. Saxena A, Elder TJ, Ragauskas AJ. Moisture barrier properties of xylan composite films. Carbohydrate Polymers. 2011;84:1371-1377. DOI: 10.1016/j.carbpol.2011.01.039

Written By

R.A. Ilyas, S.M. Sapuan, R. Ibrahim, M.S.N. Atikah, A. Atiqah, M.N.M. Ansari and M.N.F. Norrrahim

Submitted: 25 February 2019 Reviewed: 22 May 2019 Published: 12 September 2019