Carbon Resources Conversion xxx (2018) xxx–xxx

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Carbon Resources Conversion

CHINESE ROOTS
GLOBAL IMPACT
journal homepage: www.keaipublishing.com/en/journals/carbon-resources-conversion/

Nanocellulose: Extraction and application

Patchiya Phanthong a, Prasert Reubroycharoen c, Xiaogang Hao d, Guangwen Xu e, Abuliti Abudula a,
Guoqing Guan a,b,⇑
a
Graduate School of Science and Technology, Hirosaki University, 1-Bunkyocho, Hirosaki 036-8560, Japan
b
Department of Renewable Energy, Institute of Regional Innovation (IRI), Hirosaki University, 2-1-3, Matsubara, Aomori 030-0813, Japan
c
Department of Chemical Technology, Chulalongkorn University, Bangkok 10330, Thailand
d
Department of Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, China
e
Institute of Industrial Chemistry and Energy Technology, Shenyang University of Chemical Technology (SYUCT), Shenyang 110142, China

a r t i c l e i n f o a b s t r a c t

Article history: Recently, nanocellulose and its applications gain high attraction in both research and industrial areas due
Received 4 February 2018 to its attractive properties such as excellent mechanical properties, high surface area, rich hydroxyl
Revised 18 April 2018 groups for modification, and natural properties with 100% environmental friendliness. In this review,
Accepted 24 May 2018
the background of nanocellulose originated from lignocellulosic biomass and the typical extraction meth-
Available online xxxx
ods and general applications are summarized, in which the nanocellulose extraction methods related to
ball milling are mainly introduced. Also, an outlook on its future is given. It is expected to provide guid-
Keywords:
ance on the effective extraction of nanocellulose from biomass and its most possible applications in the
Biomass
Cellulose
future.
Nanocellulose fiber Ó 2018 Publishing services by Elsevier B.V. on behalf of KeAi Communications Co., Ltd. This is an open
Extraction access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
Application
Outlook

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2. Lignocellulosic biomass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3. Nanocellulose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
4. Application of nanocellulose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
5. Extraction of nanocellulose from lignocellulosic biomass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
5.1. Biomass pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
5.2. Extraction of nanocellulose. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
6. Extraction of nanocellulose with the assistance of ball milling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
7. Conclusions and future prospects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00

1. Introduction more and more important for their daily life since they are friendly
to nature. Nanocellulose is a natural nanomaterial which can be
In the 21st century, when humans become aware of environ- extracted from plant cell wall. With its nanometer size in diameter,
mental conservation, applications of renewable resources become nanocellulose consists of attractive properties such as high
strength, excellent stiffness, and high surface area [1,2]. In addi-
tion, with its structure, nanocellulose contains a plentiful of hydro-
⇑ Corresponding author at: Energy Conversion Engineering Group, Institute of xyl groups which are accessible for surface modification.
Regional Innovation (IRI), Hirosaki University, 2-1-3, Matsubara, Aomori 030-0813, Nanocellulose can be used in various fields in our life, such as
Japan. Fax: +81 17 735 5411.
biomedical products, nanocomposite materials, textiles, and so on.
E-mail address: guan@hirosaki-u.ac.jp (G. Guan).

https://doi.org/10.1016/j.crcon.2018.05.004
0950-0618/Ó 2018 Publishing services by Elsevier B.V. on behalf of KeAi Communications Co., Ltd.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Please cite this article in press as: P. Phanthong et al., Nanocellulose: Extraction and application, Carbon Resour. Convers. (2018), https://doi.org/10.1016/j.
crcon.2018.05.004
2 P. Phanthong et al. / Carbon Resources Conversion xxx (2018) xxx–xxx
Nowadays, nanocellulose gets high attraction from research and
industries. The study of nanocellulose is not only about its extrac-
tion from biomass, but also the new applications in various fields.
The aim of this review is to make a brief summary on the study of
nanocellulose, including the typical extraction methods and the
general and special applications. An outlook on its future is also
given. It is expected to provide guidance on the effective extraction
of nanocellulose from biomass and its most possible applications in
the future.
2. Lignocellulosic biomass
Lignocellulosic biomass includes various natural organic mat-
ters which mostly refer to the plants or plant based materials,
which is the largest amount of sustainable carbon material group
and the most promising feedstock for the sustainable production
of biochemical, bioethanol, and biofuels [3]. Especially, lignocellu-
losic biomass is a source of natural fiber which can substitute the
petroleum-based polymers due to its outstanding environmentally
friendly properties. Furthermore, the wastes from biomass such as
agricultural wastes and forest residues have high potential for
reuse as fuel or feedstock for production of high value-added mate-
rials without the competition with human and animal food chains.
Cell wall structure of lignocellulosic biomass mainly consists of
three kinds of polymer, i.e. lignin, hemicellulose, and cellulose.
However, the composition and the content of these three compo-
nents are varied due to the difference in species, types, and sources
of lignocellulosic biomass [4,5]. Lignin represents about 10–25% by
weight of dry lignocellulosic biomass [6–8]. In plant cell walls, lig-
nin serves as the binder which holds between and around cellulose
and hemicellulose complexion (Fig. 1). With its binding function,
lignin provides the stiffness, compressive strength, resistant to
decay, and water impermeability to plant cell wall. Lignin consists
of the cross-linked amorphous copolymer synthesized from the
random of three different phenylpropane monomers, i.e., p-
coumaryl, coniferyl, and sinapyl alcohols which contains zero,
one, and two of methoxyl groups, respectively [9–11]. The ratio
of these three primary monomer units depends on the species
and sources of lignocellulosic biomass. Recently, the isolation of
lignin from lignocellulosic biomass and the depolymerization of
lignin are mainly studied for the production of biofuels and chem-
icals from natural materials [10,12]. In addition, lignin-based car-
bon materials are also applied for catalysis, energy storage, and
pollutant removal, which are attractively developed [11].
Hemicellulose represents about 20–35% in lignocellulosic bio-
mass [6–8]. Hemicellulose is the heteropolymer which is com-
posed by the short, linear, and branched chains of different kinds
of monomers such as pentoses and hexoses [13,14]. The common
types of hemicellulose are xylans and glucomannans. Xylans are
abundantly composed in hardwood while glucomannans are
mostly found in softwood [15,16]. Hemicellulose adheres to the
cellulose fibrils through hydrogen bonds and Van der Waal’s inter-
actions (Fig. 1). In addition, it also cross-links with lignin [15]. The
imbedding of hemicellulose with cellulose and lignin relates to the
strength in structure of plant cell wall. Hemicellulose can be
hydrolyzed by acid, alkali, or enzymes in mild conditions for pro-
Fig. 1. Main structure of plant cell wall in lignocellulosic biomass which is
consisted of lignin, hemicellulose, and cellulose.
Please cite this article in press as: P. Phanthong et al., Nanocellulose: Extraction and application, Carbon Resour. Convers. (2018), https://doi.org/10.1016/j.
crcon.2018.05.004
OH
OH
O *
* HO O
O
HO O
OH
OH n
Fig. 2. Schematic of cellobiose.
duction of fuel ethanol and the valuable chemicals from its oligo-
mers or monomers which can be used for food, cosmetic, mining
industries and so on [15,16].
Cellulose is the major component in lignocellulosic biomass
which is mainly localized in the plant cell wall at around 35–50%
[6–8]. It is composed of the linear homopolysaccharide of b-1,4-
linked anhydro-D-glucose units with the repeating unit of cel-
lobiose (Fig. 2) [17]. The monomer of cellobiose, named anhy-
droglucose unit, consists of three hydroxyl groups which form
strong hydrogen bond with the adjacent glucose unit in the same
chain and with the different chains, called as intramolecular and
intermolecular hydrogen bonding networks, respectively (Fig. 3)
[17]. These hydrogen bonding networks are strong and tightly
packed in the crystalline parts of cellulose fibrils which lead to
the tough, strength, fibrous, insoluble in water, and high resistant
to most organic solvents in plant cell wall [18–20]. The orientation
of glucose molecules and hydrogen bonding networks in cellulose
has wide orientation, resulting in different allomorphs of cellulose
[17]. The variation of cellulose allomorphs depends on the source
of lignocellulosic biomass and the treatment method. Generally,
there are four types of cellulose allomorph namely cellulose types
I, II, III, and IV [19,20]. Cellulose type I is the general allomorph of
cellulose in nature or native cellulose which is the parallel packing
of hydrogen-bond network. Cellulose type II comes from the chem-
ical regeneration of cellulose type I by dissolving in a solvent or
swelling in acid or alkaline solution. With these chemical regener-
ations, cellulose type II is composed by the different arrangements
of antiparallel packing of hydrogen-bond network. Cellulose type
III can be obtained from the ammonia treatment of cellulose I or
II, while cellulose type IV is the modification of cellulose III by
heating up to 260 °C in glycerol [19,20]. With its plentiful carbon,
hydroxyl groups, monomers of glucose, cellulose is the most natu-
ral source for the production of carbon-based materials, valuable
chemicals, textiles, papers, and so on [20,21].
3. Nanocellulose
With various hydroxyl groups and strong hydrogen bonding
networks, cellulose fiber is composed of the outstanding physical
and mechanical properties [1,2]. However, cellulose fibrils aggre-
gate with the highly ordered regions (crystalline structure) and
the disordered regions (amorphous structure) [17]. At the crys-
talline parts, the chain molecules are of orderly packing which pro-
motes high stiffness and strength of cellulose. In other ways, the
amorphous parts contribute to the flexibility of the bulk material
[2]. Within the aggregation of ordered and disordered regions, cel-
lulose fibers contain 3–100 mm of size in diameter with 1–4 mm in
length for general lignocellulosic biomass [20].
Nanocellulose is the natural fiber which can be extracted from
cellulose. The special attention is the size of nanocellulose fiber
which generally contains less than 100 nm in diameter and several
micrometers in length. Nanocellulose is a biodegradable nanofiber
with light weight, low density (around 1.6 g/cm3) and outstanding
 P. Phanthong et al. / Carbon Resources Conversion xxx (2018) xxx–xxx 3

Fig. 3. Intramolecular ( ) and intermolecular ( ) hydrogen bonding networks in cellulose structure.

strength property. Especially, it has high stiffness up to 220 GPa of
elastic modulus which is greater than Kevlar fiber. Moreover,
nanocellulose has high tensile strength up to 10 GPa which is
greater than cast iron and its ratio of strength to weight is 8 times
higher than stainless steel. In addition, nanocellulose is transparent
and full of the reactive surface of hydroxyl groups which can be
functionalized to various surface properties [1,2,17,22].
Nanocellulose can be categorized into three main types;
nanocrystalline cellulose, nanofibrillated cellulose, and bacterial
nanocellulose ones. Although all types are similar in chemical com-
position, they are different in morphology, particle size, crys-
tallinity, and some properties due to the difference of sources
and extraction methods [17,20].
Nanocrystalline cellulose, also known as cellulose nanocrystals,
nanocrystal of cellulose, or cellulose nanowhiskers, is nanocellu-
lose with high strength, which is usually extracted from cellulose
fibrils by acid hydrolysis [1,2]. It has the short-rod-like shape or
whisker shape with 2–20 nm in diameter and 100–500 nm in
length. Also, it contains 100% of cellulose chemical composition
mainly in crystalline regions (high crystallinity around 54–88%)
[17,20]. Fig. 4 shows the schematic of nanocrystalline cellulose
which can be extracted from cellulose fibrils by acid hydrolysis.
The amorphous parts are hydrolyzed and removed by acid while
the crystalline parts are still maintained [2,17]. Inference from this
extraction method is nanocrystalline cellulose contains high
crystallinity with a short-rod shape.
Nanofibrillated cellulose, also known as cellulose microfibril,
microfibrillated cellulose, cellulose nanofiber, cellulose nanofibril,
or nanofibrillar cellulose, is the long, flexible, and entangled
nanocellulose which can be extracted from cellulose fibrils by
mechanical methods. It has the long fibril shapes with 1–100 nm
in diameter and 500–2000 nm in length [23,24]. Also, it contains
100% of cellulose chemical composition with both of crystalline
and amorphous regions [1,2]. Fig. 5 shows the schematic of
nanofibrillated cellulose which can be extracted from cellulose
chains by the cleavage of fibrils in longitudinal axis from the force
which is applied by mechanical process [17]. Comparing with
nanocrystalline cellulose, nanofibrillated cellulose has the longer
length with high aspect ratio (length to diameter), high surface
area, and high extensive of hydroxyl groups which is easily acces-
sible for surface modification [20].
Bacterial nanocellulose is another kind of nanocellulose which
is different from nanocrystalline cellulose and nanofibrillated cel-
lulose. Nanocrystalline and nanofibrillated celluloses can be
extracted from lignocellulosic biomass (top-down process) but
bacterial nanocellulose is produced from building up of low molec-
ular weight of sugars by bacteria mainly by Gluconacetobacter
xylinus for a few days up to two weeks (bottom-up process)
[23–25]. As such, the bacterial nanocellulose is always in the pure
form without other components from lignocellulosic biomass such
as lignin, hemicellulose, pectin and so on. Bacterial nanocellulose
has the same chemical compositions as other two kinds of

Fig. 4. Schematic of nanocrystalline cellulose which can be extracted from cellulose chains using acid hydrolyzed amorphous region and left only crystalline region.

Fig. 5. Schematic of nanofibrillated cellulose which can be extracted from cellulose chains using mechanical process to cleavage the fiber into nanometer size in diameter.

Please cite this article in press as: P. Phanthong et al., Nanocellulose: Extraction and application, Carbon Resour. Convers. (2018), https://doi.org/10.1016/j.
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4 P. Phanthong et al. / Carbon Resources Conversion xxx (2018) xxx–xxx
Fig. 6. Schematic of hairy cellulose nanocrystalloids which can be extracted from cellulose chains by chemical treatment. The amorphous parts are solubilized while the
cleaving of some amorphous chains are protruded at both ends of crystalline regions.
nanocelluloses. It is in the form of twisting ribbons with the aver-
age diameters of 20–100 nm and micrometer lengths with large
surface area per unit [23–25].
Recently, hairy cellulose nanocrystalloid (HCNC) has been
reported by van de Ven and coworkers. It can be extracted from
cellulose chains by a chemical treatment method, but neither acid
hydrolysis nor mechanical methods. As a result, the amorphous
regions are solubilized but crystalline regions remained similar
to the extraction of nanocrystalline cellulose using conventional
methods. It is worth noting that HCNC consists of some cellulose
chains which can be cleaved and protruded from both ends of crys-
talline region as shown in Fig. 6 [26–29]. As such, HCNC has high
crystallinity and mainly in rod-shaped dimension similar to
nanocrystalline cellulose but it also contains both of crystalline
and amorphous parts similar to nanofibrillated cellulose. HCNC
consists of various kinds of derivatives depending on its protruded
tails which are affected from the different chemical reactions
[26–31].
Sterically stabilized nanocrystalline cellulose (SNCC) is one typ-
ical derivative of HCNC. It can be produced by chemical reaction
with periodate (IO4 ) followed by heating treatment. The negative
charges of periodate ions can break C2AC3 bonds of glucose units.
Meanwhile, it can also convert the C2AC3 hydroxyl groups into
aldehydes. As a result, the amorphous regions of cellulose chains
can be penetrated while the dialdehyde chains can be created
and cleaved at the ends of remaining crystalline regions. With
the high reactivity of dialdehyde chains, SNCC can be functional-
ized with other chemical groups without any charges [26,28].
Electrosterically stabilized nanocrystalline cellulose (ENCC) is
another kind of HCNC. It can be extracted from cellulose chains
by periodate/chlorite oxidation reaction. As a result, the rod-
shaped crystalline parts are extracted and protruded by the dicar-
boxylated chains. With dicarboxylated chains, ENCC can be more
highly charged, resulting in higher colloidal stability compared to
the general nanocrystalline cellulose [26,27,32,33].
4. Application of nanocellulose
With the excellent properties and biodegradable, nanocellulose
is attractive for applications in many fields such as nanocomposite
materials, surface modified materials, and transparent paper with
special functions [23].
Nanocomposite materials made using nanocellulose always
have some special properties such as high mechanical strength
and high thermal properties with lightweight and transparency
[2,22,23]. To date, nanocellulose has been used as the filler in poly-
mer matrix due to its excellent mechanical properties. Such
nanocomposite materials can be applied in many fields in our daily
life. The windmill blade with high strength structure, lightweight
armor, flexible batteries, and others have been made from nanocel-
lulose [34–36]. Wang et al. [37] studied the mechanical properties
of synthetic polymers made by adding of nanocellulose extracted
from soybean to three kinds of different polymers, and found that
Please cite this article in press as: P. Phanthong et al., Nanocellulose: Extraction and application, Carbon Resour. Convers. (2018), https://doi.org/10.1016/j.
crcon.2018.05.004
the tensile strength and stiffness of the polymer reinforced by
nanocellulose are significantly increased when compared with
the pure base polymers.
Poly(lactic acid) (PLA) is one of the main attracting polymeric
materials for nanocomposite materials due to its renewable prop-
erties. The composites of nanocellulose and PLA are widely studied
because both of them are renewable materials. Robles et al. [38]
studied the using of nanocellulose as the reinforcement in poly
(lactic acid) to form the new composite materials, and found that
the nanocellulose enhanced the interaction among matrix fillers.
Moreover, the thermal properties and crystallization were also
improved.
With high surface area and abundant of hydroxyl groups,
nanocellulose can be used for surface modification. The most com-
mon method is direct chemical modification or covalent attach-
ment with hydroxyl groups of nanocellulose surface [1,17]. Also,
the polymer grafting onto nanocellulose or grafting from nanocel-
lulose is widely used for the modification of grafted polymers and
nanocomposite materials. One of the main applications from the
surface modification of nanocellulose is the fabrication of
amphiphobic surface. Amphiphobic surface is the surface which
can protect both polar and non-polar liquids [39]. This anti-
wetting property relates to the special surface with properties of
self-cleaning, anti-bacterial, anti-reflective, corrosion resistant
and so on [39–41]. The main role of nanocellulose is adding the
hydroxyl group onto the surface of substrates for enhancing the
hydrophobization with chemicals, leading to the change in wetta-
bility of surface. Other chemical reactions such as etherification,
silylation, carbanylation, and amidation, are also used for modifica-
tion of nanocellulose by reaction with the hydroxyl groups in it for
various applications and specific properties [17,42]. Phanthong
et al. [43] fabricated the amphiphobic nanocellulose-modified
paper. Firstly, nanocellulose was coated on the surface of filter
paper, then the coated-paper was treated by chemical vapor depo-
sition with trichloro(1H,1H,2H,2H-tridecafluoro-n-octyl)silane.
The obtained paper showed superhydrophobicity and oleophobic-
ity repelling from polar and non-polar liquids in several environ-
ments. This kind of novel nanocellulose-modified paper can be
applied in the areas which need the anti-corrosion and self-
cleaning surfaces.
Besides excellent mechanical property, nanocellulose paper is
transparent, optically clear, and foldable. Such transparent papers
can be applied to electronic devices, solar cells, flexible displays,
flexible circuits instead of the conventional papers [44–47]. Nogi
et al. [48] fabricated the transparent nanocellulose paper from
wood flour, and found that the obtained paper showed the opti-
cally transparent, high-strength (223 MPa), high modulus (13
GPa), and minimal thermal expansion (8.5 ppm K 1) which is suit-
able for electronic devices.
Due to its low toxicity, renewable, good biocompatibility, and
excellent physical properties, nanocellulose is also widely applied
in medical field [23]. Hakkarainen et al. [49] used the nanofibril-
lated cellulose from the bleached birch pulps for wound dressing,
 P. Phanthong et al. / Carbon Resources Conversion xxx (2018) xxx–xxx
and found that the nanofibrillated cellulose can be highly biocom-
patible with the skin graft donor sites. Nanocellulose dressing can
be well adhered with wound and easily detached by itself after
skin recovery [23]. Other applications of nanocellulose in the med-
ical field such as drug delivery into target cells, implant of soft tis-
sue, blood vessel replacements and so on are also investigated in
recent years [50,51].
The novel type of hairy cellulose nanocrystalloid which consists
of nanocrystalline cellulose protruding with the functionalized
chains at both ends can be also widely applied. Hosseinidoust
et al. [52] extracted nanocellulose from softwood pulp sheet by
chemical treatment. As a result, the nanocrystalline celluloses with
different surface charges were obtained from different amounts of
carboxyl contents in protruding chains. It can be found that
nanocrystalline cellulose with carboxylated chains are not aggre-
gated in serum and can be uptaken by various cells which is suit-
able as the carrier for nanomedicine. Yang et al. [53] fabricated
transparent films from electrosterically stabilized nanocrystalline
cellulose (ENCC) with three different ways of modification. The
obtained films consisted of carboxyl groups in protruding chains
of ENCC showed 87% of light transmittance. Moreover, the trans-
parent films showed the hydrophobicity after treating with
trichloromethylsilane. Such natural films can be applied as flexible
packaging and other biodegradable products. In addition, ENCC can
be used for removal of copper ions in wastewater treatment. Shei-
khi et al. [33] extracted ENCC from wood fibers by periodate/chlo-
rite oxidation, then nanocrystalline cellulose with dicarboxylated
protruding chains was obtained. With the highly charged property
from dicarboxylated chains, ENCC was found to be able to remove
copper up to 185 mg/g. This is another application of nanocellulose
as a candidate for removal of heavy metal ions from wastewater. In
addition, cross-linking bifunctional hairy nanocrystalline cellulose
and carboxymethylated chitosan were successfully fabricated as
aerogels [54]. This biodegradable aerogels contain highly porous
and negative charges which related to the excellent performance
on adsorption of methylene blue dye up to 785 mg/g of adsorption
capacity. This opened the new application fields of bio-adsorbents
based on nanocellulose.
Besides the above applications, nanocellulose can be also
applied in other fields. For instances, it can be used as the
thickener in cosmetics, the texturing agent in food, filler of special
textiles, biodegradable package, CO2 adsorbent, and oil recovery
[55–58].
5. Extraction of nanocellulose from lignocellulosic biomass
Due to the outstanding properties of nanocellulose and possibil-
ity for the future applications, the study of nanocellulose extrac-
tion from lignocellulosic biomass is very attractive, especially for
the extraction from agricultural residues. Fig. 7 shows the sche-
matic of nanocellulose extraction from lignocellulosic biomass
which consists of two main steps. Firstly, the non-cellulosic com-
ponents, such as lignin, hemicellulose, and other compounds, are
removed by the pretreatment. Then, nanocellulose is extracted
from cellulose fibrils by various extraction methods [59,60].
Fig. 7. Schematic of nanocellulose extraction from lignocellulosic biomass.
Please cite this article in press as: P. Phanthong et al., Nanocellulose: Extraction and application, Carbon Resour. Convers. (2018), https://doi.org/10.1016/j.
crcon.2018.05.004
5
5.1. Biomass pretreatment
Nowadays, the agricultural wastes are attractive for being the
source of nanocellulose production. Not only it is high available
in nature, but also the using of agricultural residues can improve
the value from non-valuable wastes to high profits of nanocellulose
[61–63]. Moreover, the efficient use of the agricultural wastes is
good for environment. As indicated above, lignocellulosic biomass
consists of cellulose and non-cellulosic materials such as lignin,
hemicellulose, and other compounds. The pretreatment of biomass
is an important step for removing other non-cellulosic components
and remaining with cellulosic materials for further extraction of
nanocellulose [59,60].
The two classical methods for biomass pretreatment are acid-
chlorite treatment and alkaline treatment. The acid-chlorite treat-
ment, also known as delignification process, or bleaching process,
is widely used in pulp industries [64,65]. It can remove most of lig-
nin and other components by the combination of distilled water,
sodium chlorite, and acetic acid stirring with lignocellulosic bio-
mass at 70–80 °C for 4–12 h [61–64]. The acetic acid and sodium
chlorite are fed to the mixtures at interval time, i.e., at every hour,
for controlling the pH value. After that, the mixture is kept stirring
overnight, followed by washing with distilled water until reaching
the neutral pH. The obtained solid products are collected and dried
in oven at 50 °C, which is defined as holocellulose, mainly includ-
ing hemicellulose and cellulose in the fibers. The white color fiber
of holocellulose indicates the successful removal of lignin and
other impurities [62,63,66].
The alkaline treatment is the application of alkaline for remov-
ing the amorphous polymer of hemicellulose and the remaining of
lignin [61–63]. The generally used alkaline is sodium hydroxide
(4–20 wt%), which is always stirred with holocellulose for 1–5 h
[63,64]. Then, the obtained solid products are washed by distilled
water until reaching the neutral pH and finally dried in an oven
at 50 °C. The obtained fiber products from this treatment are
mainly in the form of cellulose, and other non-cellulosic materials
have been removed [66].
Recently, many groups used these biomass pretreatment meth-
ods for removing non-cellulosic materials in agriculture wastes.
For instance, Johar et al. [63] pretreated rice husks with alkaline
following by a bleaching process. They found that the content of
cellulose was increased from 35 wt% in untreated rice husks to
96 wt% in products after alkaline and bleaching pretreatments.
Moreover, lignin, hemicellulose and other non-cellulosic materials
were not detected in products. Other agricultural wastes such as oil
palm empty fruit bunch [59,60], sugarcane bagasse [61,67,68],
pineapple leaf [62], apple stem [66], coir fiber [69], mulberry bark
[70], rice hulls and bean hulls [71], and cotton linters [72] were
also pretreated prior to the nanocellulose extraction.
5.2. Extraction of nanocellulose
Several techniques have been developed for the extraction of
nanocellulose from cellulosic materials. The different extraction
methods resulted in the differences in types and properties of
6 P. Phanthong et al. / Carbon Resources Conversion xxx (2018) xxx–xxx
the obtained nanocellulose [73]. In this section, the main extrac-
tion methods are categorized to three techniques: acid hydrolysis,
enzymatic hydrolysis and mechanical process.
Acid hydrolysis is one of the main processes for the extraction
of nanocellulose from cellulosic materials. Due to the combination
of ordered and disordered regions in cellulose chains, the disor-
dered regions can be easily hydrolyzed by acid and the ordered
parts are left as the remaining [17,20]. Sulfuric acid is the acid
mostly used for acid hydrolysis [74,75]. It can not only strongly iso-
late nanocrystalline cellulose, but also make the nanocellulose dis-
persed as a stable colloid system due to the esterification of
hydroxyl group by sulfate ions [76,77]. The main controlling fac-
tors which affect the properties of obtained nanocellulose are reac-
tion time, temperature, and acid concentration [20,73]. The main
drawback of acid hydrolysis is the acid wastewater generated from
the washing process in order to neutralize the pH value of the
nanocellulose suspension. The washing process is usually per-
formed by adding cold water followed by centrifugation until neu-
tral pH is reached [63]. Another method for washing the obtained
products is using the alkaline such as sodium hydroxide to neutral-
ize pH value [78]. For example, Maiti et al. [79] extracted nanocel-
lulose from three different types of biomass by acid hydrolysis
with 47% sulfuric acid. After completion of reaction, the acid was
moved out by washing with deionized water and centrifugation
first and then, 0.5 N of sodium hydroxide was applied for neutral-
izing the suspension, followed by washing again with distilled
water.
2,2,6,6-Tetramethylpiperidine-1-oxyl radical (TEMPO) can be
used as the catalyst with the primary oxidant as hypochlorite in
order to oxidize hydroxyl group of cellulose to carboxylates [80–
82]. As such, the obtained nanofibrillated cellulose is approxi-
mately 3–4 nm in diameter and a few microns in length with a car-
boxylic acid surface [81,82]. The TEMPO-mediated oxidation is
realized by TEMPO/NaBr/NaClO in water with a high pH value,
by which TEMPO and NaBr can be dissolved and then, the oxida-
tion starts when NaClO is added. Moreover, another alternative
TEMPO/NaClO/NaClO2 oxidation system can be also used for this
process under neutral or weak acid conditions [24,81]. TEMPO-
oxidized cellulose nanofibers always contain uniform width (3–4
nm) with a high aspect ratio which can be applied as transparent
and flexible display, gas-barrier film for packaging, and nanofiber
filling for composite materials [81,82].
Enzymatic hydrolysis is the biological treatment process, in
which enzymes are used for digesting or modifying cellulose fibers
[21]. Generally, the biological treatment with enzyme can be per-
formed in mild conditions; however, long time of operation is
needed [21,83]. To solve this problem, the enzymatic hydrolysis
is always incorporated with other methods. Moniruzzaman et al.
[83] studied the separation of cellulose fibers from wood chips
by pretreatment with ionic liquid for enhancing the accessible sur-
face area, followed by enzymatic hydrolysis with laccase. The
obtained nanocellulose showed higher crystallinity and thermal
stability than the native wood fibers.
Mechanical process is the isolation of cellulose fibrils by apply-
ing high shear force to cleavage the cellulose fibers in longitudinal
axis, resulting in the nanofibrillated cellulose [2,21,22]. The mostly
used mechanical approaches include high pressure homogeniza-
tion, ultrasonication, and ball milling methods.
High pressure homogenization (HPH) is always performed by
passing cellulose slurry into a vessel with high pressure and high
velocity [21]. The impact force and shear force in fluid are gener-
ated to cleavage cellulose microfibrils into nanometer size in diam-
eter. For examples, Li et al. [68] isolated nanocellulose from
sugarcane bagasse by high pressure homogenization. The obtained
nanocellulose had a diameter of 10–20 nm with lower crystallinity
than the original cellulose. Wang et al. [84] extracted nanocellulose
Please cite this article in press as: P. Phanthong et al., Nanocellulose: Extraction and application, Carbon Resour. Convers. (2018), https://doi.org/10.1016/j.
crcon.2018.05.004
from cotton cellulose by high pressure homogenization and the
obtained nanocellulose had a diameter of about 20 nm with lower
thermal stability and crystallinity than the raw cotton cellulose.
The decreasing of crystallinity occurred since the intermolecular
and intra-molecular hydrogen bondings of cellulose were broken
during the high pressure homogenized process.
Ultrasonication is a process for the defibrillation of cellulose
fiber with the hydrodynamic forces of the ultrasound [2,21]. In this
method, the mechanical oscillating power is produced, resulting in
the formation, expansion, and implosion of microscopic gas bub-
bles when the liquid molecules absorb ultrasonic energy [85,86].
For example, Tang et al. [87] extracted nanocellulose from pure
wood pulp filter paper by the ultrasonication for 5 h at 70 °C and
obtained nanocellulose with a size of 10–100 nm in width and a
yield of 85.38%.
Ball milling is another mechanical method which can defibril-
late cellulose fibers. Due to the centrifugal force from the rotating
jar, the shear forces are created among balls and between balls and
the surface of jar [88,89]. As a result, the cellulose fibrils are
cracked to the smaller size in diameter [90–92].
However, the main drawback of mechanical process is the high
energy consumption. Therefore, the mechanical process is gener-
ally combined with other pretreatment method for decreasing
energy [21].
With various laboratory scale studies in order to develop new
extraction methods, some methods have already been applied in
pilot scale and at industrial level. The production of nanocellulose
was firstly started in a pilot plant scale in 2011 [93]. Nowadays,
nanocellulose production is expanding in industrial scale which
is widely spread mainly in Canada, USA, Europe, and Asia such as
China, Japan, Iran, and India [94]. The extraction methods currently
available in industries are mainly those conventional methods
such as sulfuric acid hydrolysis for production of nanocrystalline
cellulose and mechanical treatment for production of nanofibril-
lated cellulose [93,94]. This is because they are the successful
extraction ways in lab scale which have been developed for many
decades prior to launching in industry scale. However, the major
economic barrier of the current nanocellulose extraction is the
multi-step process, including high cost of chemicals, high cost of
production and maintenance of equipment operated in acidic envi-
ronments, difficult acid wastewater treatment for the processes
such as acid hydrolysis method, and high energy consumption
for the mechanical treatment way. Because of these reasons, the
better option of extraction method for the scale up is the one-
step process which can directly extract nanocellulose from bio-
mass residues.
It is worth noting that ball milling method becomes a high
potential for further development in extraction and application
of nanocellulose. The details will be discussed in the next section.
6. Extraction of nanocellulose with the assistance of ball milling
The study of ball milling with cellulose started from 1940s
[95,96]. However, when ball milling was used for grinding native
cellulose fibers, the amorphous cellulose was obtained. The
decreasing of crystallinity, size and morphology, and the changing
of crystalline lattice were detected from ball-milled cellulose. Her-
mans and Weidinger [95] studied the recrystallization of amor-
phous cellulose in 1946. The vibrating ball mill was used for
defibrillation of ramie fibers, and the powder of wood pulp fibers
was obtained after 4 h of milling accompanying by the formation
of amorphous products. Moreover, from XRD analysis, it can be
found that the crystalline pattern was also changed from cellulose
type I to cellulose type II form after ball milling. In the next 10
years, Howsmon and Marchessault [96] studied the effect from ball
 P. Phanthong et al. / Carbon Resources Conversion xxx (2018) xxx–xxx
milling of wood pulp cellulose up to 150 h of milling in dry state.
They found that the depolymerization of cellulose occurred due
to the severe mechanical process which led to the significant
decreasing of crystallinity. Moreover, the recrystallization, which
depended on the original lattice and conditions of ball milling,
was investigated. Cellulose type I, II, or IV was the end product
after recrystallization which depended on the conditions of ball
milling. This is the early study of ball milling of cellulose and bio-
mass which encouraged other researchers to study it thereafter.
Ball milling has been widely used for grinding materials and
particle refinement since 1990s. The main components of ball
milling machine consist of milling balls (or grinding media) with
various sizes contained in the milling jar (or milling beaker, milling
vessel). Nowadays, there are various types of ball millers widely
used in industry and laboratory such as planetary ball mill, mixer
ball mill, and vibration ball mill [97]. Among these, the planetary
ball mill is mostly used for defibrillation of cellulose and biomass.
Planetary ball mill is a mechanical process originated from the
collision between balls to balls and the friction of balls to the wall
of milling jar which moved in rotation as shown in Fig. 8 [88–90].
The collision from the moving balls and jar led to the grinding of
materials due to the frictional effects. This can lead to the smaller
size with large surface areas of materials. However, there are var-
ious variable factors which affected the characteristics of ball-
milled products such as, the number and size of balls, the milling
speed, the state of milling (dry or wet state), the weight ratio
between balls and materials, and milling time [88–92].
Ago et al. [98] studied the characteristics of cotton-derived cel-
lulose after ball milling with different water amount (0–50 wt%) at
400 rpm for 2 h. It is found that at dry state (0 wt% of water con-
tent) and with a little amount of water (10 wt%), the crystalline
type of cellulose was changed from cellulose type I to almost amor-
phous state. However, with the water content of 30 wt%, the crys-
talline type of cellulose was changed from cellulose type I to the
stable state of cellulose type II. This implies that the specific
amount of water in milling jar has great effects on the rearrange-
ment in the crystalline structure by the external force from ball
milling. Ouajai and Shanks also studied the characteristics of
ball-milled hemp cellulose [99]. It is found that the cellulose struc-
ture was broken into finer parts after ball milling while the surface
area was increased almost linearly with the milling time. However,
the amount of water, mechanical shearing force applied to ball-
milled fibers, and the drying rate led to the recrystallization of
amorphous cellulose. The effect of solvent added in ball miller
was investigated by Ago et al. in 2007 [100]. Cotton-derived cellu-
lose was ball-milled at 200 rpm for 4 and 8 h with 40 %(v/w) of
water, toluene, 1-butanol, and without any solvents. It is found
that ball milling with different kinds of solvents led to different
morphologies of ball-milled cellulose. This study also confirmed
that ball milling without solvent (or dry state) led to the occur-
rence of amorphous with lower crystallinity than the original fibers
Fig. 8. Schematic of planetary ball milling.
Please cite this article in press as: P. Phanthong et al., Nanocellulose: Extraction and application, Carbon Resour. Convers. (2018), https://doi.org/10.1016/j.
crcon.2018.05.004
7
and the fibers ball milled with solvents (Fig. 9a). In addition, ball-
milling with water affected the morphology by the cracks in the
concentric direction of fiber and the aggregation to globular parti-
cles in some areas (Fig. 9b). However, ball milling with toluene led
to the plate-like particles with no deep crack on the surface of
fibers (Fig. 9c) while the mixture of globular and plate-like parti-
cles was formed from the ball milling with 1-butanol (Fig. 9d).
Such studies in 2000s became the basic knowledge for ball milling
of cellulose and the extraction of nanocellulose in the following
decades.
Due to the significant decrease in size and crystallinity of cellu-
lose, the ball milling can be used as a pretreatment process prior to
hydrolysis of cellulose and biomass in order to produce valuable
chemicals. Zhao et al. [101] investigated the crystallinity of ball-
milled a-cellulose at 60 rpm for 1, 2, and 6 days prior to sulfuric
acid hydrolysis at 175 °C in a fluidized sand bath. It is found that
the crystallinity was decreased from 0.77 of the as-received cellu-
lose to 0.52 of the ball-milled after 6 days. However, with the obvi-
ous decrease of crystallinity from the ball milling for 6 days, the
conversion of cellulose to glucose by acid hydrolysis reached the
highest. This implies that the increasing of ball milling time led
to the increasing of cellulose conversion to glucose. Yu and Wu
[102] used the ball milling for the reduction of crystallinity of cel-
lulose prior to the hydrolysis in hot-compressed water in order to
produce glucose. They also confirmed that the ball milling was
effective for the increase in the reaction rate of cellulose hydrolysis
with over 80% conversion to glucose after the ball milling for 7 h.
Ball milling was also used for pretreatment of actual biomass prior
to convert them to sugar. Zakaria et al. used ball milling for the
pretreatment of empty fruit branch and frond fiber of oil palm
prior to the sugar production by enzymatic hydrolysis [103]. They
found that the increasing of ball milling time can increase the sur-
face area of biomass so that the hydrolysis by enzyme was
enhanced. With 60 min of ball milling time prior to the hydrolysis,
the frond fiber of oil palm can be converted to glucose with a yield
up to 87%. Yuan et al. also used ball milling for the pretreatment of
camphorwood sawdust and rape-straw prior to glucose production
by hydrothermal hydrolysis [104]. They concluded that ball milling
parameters affected the cellulose conversion in the order of milling
speed > milling time > mass ratio of balls to biomass. Moreover, the
optimum milling condition was 450 rpm of milling speed, 2 h of
milling time, and 30:1 of mass ratio between balls and biomass.
This condition led to the conversion of biomass to sugar with a
yield up to 37.8% which was four-times of conversion of raw mate-
rial. Ball milling was also used for the pretreatment of cellulose
prior to acid hydrolysis in order to effective extraction of nanocel-
lulose. Phanthong et al. [105] studied the effect of ball milling of
cellulose paper with different milling conditions prior to the sulfu-
ric acid hydrolysis in a low concentration condition. It is found that
the pretreatment by ball milling resulted in the smaller size of fiber
in diameter which can promote acid hydrolysis in mild conditions.
In the early 2010s, ball milling was directly used for the extrac-
tion of nanocellulose as tabulated in Table 1. Baheti et al. studied
the ball milling of jute fiber wastes in order to produce nanocellu-
lose [88]. In their study, the Jute fiber wastes were pretreated by
chemicals in order to remove lignin and hemicellulose prior to
defibrillate by the ball milling. The comparison of dry state and
wet state (milling with deionized water) of the ball milling was
also performed. They found that after the ball milling of cellulose
from jute fiber wastes for 1 h in dry and wet states, the particle size
distribution derived by the dry state ball milling was wide from
100 to 10,000 nm while the ball milling in the wet state led to a
narrow particle size distribution in the range of 100–1000 nm. This
is because the raw materials were stuck and aggregated on the
milling balls and jar wall in a dry state ball milling which affect
the size distribution wide. Moreover, this phenomenon was not
8 P. Phanthong et al. / Carbon Resources Conversion xxx (2018) xxx–xxx

Fig. 9. SEM images of cotton-derived cellulose after ball milling in (a) dry state, (b) water, (c) toluene, and (d) 1-butanol [100]. [Reprinted by permission from Springer Nature,
Copyright Ó 2007].

Table 1
Progress of nanocellulose extraction by ball milling.

Year Raw material State Milling condition Size of nanocellulose Reference

2012 Jute fiber wastes Wet (deionized water) 3 h, 850 rpm, 10:1 of BMR* <500 nm in diameter Baheti et al. [88]
2015 Northern bleached Wet (10 wt% in water) 1.5 h, 0.4–0.6 mm of ball 100 nm in diameter Zhang et al. [106]
softwood pulp kraft diameters, 40:1 of BMR
2015 Australian native grass Wet (1 %w/v aqueous 30 min, 1000 rpm, 0.4 mm of 8.7 ± 4.8 nm in diameter with few Amiralian et al. [107]
(Triodia pungens) dispersion) ball diameters microns in length
2016 Sugarcane bagasse Wet (50 mL of deionized 1 h, 0.5 mm of ball diameters, 240 ± 12 nm in diameter with Sofla et al. [108]
water) 80:1 of BMR 10 mm in length
2016 Kenaf fibers and wheat Wet (10 mL of 80% ethanol/ 2 h, 12.7 mm of ball diameters 8–100 nm in range Nuruddin et al. [109]
straw water mixture)
2017 Cellulose powder Wet (BMIMCl and distilled 2 h, 400 rpm, 12:1 of BMR 10–25 nm in diameter and Phanthong et al. [110]
water) micrometer scale in length
*
BMR = Weight ratio of balls to materials.

found in a wet state ball milling. It can be concluded that the addi-
tion of water or liquid during the ball milling can protect it from
the agglomeration of materials inside the instruments and results
in the narrow particle size distribution in nanometer scale. How-
ever, with this first study of using ball milling for extraction of
nanocellulose, the obtained size was still as large as around 500
nm of diameter which need to further adjust milling conditions
for decreasing the size smaller than 100 nm. Zhang et al. studied
in detail the ball milling conditions which could affect the produc-
tion yield of nanocellulose rather than amorphous particulates
[106]. They used Northern bleached softwood kraft as raw mate-
rial, and the sheet of dry pulp was soaked in 10 wt% water over-
night before ball milling at different conditions. It is found that
the size of milling balls is important for controlling the fiber prod-
ucts. Moreover, ball milling time and weight ratio of ball to mate-
rial were also important for controlling the collisions between balls
and raw materials in order to result in the producing of fibrous
morphology within 100 nm of diameter of nanocellulose products.
An Australian native grass (Triodia pungens) was used for the
extraction of cellulose nanofibrils via three different mechanical
processes by Amiralian et al. [107]. Ball milling was used for an
aqueous dispersion of grass (1% w/v) at 25 °C for 0.5–3 h at 1000
and 3000 rpms of milling speed. As a result, at 1000 rpm for 0.5
h, cellulose nanofibrils with 8.7 ± 4.8 nm in diameter and few
microns in length were obtained. However, with a higher milling
speed of 3000 rpm, the obtained nanofibers were obviously shorter
in diameter and length, that is, 8 ± 2 nm in diameter with 341 ± 1
00 nm in length. It is obvious that the high milling speed and
longer milling time can lead to the decreasing of aspect ratio of
the final nanocellulose product. In comparison with other two
mechanical methods (high pressure homogenizer and ultrasonica-
tion), it is found that the high pressure homogenizer was suitable

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crcon.2018.05.004
 P. Phanthong et al. / Carbon Resources Conversion xxx (2018) xxx–xxx
for the extraction of nanocellulose from this native grass, and the
obtained nanocellulose had an average size in diameter of 4.5 nm
and several microns in length. However, as for crystallinity, it is
found that the yields of nanocellulose extracted by the ball milling
and high pressure homogenizer were almost the same, i.e., 69%. In
contrast, the ultrasonication way resulted in a lower yield. Sofla
et al. found that nanocellulose can be extracted from ball milling
of sugarcane bagasse, and the obtained nanocellulose had a higher
aspect ratio when compared with the nanocellulose extracted by
the acid hydrolysis way [108]. Meanwhile, even though the
obtained nanocellulose had the similar chemical composition, the
crystallinity of nanocellulose from acid hydrolysis had a higher
value than that from the ball milling since the amorphous region
can be penetrated and removed out by acid. However, a higher
thermal stability was found in nanocellulose prepared by ball
milling than that prepared by acid hydrolysis. This study was the
first comparison of chemical and mechanical methods for the
extraction of nanocellulose from biomass. Nuruddin et al. studied
the extraction of nanocellulose from kenaf fibers and wheat straw
by ball milling [109]. After 2 h of milling, nanocellulose with the
size of 8–100 nm in diameter was obtained from both of kenaf
fibers and wheat straw, indicating that ball milling can reduce
the length and diameter. Even though the crystallinity was slightly
decreased after ball milling, the obtained nanocellulose maintained
cellulose type I but was not converted to cellulose type II or
amorphous cellulose. Moreover, there is no significant change in
chemical composition and thermal stability of the obtained
nanocellulose when ball milling was used.
For the nanocellulose extraction via ball milling, milling in a
wet state is suitable to maintain the fibrous state and prevent from
the defibrillation to amorphous state. Phanthong et al. [110] firstly
studied the extraction of nanocellulose by the combination of ball
milling with ionic liquid [110]. Ionic liquid is the group of salts
which is able to dissolve the cellulose by breaking the intramolec-
ular hydrogen bonding network. However, the dissolution of
cellulose by ionic liquid needs a high temperature or under ultra-
sonication condition. Using ball milling at room temperature was
successfully activated the dissolution in ionic liquid with a size
decrease of fiber. Fig. 10A–D shows the surface morphologies of
cellulose powder, cellulose powder after stirring with BMIMCl (1-
butyl-3-methylimidazolium chloride), ball-milled cellulose pow-
der without BMIMCl, and ball-milled cellulose powder with
BMIMCl. It is found that only by ball milling of cellulose powder
Fig. 10. SEM images of (A) cellulose powder, (B) mixing of cellulose powder and BMIMCl without ball milling, (C) ball-milled cellulose powder without BMIMCl, and (D)
nanocellulose from ball milling with BMIMCl, and (E) TEM image of nanocellulose from ball milling with BMIMCl [110]. [Reprinted by permission from Springer Nature,
Copyright Ó 2017].
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crcon.2018.05.004
9
with BMIMCl, the fibrous network of nanocellulose was obtained
as shown in Fig. 10D. Moreover, the size of obtained nanocellulose
was around 10–25 nm in width with a few micrometers in length
as confirmed by TEM image as shown in Fig. 10E. It is expected that
this one-step method for the nanocellulose extraction can be fur-
ther applied for the direct extraction of nanocellulose from
biomass.
Ball milling is also well-known for the application in
mechanochemical study. Mechanochemistry combines the
mechanical and chemical processes together. For example, the
chemical transformation of the cellulose surface can be realized
by the mechanical force from ball milling [97]. Liimatainen et al.
prepared dialdehyde cellulose by ball milling of kraft wood pulp
in the presence of sodium (meta) periodate as the oxidizing agent
[111]. The ball milling was conducted at 3500 rpm at room tem-
perature for 5–60 min. It is found that only 5 min of ball milling
can result in the decrease of the microfiber size of kraft wood pulp
to a few hundred of nanometers in diameter with the length of
below 50 mm. In addition, a longer time of ball milling led to the
increasing of accessible surface area for the obtained nanocellu-
lose, which is beneficial for the surface modification via oxidizing
agent. Sirviö et al. prepared the dialdehyde cellulose via
mechanochemistry [112], in which bleached birch was milled with
sodium (meta) periodate as oxidation agent and with metal salt
(LiCl and CaCl2) as activators. Here, ball milling was conducted at
room temperature with 2000 rpm of milling speed and up to
180 min of milling time. It is found that the dialdehyde fiber with
a high aspect ratio can be obtained in the first 15 min of milling
time. Moreover, the addition of metal salts can enhance the oxida-
tion during the ball milling. Hydrophobic films from ball milling of
microfibrillated cellulose with hexanoyl chloride (HC) were pre-
pared by Deng et al. [113], in which the effects of the volume of
HC added in ball milling (0–4 mL) and the milling time (1–12 h)
on the hydrophobicity and mechanical properties of the obtained
films were investigated. After the ball milling, the dispersion solu-
tion was coated on the film by dumping on polytetrafluoroethylene
holder under vacuum stage. It is found that at 3 h of milling with 4
mL of HC or 6 h of milling with 3 mL of HC were the optimum
milling condition for the mechanical properties. This is because
the longer time of milling led to the decreasing of fibers which
reduced the reinforcement in matrix. From this study, it can be
concluded that hydrophobicity and mechanical properties of film
can be controlled by adjusting the chemical and milling conditions.
10 P. Phanthong et al. / Carbon Resources Conversion xxx (2018) xxx–xxx
7. Conclusions and future prospects
Even though nanocellulose has various outstanding properties
and high availability in nature, the extraction of nanocellulose
from lignocellulosic biomass or cellulosic materials is still a main
challenge. Due to the strong aggregation of lignin, hemicelluloses,
and other materials in plant cell wall, the biomass pretreatment is
an essential step for removing all non-cellulosic materials. How-
ever, such a pretreatment always includes complex steps, takes a
long time, and consumes toxic chemicals and generates wastewa-
ter. In addition, the general methods for the nanocellulose extrac-
tion from cellulosic materials contain drawbacks such as the high
amount of acid waste water generation for the acid hydrolysis,
high energy consumption for mechanical process, and long reac-
tion time for enzymatic hydrolysis.
The motivation on nanocellulose study includes the develop-
ment of novel extraction methods with a facile step and less or
without wastewater. Meanwhile, the properties and yield of the
obtained nanocellulose should cross over the traditional methods.
Ball milling is an interesting and important way for effective
extraction of nanocellulose from biomass. Even though the extrac-
tion of nanocellulose with the assistance of ball milling has just
started since early of 2010s, it should attract more attention in
the future study. Here, it is not only important for the extraction
of nanocellulose directly from biomass, but also valuable for the
mechanochemical extraction of nanocellulose via ball milling in
the presence of chemicals in the future research.
Acknowledgements
This work is supported by Aomori City Government. Phanthong
P. gratefully acknowledged the scholarship from the Ministry of
Education, Culture, Sports, Science and Technology(MEXT) of
Japan.
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