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Nano Cellulose
Nano Cellulose
56
Nishtha Singh, Sonal Upadhyay, and Nidhi Mishra
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1366
Differences Among Cellulose and Nano Cellulose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1366
Applications of Nano Cellulose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1366
Different Methods of Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1367
Chemical Methods of Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1367
Synthesis Processes for Nanocellulose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1370
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1381
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1381
Abstract
Cellulose being the most ample natural-based polymer has been recently nano-
structured in the form of potential nanocellulose. Cellulose fibers at nanoscale
also known as nanocellulose or cellulosic nanoparticles have been prepared
utilizing various procedures. These serve as distinctive constituents based
on which materials are produced with enhanced potential and performance.
Basically, based on the procedures involved for the production, these have been
classified into two categories – microfibrillated cellulose and nanocrystals of
cellulose. They have the full potential to be an eco material. This chapter
highlights the synthesis and significance of nanocellulose as environmental
friendly, biodegradable, and recyclable nanoparticle making them potential can-
didates for various applications and processing of other polymer composites at
nanoscale.
Keywords
Nanocellulose · Synthesis · Biodegradable · Polymer · Hemicellulose · Lignin ·
Nanofibers · Nanocrystals · Filtration · Centrifugation
Introduction
As paper filler: Fibrillated cellulose can be used as fillers in paper as cellulose has
more strength and more amounts can be added as filler thus reducing the production
cost. Low amount of energy is required for drying purpose as there is less cellulose
56 Nanocellulose 1367
throughout the thickness. This paper has improved properties of low porosity,
low translucency, and high printing quality. And the transportation is more effi-
ciently done.
Surface coating: Nanocellulose has found application in surface coating.
Coating formulations which are starch based have been filled with zinc oxide and
cellulose nanofibrils for antibacterial paper. This paper shows bactericidal activity
against gram-negative bacteria and gram-positive bacteria. Concentration of cellu-
lose nanofibers influenced the adhesive property.
Construction: Micro-cellulose fibrils and cellulose nanomaterials can be utilized
in concrete which would increase the toughness. Significance involves reduction in
volume of cement required, thus reducing labor cost and material cost thereby
reducing the emission of corresponding greenhouse gas.
Energy: Devices converting chemical energy into electrical energy have been
defined as fuel cells. Nano cellulose-based nanocomposites have been utilized in
manufacturing of Li-ion battery, solar cells, and fuel cells [4].
Paint: Viscosity of coatings and paints can be modified by the use of nano-
cellulose. It has been used as an additive in polyurethane paints and varnishes. It
protects paints and varnishes from wearing away due to UV radiation. It provides
protection to the underlying materials. It extends the life of paints and varnishes and
reduces the cost and burden on environment of replacing the coatings.
Personal care: Cosmetic cellulose nanomaterials have been used as rheology
modifier which is non-allergic and as hydrating agent. It has been also used
in cosmetics for coating like in eyelashes, nails, etc. With increasing demands
of natural cosmetic products, it has led to increased demands of cellulose
nanomaterials.
Electronics: There is an ever-increasing demand of solar cells, transistors,
and printed electronics in information and communication area. These require
thin Polymer films. This can be provided by nanocellulose which would
provide films that will have properties of high tensile strength, smoothness at
nanoscale, low thermal expansion coefficient, and transparency (optical) [5, 6]
(Fig. 1).
Nanocellulose
biosensors
and cosmetics
diagnostics
Textile
industry
Different
processes of
preparing
Nanocellulose
a OH OH
+
O HO O H HO
O OH O OH
O O
OH OH
HO n HO n
O O
O
H H
OH Cellulose OH
Fast equilibrium H+
OH
OH
H+ HO
O
O OH
O HO
OH
n O
O
OH + HO OH
HO
O
OH
HO
H+
OH O
O
H H OH
b O
O
S
HO OH OH2+ SO3H
O HO O HO
O OH O OH
O O
OH n OH
HO HO n + H2O
O O
OH OH
Fig. 3 (a) Mechanism showing Acid hydrolysis of cellulose chain. (b) Cellulose Nano crystal
esterification process (From Lu and Hsieh 2010) [8]
Cellulose hydrolysis in
presence of metal ions
{M=Fe3+, Co2+, Ni2+}
O O
O OH
O
OH OH
HO O
HO
O
M OH
O O
O O
O
O O
OH
HO O OH O O
HO H
M
Fig. 4 Catalytic hydrolysis for preparation of nanocellulose using transition metals (From Chen
et al. [9])
Sugarcane bagasse: Industries like alcohol and sugar yield an ample amount of
sugarcane bagasse as residue every year which is being utilized for fuel and other
energy-producing processes. These residues have been also employed for the pro-
duction of paper and pulp. Their renewability and Biodegradability had led to their
processing for production of nanocellulose and microcrystalline cellulose. Majority
of the constituent of this biomass is the crystalline cellulose, and the other constit-
uents include hemicellulose, lignin, minerals, etc. nanocellulose has been obtained
utilizing the hydrolysis by strong acid like sulfuric acid. Firstly, easily available
sugarcane bagasse was acquired and cleaned. The sugarcane bagasse was grounded
56 Nanocellulose 1371
and later dried in an oven at 60 C for 16 h; 0.7% sodium chlorite solution was
utilized to bleach the grounded and dried sugarcane bagasse. The pH of 4 was
regulated by 5% acetic acid. To remove Lignin the mixture was boiled for 5 h. After
continuous washing with distilled water, it was boiled with 5% sodium sulfite
solution (250 ml) for 5 h, thus removing Lignin completely and partially removing
Hemicellulose. The Hemicellulose was separated by boiling it with 17.5% sodium
hydroxide solution (250 ml) for 5 h. Using Filtration cellulose was collected and
washed with distilled water to make it neutral. After air-drying, 50 ml DMSO
(dimethyl sulfoxide) is added in water bath maintained at 80 C for 3 h, followed
by filtration, washing, and air-drying. Hydrolysis using 60% sulfuric acid at 50 C
for 5 h is utilized for obtaining nanocellulose. Vigorous agitation is required.
Fivefold water is added to the mixture, followed by cooling and then Centrifugation
after each washing. After five consecutive washing and Centrifugation, a colloidal
suspension is obtained. In ice bath the suspension was sonicated for 5 min and then
stored at 4 C in a refrigerator [10] (Fig. 5).
China cotton, South Africa cotton, and Waste tissue paper: These materials
were mixed with 47% sulfuric acid and it is strongly stirred for 2 h at 60 C. The
suspension was centrifuged and washed with distilled water to decrease the concen-
tration of acid. 0.5 N NaOH finally neutralized the suspension followed by washing
with distilled water. The nanocellulose suspension was stored in a refrigerator [11]
(Fig. 6).
Pineapple leaf fibers: Properties like high stiffness and specific strength are
exhibited by PALF (pineapple leaf fiber). Fibrous cell bunches form the vascular
bundle system, and the fibers are in the form of ribbons. The fibers are easily
available and inexpensive. It has a high cellulose content resulting in high mech-
anical property. Pineapple leaves are by-product of pineapple cultivation.
Bromeliaceae family plant Ananus cosomus after extraction yields lignocellulosic
fiber by a process known as retting. For separation of nanofibres the method of steam
explosion is used which involves steaming at high pressure followed by decompres-
sion at a rapid rate. Pineapple fibers were cut into pieces of size 10 cm. Further
treatment followed placing the fibers in autoclave under 20 lb pressure for a duration
of 1 h after fibers were treated with NaOH (2%) in a ratio of 1:10 (fiber to NaOH).
After releasing the pressure immediately, the fibers were removed from autoclave
and NaOH was washed away with water. Mixture of acetic acid and NaOH was used
to bleach the mixture six times. Then the fibers were washed in distilled water and
dried followed by treatment with 11% oxalic acid in an autoclave until pressure of
20 lb is reached and then the pressure was released. This process was repeated for
eight times. The nanofibrils were suspended in water and stirred with mechanical
stirrer for a duration of 4 h for 8000 rpm [12] (Fig. 7).
Nanocellulose from beer industry residues: Beer industrial residue suspension
(10%) for attainment of constant weight was boiled for 1 h and then dried at 105 C.
Then it was soaked overnight in 2% NaOH, followed by washing and treatment with
12% NaOH and then autoclaving three times at 121 C for a duration of 45 min to
obtain pulp. At temperature of 105 C, the pulp was washed and dried. For removal
of lignin, treatment was done for 1 h at 75 C by a solution of NaClO2 (3%) and
1372 N. Singh et al.
NanoCellulose
CH3COOH (1.5%) two times. For removal of Hemicelluloses, the pulp was soaked
in a 3% KOH solution for a night followed by treatment for a duration of 1 h at
80 C. NaClO2 (3%) and CH3COOH (1.5%) bleached the pulp (1 h at 75 C)
followed by drying at 105 C. Hydrolysis of purified cellulose to 10% hydrochloric
acid was done for durations of 2 h, 4 h, and 6 h at 80 C. Washing was done by
centrifugation (three times) for 30 min at 4 C and 6000 rpm. Neutralized cellulose
was subjected to ultrasonic treatment for dispersion for 15 min that yielded nano-
cellulose [13] (Fig. 8).
Maize straw for preparation of Nanocellulose: Zea mays (maize straw) have
high carbon to nitrogen ratio making them resistant to degradation from microor-
ganisms in soil and thus decaying takes a longer time. Maize straw contains 28–44%
of cellulose. Cutin, pectin, and others were removed by Soxhlet method utilizing
ethyl alcohol (2 h), deionized water (4 h), and hexane (2 h) and dried at 80 C in an
56 Nanocellulose 1373
China Cotton, South Africa cotton, Waste tissue paper + 47% H2SO4 and strongly stirred
Centrifugation
oven. It was then treated with NaOH (5% w/v). The suspension of straw (1:100
straws to liquor ratio) was treated for 2 atm pressure at 121 C in an autoclave for
durations of 15, 30, 45, and 60 min. The pulp was filtered and washing was done
with deionized water till the attainment of neutralization. H2O2 (2% v/v) and tetra
acetyl ethylene diamine (0.2% w/v) was used to treat the pulp at 48 C for 12 h where
straw and liquor ratio is 1:25. The pulp was washed with deionized water. Dried pulp
was treated with acetic acid (80% in 1:33 ratio) and nitric acid (65% in 1:4 ratio) for
a duration of 30 min while stirring at 120 C. It was washed and filtrated in water
and ethyl alcohol. Purified cellulose was then treated with sulfuric acid (64%).
While stirring the hydrolysis with acid was carried out for different durations of
15,30,60,90,120,150, and 180 at temperature of 25 C. Cold deionized water was
added to stop the reaction. Ultrasonification for 15 min was done after Centrifugation
for 1 h at 3000 rpm [14] (Fig. 9).
Preparation from sisal fibers: The sisal fibers were washed with distilled water
and later dried in an oven for 24 h at 80 C and then cut into 5–10 mm length. Fibers
were boiled in a mixture of toluene/ethanol (2:1 v/v) for 6 h in a Soxhlet. The fibers
were washed, filtered with ethanol for 30 min, and later dried. Removal of lignin is
done by treatment with NaClO2 (0.7% w/v) and boiling for 2 h and treating with
NaHSO4 solution (5% w/v) followed with treatment by NaOH (17.5% w/v). Filter-
ing and washing is done with deionized water and dried in vacuum. Nanofibres are
1374 N. Singh et al.
Washed with distilled water and then dried with 11% Oxalic acid in autoclave for 8 times
obtained by acid hydrolysis. This is done with sulfuric acid solution (60%) for
30 min at 45 C while stirring [15] (Fig. 10).
Preparation of Nano cellulose from rice husk: Rice husk constituents are
cellulose, Hemicellulose, silica, and lignin. Rice husk was treated with KOH (3%
w/v in ratio of 1: 12) and boiled for 30 min and left for a night. After filtering
it was washed with distilled water, and hydrochloric acid (10%) was added.
Silica precipitate was removed. Lignocellulose residue was treated with NaClO2
(1:50 ratio) for 2 h at pH 4, then treated with sodium bisulfite solution (5%) for 1 h at
room temperature, and later dried at 100 2 C. NaOH (17.5%) was used to treat
for 8 h. The nanocellulose was obtained by treatment with sulfuric acid for 30 min
while stirring. To obtain the neutralized pH, washing was done with deionized water.
It was centrifuged and later dried using liophilizator [16] (Fig. 11).
From rubber wood fibers: Nanofibres of rubber wood were formed by two
treatments: (1) enzymatic and (2) ultrasonic. A solution of 3% was prepared by
suspending well-dried fibers (15 g) in deionized water (485 g). pH of 5 was
56 Nanocellulose 1375
Washed by centrifugation
Ultrasonic treatment
Nanocellulose
1376 N. Singh et al.
Treated with H2O2 and tetra acetyl ethylene diamine and then
washed with deionized water
Treated with H2SO4 acid and then add cold DI to stop reaction
Ultrasonification
Nanocellulose
Sisal fibres washed with distilled water and then cut into 5-10 mm in
length
Acid Hydrolysis
Nanofibres
Fig. 11 Flowchart
description of methodology of
synthesis of nanocellulose Rice husk +KOH and then boiled
using Rice husk
Silica removed
Nanocellulose
Nano fibres.
Fig. 13 Flowchart
description of methodology of
synthesis of nanocellulose by Fibres are frozen at low temperature
Cryocrushing
Fig. 14 Flowchart
description of methodology of
Suspension of cellulose fibrils is refined and diluted
synthesis of nanocellulose by
Homogenization
Conclusion
The need and demand for biodegradable and sustainable natural resources have led
to research for methods for production and use of nanocelluloses. Cellulose is
biodegradable, easily available, and cheap (relatively). Nanocellulose of different
shapes has been produced using different precursors and different methods (chem-
ical and mechanical). These nanocelluloses with improved properties have wide-
spread applications in the field of biomedical (surgical wounds, tissue engineering,
etc.), in construction, in paints, and in other applications. Nanocelluloses have also
been used as polymer nanocomposites. Being easily available and economical, the
use of natural cellulosic fibrils outweighs the limitations associated with them.
Taking into consideration environment cellulose which is biodegradable and natural
renewal polymer is an attractive combination finding role in various applications.
This chapter discusses various methods for production of nanocellulose, and also
few applications have been mentioned.
References
1. Kalia S, Dufresne A, Cherian BM et al (2011) Cellulose-based bio- and nanocomposites: a
review. Int J Polym Sci 2011:35
2. Chirayil CJ, Mathew L, Thomas S (2014) Review of recent research in nanocellulose prepara-
tion from different lignocellulosic fibers. Rev Adv MaterSci 37:20–28
1382 N. Singh et al.