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Introduction
Polymer nanocomposites have been a subject of increasing interest in recent years because of their significantly
enhanced mechanical properties and thermal stability versus
neat polymers or conventional polymer composites.1 Nanoscale cellulose fiber materials serve as promising candidates
for bio-nanocomposite production due to their abundance,
high strength and stiffness, low weight, and biodegradability.2 Isolation, characterization, and search for applications
of novel forms of cellulosevariously termed crystallites,
nanocrystals, whiskers, nanofibrils, and nanofibersare currently generating much activity.
Isolated cellulosic materials with one dimension in the
nanometer range are referred to generically as nanocelluloses. In a unique manner, these nanocelluloses combine
important cellulose properties such as hydrophilicity, broad
chemical-modification capacity, and the formation of versatile semicrystalline fiber morphologies. These morphologies
have the specific features of nanoscale materials due to their
very large surface area. Cellulose fibrils with widths in the
nanometer range are nature-based materials with unique
and potentially useful features. Most importantly, these
novel nanocelluloses allow new uses of natural cellulose
polymers in the expanding fields of nanocomposites and
sustainable materials. Nanocelluloses have high surface areas
resulting in powerful interactions with surrounding species,
such as water, organic and polymeric compounds, nanoparticles, and living cells.3
So far, a number of automotive components, appliances,
and packaging products are now being manufactured using
thermoplastic and thermoset natural fiber composites.4
Application of cellulose nanofibers in polymer reinforcement is a relatively new research field, although there is
Classification
A classification of nanocellulose material is given in Table I.
Nanocellulose nomenclature has not been used in a completely uniform manner in the past. Klemm et al.3 have
used the terms MFC, NCC, and BNC, the latter standing for bacterial nanocellulose. According to them the
name microfibrillated cellulose (MFC) was coined by the
original investigators and is widely used in the scientific
and commercial literature, whereas NCC and BNC seem
simple and descriptive. Maybe, over time, the nomenclature
nanofibrillated cellulose will prevail, and the nanocellulose
terminology will become more consistent.
Nanocellulose
A cellulose fiber consists of bundles of single cellulose fibers,
which have diameters of 2530 m. This single cellulose
fiber is made up of bundles of microfibers, which have diameters of 0.11 m. Nanofibers, which have a diameter in the
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Table I.
The Family of Nanocellulose Materialsa
Type of Nanocellulose
Synonyms
Typical Sources
Microfibrillated
Cellulose
(MFC)
Microfibrillated cellulose,
nanofibrils and microfibrils,
nanofibrillated cellulose
Nanocrystalline
Cellulose
(NCC)
Bacterial Nanocellulose
(BNC)
Bacterial synthesis
diameter: 20100 nm; different types of nanofiber
networks
Sources
Wood
Mechanical extraction of nanofibers from wood dates back
to the 1980s, when researchers produced MFC from wood
pulp using cyclic mechanical treatment in a high-pressure
homogenizer. The homogenization process resulted in
disintegration of the wood pulp and a material in which the
fibers were opened into their sub-structural microfibrils.
The resulting MFC gels consisted of strongly entangled and
disordered networks of cellulose nanofiber. Bleached kraft
pulp has often been used as the starting material for research
on MFC production.2
Agricultural Crops and By-Products
Wood is certainly the most important industrial source of
cellulosic fibers. Nevertheless, competition from different
sectors, such as the building products, furniture industries,
and the pulp and paper industry, as well as the combustion of wood for energy, makes it challenging to supply all
users with the quantities of wood needed at reasonable cost.
As a result, fibers from crops such as flax, hemp, sisal, and
others, especially from by-products of these different plants,
are likely to become of increasing interest. Other possible
examples of agricultural by-products which might be used
to derive nanocellulose include those obtained from the
cultivation of corn, wheat, rice, sorghum, barley, sugar cane,
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September/October 2014
pineapple, bananas, and coconut crops. Today, these agricultural by-products are either burned or used for low-value
products such as animal feed or in biofuel production. Because
of their renewability, crop residues can be valuable sources of
natural nanofibers.2
Bacterial Cellulose
In addition to its plant origins, cellulose fibers are also secreted
as extracellular structures by certain bacteria belonging to the
genera Acetobacter, Agrobacterium, Alcaligenes, Pseudomonas,
Rhizobium, or Sarcina. The most efficient producer of bacterial
cellulose is Acetobacter xylinum (or Gluconacetobacter xylinus),
a Gram-negative strain of acetic acid producing bacteria.3
MFC production by fibrillation of cellulose fibers into nanoscale elements requires intensive mechanical treatment.
However, depending upon the raw material and the degree
of processing, chemical treatments may be applied prior to
mechanical fibrillation. These chemical processes are aimed
to produce purified cellulose, such as bleached cellulose pulp,
which can then be further processed. There are also examples
with reduced energy demand in which the isolation of cellulose microfibrils involves enzymatic pre-treatment followed by
mechanical treatments.11
Forcing wood-based cellulose fiber suspensions through
mechanical devices, such as high-pressure homogenizers,
produces microfibrillated cellulose (MFC). Mechanical treatment delaminates fibers and liberates microfibrils that are ~20
nm wide. Pulp is produced from wood by chemical treatment. By using a mixture of sodium hydroxide and sodium
sulfide, so-called kraft pulp (almost pure cellulose fibers) is
obtained. Pulping with salts of sulfurous acid leads to cellulose
named sulfite pulp, which contains more by-products in the
cellulose fibers.
Fig. 1. TEM images of dried dispersion of cellulose nanocrystals derived from (a) tunicate (Reprinted with permission.16 Copyright 2008 American Chemical Society), (b) bacterial (Reprinted with permission.17 Copyright 2004 American Chemical Society), (c) ramie ( Reproduced18 by permission of The Royal
Society of Chemistry), (d) sisal (Reprinted with permission.19 Copyright 2006 Springer), (e) cotton (Reprinted with permission.20 Copyright 1996 American
Chemical Society), and (f) sugar beet (Reprinted with permission.21 Copyright 2004 American Chemical Society).
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Chemical Treatment
Mechanical Treatment
Grinding
Some researchers have attempted to use modified commercial grinders with specially designed disks to fibrillate
cellulose fibers. In such equipment, the cellulose slurry is
passed between a static grind stone and a rotating grind
stone revolving at a speed of about 1500 rpm. The fibrillation
mechanism of grinder treatment results from shearing forces
generated by the grinding stones. This brakes down the cell
wall structure consisting of nanofibers in a multi-layered
structure and hydrogen bonds. As a result, nanosized fibers
are individualized from the pulp.2
Cryocrushing
Cryocrushing is a method for producing nanofibers in
which fibers are frozen using liquid nitrogen followed
by the application of high shear forces.35 The objective of
cryocrushing is to form ice crystals within the cell wall.
When high impact forces are applied to the frozen fibers,
ice crystals inside the fibers exert pressure on the cell walls,
causing them to rupture and thereby liberating microfibrils.26 Bhatnagar and Sain30 obtained nanofibers with an
estimated diameter of 580 nm by applying cryocrushing
of chemically treated flax, hemp, and rutabaga fibers. The
cryocrushed fibers may then be dispersed uniformly into a
water suspension using a disintegrator before high-pressure
fibrillation. Cryocrushing combined with a high-pressure
fibrillation process was used also by Wang and Sain26,27
for isolation of nanofibers with diameters in the range of
50100 nm from soybean stock.
Sonication
Ultrasound is a part of the sound spectrum in the range of
20 KHz to 10 MHz generated by a transducer that converts
mechanical or electrical energy into high-frequency acoustical energy. High-intensity ultrasonication (HIUS) waves can
produce a very strong mechanical oscillating power due to
cavitation, which is a physical phenomenon that includes
the formation, expansion, and implosion of microscopic gas
bubbles when the molecules in a liquid absorb ultrasonic
energy. Within the cavitation bubble and the immediate surrounding area, violent shock waves are produced, resulting
in temperatures up to 5000 C and pressures of greater than
500 atm at implosion sites. Ultrasonic radiation is hence
used in many processes, including emulsification, catalysis,
homogenization, disaggregation, scission, and dispersion.36
Isolation of fibrils from several cellulose resources (e.g.,
regenerated cellulose fiber, pure cellulose fiber, MCC, and
pulp fiber) can be performed using HIUS energy in a bath
process. A mixture of microscale and nanoscale fibrils can be
obtained. The temperature of the fiber suspension increased
at a faster rate when the power was higherthe higher the
power, the better the fibrillation. The temperature of the
water suspension could reach up to 91 C without water
cooling. The higher the temperature, the better the cellulose
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Fig. 2. Methods of production of nanocelluloses from macroscopic cellulose fibers (Reprinted with permission.38 Copyright 2007 American
Chemical Society).
fibrillation, whereas the longer the raw fiber, the lower the
fibrillation. The cellulose concentration of the suspension
depends on the dimensions of the cellulose fiber, resulting
in lower concentrations when the fiber was longer. A larger
distance from the HIUS probe tip to the beaker bottom was
not beneficial to fibrillation.37 Fig. 2 summarizes nanocellulose production mechanisms.38
Conclusion
Growing research efforts have recently been reported regarding the formation and use of nanocelluloses, particularly
in the last seven years. It was confirmed that MFC, which
exhibits gel-like properties, can be obtained by a purely
mechanical process such as high-pressure homogenizer. A
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References
1.
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6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
DOI: 10.14504/ajr.1.5.3
Author
Mohammad Tajul Islam, assistant professor, Dept. of
Textile Engineering, Ahsanullah University of Science
and Technology, 141-142 Love Rd., Tejgaon I/A, Dhaka-1208, Bangladesh; phone +88.02.8870422, ext. 702; fax
+88.02.8870417; tajul.dtt@aust.edu.
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