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ICADME 2019 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 670 (2019) 012058 doi:10.1088/1757-899X/670/1/012058
Overview of cellulose nanocrystals: extraction,
physicochemical properties and applications
W L Lim1, A A N Gunny2,3 and F H Kasim1,2
1
School of Bioprocess Engineering, Universiti Malaysia Perlis, Kompleks Pusat
Pengajian Jejawi 3, 02600, Arau, Perlis, Malaysia
2
Centre of Excellence for Biomass Utilization, School of Bioprocess Engineering,
Universiti Malaysia Perlis, 02600, Arau, Perlis, Malaysia
3
Department of Chemical Engineering Technology, Faculty of Engineering, Universiti
Malaysia Perlis, Kampus UniCITI Alam, Sungai Chuchuh, 02100, Padang Besar,
Perlis, Malaysia
Abstract. The development of cellulose nanocrystal (CNC) has attracted significant attention
over the past few decades owing to its unique and superior properties. To date, acid hydrolysis
process is still the most frequently used method to treat cellulosic material for the production of
CNC. The main reason being that acid hydrolysis method is highly effective in removing the
amorphous regions within the cellulose microfibrils while retaining the crystalline domains,
thereby yielding CNC. CNC exhibits various outstanding characteristics such as large specific
surface area, high aspect ratio, good thermal and mechanical properties, lightweight, high
stiffness and high tensile strength. Owing to this, CNC has been subjected into a wide array of
research, including implementation as reinforcing agent in nanocomposites and sustainable
bio-materials to be utilized in various potential areas of industrial application. Overall, this
review summarizes the current knowledge on the isolation, physicochemical properties and
applications of CNC.
1. Nanocellulose
Nanocellulose refers to cellulose in the nanometer scale, also known as cellulose nanomaterial which
commonly derived from disintegration of the naturally occurring biopolymer or produced by bacteria
[1]. Nanocellulose can be divided into three main types; cellulose nanocrystal (CNC), cellulose
nanofibril (CNF) and bacterial cellulose (BC). Although all these three types are relatively similar in
chemical composition, but somehow different in morphological structure, particle size, crystallinity
and physicochemical properties due to the varied sources and extraction methods [2]. The elementary
fibrils in cellulosic fiber generally consist of highly ordered regions (crystalline structure) and
disordered regions (amorphous structure) which can be segregated through mechanical, chemical and
enzymatic methods in order to produce either CNF or CNC. In general, Nanocellulose exhibits
excellent physical and mechanical properties due to the presence of hydroxyl groups and strong
hydrogen bonding network [3].
1.1. Cellulose Nanocrystal (CNC)
Cellulose nanocrystal with other terminologies also known as nanocrystalline cellulose (NCC),
cellulose nanowhisker (CNW) or rod-like cellulose microcrystals. Individual cellulose molecules are
linked together to form elementary fibrils. Each elementary fibril contains nano-sized and highly
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ICADME 2019 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 670 (2019) 012058 doi:10.1088/1757-899X/670/1/012058
crystalline rod shaped fragments, commonly referred as CNC [2]. Each CNC rod generally has a width
about 2-30 nm and length of few hundred nanometers. However, the physical dimensions of CNC rod
are vary depending on several factors, including the source of the cellulose, hydrolysis conditions and
the ionic strength of acid. CNCs have high distribution in length due to the diffusion-controlled nature
of the acid hydrolysis process [4]. CNCs can be extracted from many different cellulosic resources
such as cellulose enriched pulp, microcrystalline cellulose and cotton via acid hydrolysis method [5].
2. Extraction of CNC
The initial concept of isolating CNC using acid hydrolysis method was introduced by Nickerson and
Habrle [6]. In the 1950s, a stable colloidal suspension of CNC was first obtained by Rånby through a
controlled sulfuric acid-catalyzed degradation of cellulose fibers [7]. During the controlled acid
hydrolysis process, amorphous regions of elementary nanofibril are preferentially hydrolyzed when
the hydronium ions infiltrate the cellulose chains in amorphous domains, triggering hydrolytic
cleavage of the glycosidic bonds by releasing individual crystallites while leaving the crystalline
domains intact [4].
There are many different types of strong inorganic acids such as sulphuric acid (H2SO4),
hydrochloric acid (HCl), phosphoric acid (H3PO4), hydrobromic acid (HBr), phosphotungstic acid
(PTA) and nitric acid (HNO3) have been successfully used for the production of CNCs [8]. All these
strong inorganic acids are diluted to the desired concentration before treating with cellulosic fiber
under strictly controlled conditions of temperature, agitation speed and reaction time. Among all the
inorganic acids, H2SO4 and HCl are the most common inorganic acids used for CNC preparation.
Many studies have reported that 55-65 wt. % of H2SO4 or 25-30 wt. % of HCl at moderate temperature
(40-60 °C) were applied in acid hydrolysis along with subsequent mechanical and ultrasound
disintegration of the hydrolyzed cellulose in aqueous suspension [9].
However, there are many alternative methods in extracting and improving the yield of CNC have
been introduced since the beginning of twenty-first century such as cation-exchange resin-catalyzed
hydrolysis [10], ultrasonic-assisted sulphuric acid hydrolysis [11], two-stage mildly acidic ionic
liquid-mediated hydrolysis [12] and acidic deep eutectic solvents (DESs) treatment [13]. Owing to the
emergence of DES, choline chloride (ChCl) has been successfully combined with organic acids such
as oxalic acid, p-toluenesulfonic acid monohydrate and levulinic acid to produce acidic DES which
used in acid hydrolysis of cellulosic fibers. In addition, Sirviö reported that these acidic DESs could
provide a green alternative pathway for CNC production [13].
3. Physicochemical properties of CNC
3.1. Specific surface area
Specific surface area (SSA) can be defined as the total surface area of a material per unit of mass. The
SSA of a non-porous material increases as the size of a particle decreases. For nanocellulose, the SSA
can be measured from the average geometrical dimensions of the particles, assuming that each CNC
rod-like geometry with a density of 1.5 or 1.6 g/cm3 [4]. Moreover, the SSA can be also determined by
Brunauer-Emmett-Teller (BET) surface area analysis from nitrogen gas adsorption isotherms at 77k
using a surface area or porosity analyzer [14]. However, the determination of SSA using nitrogen gas
adsorption isotherm is often inaccurate due to the irreversible aggregation of the CNC upon oven
drying [4]. Spray dried CNC, freeze dried CNC and spray-freeze dried CNC extracted from bleached
kraft pulp with SSA of 0.5 m2/g, 17.2 m2/g and 56.4 m2/g, respectively were reported by Abdallah and
Kamal [15]. Therefore, the CNC with high specific surface area is potentially useful in various nano-
applications, especially applied as porous template for the preparation of aerogel [4].
3.2. Thermal stability
Thermal stability is one of the important physical property which plays an essential role in preparation
of the CNC reinforced nanocomposites. The thermal stability of CNC can be determined using
thermogravimetric analysis (TGA). For CNC, the thermal stability is varied depending on the types of
surface chemistry [16]. For instance, the introduction of negatively charged sulphate half ester groups
2
ICADME 2019 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 670 (2019) 012058 doi:10.1088/1757-899X/670/1/012058
on the CNC surface obtained via dilute acid hydrolysis using sulphuric acid significantly affect the
thermal stability of CNC. During the acid hydrolysis, partial esterification of hydroxyl groups of
cellulose along with substitution by sulphonic acid groups (-SO3H) occur, significantly reduces the
thermal stability of CNC. Morais reported that the pure cellulosic fiber obtained from cotton linter
decomposes with a maximum rate at 340 °C while the isolated CNC degrades at 288 °C [17].
Moreover, the increasing of sulfonic acid groups content in CNC also leads to lower thermal stability
[18]. However, the thermal stability of CNCs isolated via HCl and H3PO4 acid hydrolysis tend to be
higher in which decompose at 325 °C and 350 °C respectively. Therefore, CNC with lower thermal
stability may limit its use as reinforcing filler to produce bio-nanocomposites at high temperature in
manufacturing process [16].
3.3. Aspect ratio
Aspect ratio is defined as the ratio of the length to the width. It is an important parameter to
determines the anisotropic phase formation and reinforcing properties. In general, the aspect ratio of
CNCs which isolated from cellulosic materials such as cotton, sisal, flax and jute via acid hydrolysis
ranging between 16 and 50 [2]. Some literature reported that the CNC prepared from the rare marine
creatures, also known as tunicates has higher aspect ratio (70-100) [19]. In fact, CNC with higher
aspect ratio has greater reinforcement capacity when added into the nanocomposite materials.
Consequently, this can improve the mechanical properties of the nanocomposite such as tensile
modulus due to the alignment of high aspect ratio filler particles which increases the surface area of
the fillers [20]. Owing to this, CNC with higher aspect ratio has great potential in filter and composite
membrane applications for air and water purification [4].
4. Application of CNC
CNC has been used in various applications owing to its availability and remarkable physical
properties. For instance, CNC exhibits high thermal conductivity and low coefficient of thermal
expansion which may suitable for the use in applications such as electronic devices and packaging.
Moreover, CNC often chosen as the nano-sized filler that act as reinforcement to improve the
mechanical and barrier properties of the matrix in bio-nanocomposite material. This is due to the CNC
generally has a high aspect ratio and large specific surface area that could provide better reinforcing
effects [21].
CNC has also been applied in the production of hydrogels and aerogels owing to its light weight
and toughness. The hydrophilic surfaces of CNC serve as building blocks to form the gels, which
enables crosslinking with other different metals, organic materials and polymers via hydrogen
bonding, covalent bond or ionic interactions [22]. In coating industry, the durability of water soluble
paints can be improved by incorporating CNC. The reason being that CNC acts as the thickening and
stabilizing agent that enhances the mechanical properties, scratch resistance and UV-shielding
property [23]. CNC is also serving as an important cosmetic ingredient that improves the sensation and
nourishment in facial and body applications. This is owing to the CNC having high dispersion stability
in water and water holding capability for a long period of time [4]. Furthermore, CNC can form a very
dense and resistant mats because of its strength to weight ratio which is eight times stronger than
stainless steel. This feature allows the CNC to be applied in manufacturing of bullet-proof vests and
body armor.
In medical application, CNC is widely utilized due to its excellent physical properties such as
extended surface area, surface functionality, biocompatibility, biodegradability and low toxicity. This
allow the CNC to be used in drug delivery, enzyme or protein immobilization, tissue skeleton for cell
culture and macroscopic biomaterials [24]. Moreover, CNC has been added into composite membrane
and adsorbent materials for the removal of contaminants. This is attributed to its high aspect ratio and
specific surface area, large retention capacity and environmental inertness. Consequently, the
pollutants such as heavy metal ions are binding to the active sites, thereby enhancing the filtration
efficiency [25].
3
ICADME 2019 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 670 (2019) 012058 doi:10.1088/1757-899X/670/1/012058
5. Conclusion
In conclusion, CNC is a rod-like nanoparticle that can be isolated from cellulosic sources through acid
hydrolysis process. CNC generally has many outstanding physical properties, including low density,
high aspect ratio and specific surface area, good thermal and mechanical properties that plays a vital
role as an intermediate in sustainable biomaterials and nanocomposites. Therefore, the transformation
of cellulose into CNC is perceived as a milestone in the field of materials science and engineering.
This is proven by the global attention in which CNC have been utilized in various applications such as
electronic devices, packaging, bio-nanocomposites, medical, filter, membranes and etc.
Acknowledgments
The authors thank to Ministry of Education for financing the research under Fundamental Research
Grant Scheme (FRGS 9003-00680)
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