03 13714 Cintil PDF
03 13714 Cintil PDF
03 13714 Cintil PDF
37 (2014) 20-28
Rev. J.Ch. Cintil, M. Lovely and Th. Sabu
Abstract. Lignocellulosic fibers have become the focus of intense interest in recent years. They
have attracted the attention of scientists and technologies worldwide because of their tremen-
dous advantages and now it is possible to isolate cellulose nanofibrils and nanowhiskers from
various lignocellulosic wastes. Studies in this area have shown that both cellulose nanofibrils
and nanowhiskers could be used as reinforcing fillers to improve mechanical and barrier prop-
erties of different types of polymer systems which include rubbers, thermoplastics and thermo-
sets. This review paper provides an overview of recent progress made in the area of nanocellulose
and nanowhiskers preparation from various natural fibers. A thorough review of the various
techniques being currently used for the isolation of cellulose nanofibers and nanowhiskers has
been presented. Finally, the emerging applications of these materials in various fields including
nanocomposite preparation have been presented.
k( 4Se
P]RTSFc
dSh6T]c
Ta6 c
S
Review of recent research in nano cellulose preparation from different lignocellulosic fibers 21
Fig. 1. Scheme of the cellulose cell wall and microfibril organization, Reprinted with permission from
G. Siqueira, J. Bras and A. Dufresne, Polymers vol 2, 2010 728, (c) 2010 MDPI.
extensively studied the extraction of nanofibers from and cell structure of natural fibers are quite compli-
the natural plant cellulose fibers. The main aim of cated. Each fiber is essentially a composite in which
this paper is to provide a comprehensive review on rigid cellulose microfibrils are embedded in a soft
different approaches being used to isolate cellulose matrix mainly composed of lignin and hemicellulo-
nanofibrils and nanowhiskers from different lignocel- ses [14]. The properties of cellulosic fibers are
lulosic fibers. The morphology and properties of strongly influenced by many factors like chemical
nanofibers and nanowhiskers obtained from various composition, internal fiber structure, micro fibril angle
lignocellulosc waste materials (extracted using vari- and cell dimensions which differ from different parts
ous techniques) have been discussed and com- of a plant as well as from different plants. The me-
pared. Finally, the applications of these nanoscale chanical properties of natural fibers also depend on
materials have been reviewed. their cellulose type because each type of cellulose
has its own crystalline organization, which can de-
2. STRUCTURE OF termine the mechanical properties [15]. An elemen-
LIGNOCELLULOSIC FIBERS tary plant fibre is a single cell typically a length from
1 to 50 mm and a diameter of around 10-50 m.
Lignocellulosic fibers are one of the major renew- Plant fibres are like microscopic tubes and it con-
able resource materials throughout the world. There sists of several cell walls. These cell walls are formed
are about 2000 species of useful fibre plants in vari- from cellulose microfibrils of diameter 10-30 nm and
ous parts of the world and these are used for many are made up of 30-100 cellulose molecules. Fig. 1
applications. Now industrialists utilize the locally shows the scheme of the cellulose cell wall and
grown fibres as substitute for expensive synthetic microfibril organisation. Extraction of fibres from the
fibres. Natural fibers basically constituted of cellu- plant stems is achieved by various methods. Ret-
lose, lignin and hemicellulose. Pectin, pigments and ting is a process of controlled degradation of the
extractives can be found in lower quantities. plant stem to allow the fibre to be separated from
For this reason natural fibers are also referred the woody core and thereby improving the ease of
as cellulosic fibers [13]. The chemical composition extraction of the fibres from the plant stems. Ret-
22 J.Ch. Cintil, M. Lovely and Th. Sabu
ting procedures can be divided into biological, me- mainly used as a rheology control agent and as a
chanical, chemical and physical fibre separation binder in the pharmaceutical industry [29].
process [16].
4. ISOLATION OF MICROCRYALLINE
3. STRUCTURAL ORGANIZATION OF CELLULOSE, CELLULOSIC
CELLULOSE NANOFIBRILS AND
Cellulose is considered to be the most abundant NANOCRYSTALS
renewable polymer on earth. This structural mate- Methods for producing MFC were first reported by
rial is organized as microfibrils linked together to Herrick et al. [30] and Turbak et al. The principle of
form cellulose fibers. It is biosynthesized by a num- their methods was to pass dilute cellulosic wood
ber of living organisms ranging from higher to lower pulp-water suspensions through a mechanical ho-
plants, some amoebae, sea animals, bacteria and mogenizer, in which a large pressure drop facilitated
fungi [17]. Cellulose consists of a linear micro fibrillation [3]. The manufacture of MFC is now
homopolysaccharide composed of D-glucopyranose generally performed by a mechanical treatment con-
units linked together by -1-4-linkages. Each mono- sisting of refining and high pressure homogenizing
mer bears three hydroxyl groups and these hydroxyl process [21,32-33]. Cryocrushing is an alternative
groups and their ability to form hydrogen bonds play method for producing nanofibers in which fibers are
a major role in directing the crystalline packing and frozen using liquid nitrogen and high shear forces
also governing the physical properties of cellulose are then applied. Alemdar and Sain (2008) extracted
[18]. Cellulose micro fibrils are the basic structural MFC from wheat straw and soy hulls via mechani-
component of cellulose formed during the biosyn- cal treatment. In such equipment the cellulose slurry
thesis. The chains of poly- -(1 4)-D-glucosyl resi- is passed between a static grind stone and a rotat-
dues aggregate to form a fibril which is a long thread- ing grind stone revolving at 1500 rpm [35]. A major
like bundle of molecules laterally stabilized by in- obstacle that needs to be overcome is the high en-
termolecular hydrogen bonds [19-21]. Individual cel- ergy consumption connected to the mechanical dis-
lulose microfibrils have diameters ranging from 2 to integration of the fibers to MFC. By combining the
20 nm. Each microfibril can be considered as a string mechanical treatment with certain pre-treatments it
of cellulose crystals linked along the micro fibril axis is possible to decrease the energy consumption.
by disordered amorphous domains [22]. The anoma- Before mechanical processing, a number of re-
lies exist in the literature regarding the nomencla- searchers have applied alkaline treatment of fibers
ture applied to cellulosics are reviewed by Siro and in order to disrupt the lignin structure and help to
Plackett 2010 [3]. The term microfibril is generally separate the structural linkages between lignin and
dbTSc STbRa XQTc WT(l ] c WX
RZU X
QadbRT[ [d carbohydrates [20,36]. Purification by mild alkali
lose structures with the length of several microns treatment results in the solubilisation of lignin, pec-
formed during cellulose biosynthesis in higher plants. tins and hemicelluloses. Oxidation pre-treatment is
Depending on their origin the micro fibril diameters another method. Saito et al. (2006) introduced an
may vary. Nanofibrils and nanofibers are also used oxidation pre-treatment of cellulose, applying
as synonyms for micro fibril. Even though the thick- 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) radi-
]Tbb U@96 ]P] T[ T T]c bXbPbb P[ [Pb)l cals before mechanical treatment [37]. Softwood
] X cXbc hX RP[[hX ]c WTa P]VT U( l ] bX ]RT and hardwood celluloses were oxidized by 2,2,6,6-
MFC usually consists of aggregates of cellulose tetramethylpiperidine-1-oxyl radical (TEMPO)-medi-
microfibrils [23]. When subjected to acid hydroly- ated oxidation. The TEMPO-oxidized cellulose fi-
sis, cellulose microfibrils undergo transverse cleav- bers were converted to transparent dispersions in
age along the amorphous regions and the use of water, which consisted of individual nanofibers 3"4
sonication results in a rod-like material with a rela- nm in width. Films were then prepared from the
tively low aspect ratio referred as cellulose whis- TEMPO-oxidized cellulose nanofibers (TOCN) and
kers [24]. Other synonyms for cellulose whiskers characterized from various aspects. AFM images
include nanowhiskers [25], nanorods [26], and rod- showed that the TOCN film surface consisted of
like cellulose crystals [27]. Strong hydrogen bond- randomly assembled cellulose nanofibers [9]. Sys-
ing between the individual cellulose crystals pro- tematic diagram of individualization of nano-sized
motes re-aggregation [28] which leads to another plant cellulose fibrils by surface carboxylation us-
cellulose structure called microcrystalline cellulose ing TEMPO catalyst is shown in Fig. 2. TEMPO-
(MCC). MCC is a commercially available material mediated oxidation is a promising method for sur-
Review of recent research in nano cellulose preparation from different lignocellulosic fibers 23
Fig. 2. Systematic diagram of individualization of nano-sized plant cellulose fibrils by surface carboxylation
using TEMPO catalyst. (Image: Dr. Isogai/University of Tokyo), Reprinted with permission from H. Fukuzumi,
T. Saito, T. Iwata, Y. Kumamoto and A. Isogai, Biomacromolecules vol 10, 2009, p. 162, (c) 2010 Americal
Chemical Society.
face modification of native celluloses by which car- in two distinct stages. Initially wood fibers were sub-
boxylate and aldehyde functional groups can be in- jected to a chemical process to eliminate lignin and
troduced into solid native celluloses under aqueous hemicellulose [42]. Then these fibers were mechani-
and mild conditions [38]. cally separated into nanofibers using high intensity
Enzymatic pre-treatment is another method for ultrasonication as shown in Fig. 3. The diameter
reducing energy consumption. Henriksson et al. distributions of the resulting nanofibers were depen-
(2007) and Paakko et al. (2007) found that dent on the output power of the ultrasonic treatment.
endoglucanase pre-treatment facilitates disintegra- They also isolated cellulose nanofibers (CNFs) by
tion of wood fiber pulp into MFC nanofibers. More- chemical ultrasonic treatment from four kinds of plant
over, the MFC produced from enzymatically pre- cellulose fibers and made a comparative study. The
treated cellulosic wood fibers showed more chemical composition, morphology, crystalline
favourable structure than nanofibers produced by acid behaviour, and thermal properties of the nanofibers
hydrolysis [33,39]. Literature study reveals that dif- and their intermediate products were characterized
ferent preparation methods were adopted for the iso- and compared [43]. The CNFs extracted from wood,
lation of cellulose nanofibrils. Dufresne et al. (2000) bamboo, and wheat straw fibers had uniform diam-
tried mechanical treatment on bleached potato and Tc Ta bU l ] " fWTa TPbc WTU[
PgU X
QTabfTa T] c
obtained nanofibers with a dimension 5 nm in width uniformly nanofibrillated because of their initially high
[40]. Iwamoto et al. (2005) obtained nanofibers with cellulose content.
PfX ScW U l ] U a Za PUc d[ Qh PbbX ]V Leyva et al. (2011) produced cellulose nanofibers
through a refiner of gap 0.1 mm (30 times) followed from durum wheat straw and characterized it to study
by homogenization [41]. Wang and Sain (2007) used its potential as reinforcement fibers in biocomposites
cryocrushing method for soybean stock and ob- [44]. Cellulose nanofibers were produced via an
cPX]TS]P] U XQTab UfX ScW l ] N ),O ]P] electrospinning method using trifluoroacetic acid
other study Alemdar and Sain (2008) obtained (TFA) as the solvent. The nanofibers were approxi-
nanofibers from wheat straw by cryocrushing fol- mately 270 nm in diameter. Alemdar et al. (2007)
lowed by fibrillation and subsequent homogeniza- extracted cellulose nanofibers from the agricultural
tion. The nanofibrils have 20l ( ] X ]fX Sc WcWT residues (wheat straw and soy hulls) by a chemi-
PYa Xc
hPad]S) l ] [35]. Chen et al. (2011) mechanical technique and the structure of nanofibers
individualized cellulose nanofibers from poplar wood were investigated by transmission electron micros-
24 J.Ch. Cintil, M. Lovely and Th. Sabu
Fig. 3. Procedure for the separation of cellulose nanofibers from polar wood, Reprinted with permission from
W. Chen, H. Yu, Y. Liu and Y. Hai, Carbohydrate Polymers vol. 83, 2011, p. 1804, (c) 2011 Elsevier.
copy [35]. The wheat straw nanofibers have diam- it facilitates both mechanical interlocking and the
eters in the range of 10-80 nm and lengths of a few bonding reaction due to the exposure of the hydroxyl
thousand nanometers. By comparison it is found groups to chemicals such as resins and dyes. The
that the soy hull nanofibers had diameter 20-120 percentage crystallinity in fibers was in the order
nm and shorter lengths than the wheat straw PALF > banana > jute and this order agrees with
nanofibers. In another study, Mandal et al. (2011) the values of cellulose content determined in these
synthesized nanocellulose with a reasonable con- samples. Cherian et al. (2010) employed steam
tent of cellulose II from waste sugarcane baggase, explosion process for the successful extraction of
by acid hydrolysis. They obtained it in the form of a cellulose nanofibrils from pineapple leaf fibers [48].
stable suspension where the surface anionic Steam coupled acid treatment on the pineapple leaf
charges help to bring the necessary stabilization of fibers is found to be effective in the depolymerisation
the nanocellulose [45]. Leitner et al. (2007) isolated and defibrillation of the fibre to produce nanofibrils.
cellulose from sugar beet chips, a by-product of The developed nanocellulose promises to be a very
sugar production by wet chemistry [46]. Further pro- versatile material having wide range of biomedical
cessing of the cellulose with a high-pressure ho- applications and biotechnological applications. Das
mogenizer led to the disruption of cell walls into et al. (2010) extracted spherical and elliptical shaped
nanofibrils. Cellulose sheets obtained by casting and jute nanofibers from jute fibers by acid hydrolysis
slow evaporation of water showed higher strength and were incorporated as reinforcing filler in a bio-
and stiffness when compared to unhomogenised copolymer matrix by the melt mixing method [49].
cellulose. The addition of prepared cellulose Jute nanofibers (JNFs) were prepared by treating
nanofibrils to a polyvinyl alcohol and a phenol-form- jute fibers with alkali and dimethyl sulfoxide (DMSO)
aldehyde matrix respectively demonstrated excel- and then applying acid hydrolysis. Biocopolyester
lent reinforcement properties. Abraham et al. (2011) matrix was reinforced with JNFs at three different
obtained an aqueous stable colloid suspension of loadings (5, 10, and 15 wt.%) and the JNF-loaded
cellulose nano fibrils from three different lignocellu- biocomposites were characterized by different tech-
losic fibres namely banana, jute and pineapple leaf niques. The enhancement in properties was high-
fibre (PALF) using steam explosion technique along est for 10 wt.% JNF-loaded composites indicating
with mild chemical treatment [47]. These processes the most uniform dispersion in this material.
included chemical procedures such as alkaline ex- Deepa et al. (2011) extracted cellulose nanofibers
traction, bleaching, and acid hydrolysis. On remov- from banana fibers by steam explosion technique
ing the noncellulosic constituents of the fibres by and these banana fiber specimens were thermo
chemical treatment, the degree of crystallinity gravimetrically analyzed to compare the degrada-
changed and the trend was same in all these three tion characteristics of the chemically treated fibers
fibres. The removal of surface impurities on plant with the untreated fiber [50]. The fibers exhibited
UXQaTbX bPSe P]cPVT dbX ]U XQa
Tl Pc aXgPSWTb X]" Pb three main weight loss regions. The initial weight
Review of recent research in nano cellulose preparation from different lignocellulosic fibers 25
Fig. 4. Transmission electron micrographs of cellulose whiskers. (a) 1B (bleaching), 120 min (treatment
time); (b) 1B, 150 min; (c) 1B, 180 min; (d) 4B, 120 min; (e) 4B, 150 min; (f) 4B, 180 min. Scale bars: 100
nm, Reprinted with permission from M.F. Rosa, E.S Medeiros, J.A. Malmonged and K.S. Gregorski, Carbo-
hydrate Polymers vol. 81, 2010, 83, (c) 2010 Elsevier.
applications. Lars Berglund and co-workers have paper strength with additive of nanocellulose par-
been developing a number of novel materials based ticles or nanofibrillated cellulose to paper composi-
on cellulose nanofibers like foams, aerogels, tions [65]. Henriksson et al. (2008) reported the for-
]P] P Ta "P]Sbc Pa RWl]P] R T[[
d[b Tcomposites. mation of very dense nano papers (density 1-1.2 g/
Polymer foams are of interest in various applica- cm3) from the dispersion of nanofibrillated cellulose
tions. Svagan et al. (2007) prepared biofoams based with excellent mechanical properties like Young
on amylopectin rich potato starch and cellulose modulus of 10-14 GPa and tensile strength of 130-
nanofibers from wood pulp [23]. This novel concept 214 MPa [60]. These characteristics are like that of
of cellulose nanocomposite biofoams is of interest regenerated cellulose films and 2-5 times higher than
in biomedical applications as well as in packaging that of common papers formed after conventional
material applications. Aerogels are a new class of beating process. Nanocellulose can also be used
materials for catalysis applications and in structures as a reinforcing filler to prepare composites with
for liquid storage. They have exceptional thermal solutions of water soluble polymers, as well as with
insulation properties. In the study by Paakko et al. acrylic and other latex to change the viscosity and
(2007) aerogels were prepared by freeze drying of increase mechanical properties of dry composites.
cellulose nanofibril water suspensions [33]. Cellu- Another application is the addition of nanocellulose
lose nanofibril suspensions can also be converted to biodegradable polymers, permitting both the im-
to nanopaper structures. In the study by Henriksson provement of mechanical properties and accelera-
et al. (2008) the remarkable potential of such tion in the rate of biodegradation [61]. Nanocellulose
nanopaper ie, exceptional mechanical performance in its pure state is harmless for people and is
was observed [60]. The ability of cellulose nanopaper biocompatible. So it can be used for health care
to maintain its integrity at high strains is demon- applications like personal hygiene products, cos-
strated in the study by Svagan et al. [23]. Recent metics and biomedicine. Nanocellulose dispersions
developments have shown the possibility to increase can be used for stabilization of medical suspensions
Review of recent research in nano cellulose preparation from different lignocellulosic fibers 27
against phase separation and sedimentation of [3] I. Siro and D. Placket // Cellulose 17 (2010)
heavy ingredients. Chemically modified cellulose can 459.
be a promising carrier for immobilization of enzymes [4] P.M. Visakh and S. Thomas // Waste and
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