Nanofibrillated Cellulose: Surface Modification and Potential Applications

Colloid Polym Sci (2014) 292:531
DOI 10.1007/s00396-013-3112-9
INVITED REVIEW
Nanofibrillated cellulose: surface modification

and potential applications
Susheel Kalia & Sami Boufi & Annamaria Celli &
Sarita Kango
Received: 11 September 2013 / Accepted: 31 October 2013 / Published online: 21 November 2013
# Springer-Verlag Berlin Heidelberg 2013
Abstract Interest in nanofibrillated cellulose has been increasing exponentially because of its relatively ease of preparation in high yield, high specific surface area, high strength
and stiffness, low weight and biodegradability etc. This biobased nanomaterial has been used mainly in nanocomposites
due to its outstanding reinforcing potential. Solvent casting,
melt mixing, in situ polymerization and electrospinning are
important techniques for the fabrication of nanofibrillated
cellulose-based nanocomposites. Due to hydrophilic character
along with inherent tendency to form strong network held
through hydrogen-bonding, nanofibrillated cellulose cannot
uniformly be dispersed in most non-polar polymer matrices.
Therefore, surface modification based on polymer grafting,
coupling agents, acetylation and cationic modification was
used in order to improve compatibility and homogeneous
dispersion within polymer matrices. Nanofibrillated cellulose
opens the way towards intense and promising research with
S. Kalia : A. Celli
Department of Civil, Chemical,
Environmental and Materials Engineering, University of Bologna,
Via Terracini 28, 40131 Bologna, Italy
S. Kalia (*)
Department of Chemistry, Bahra University, Shimla Hills,
Waknaghat 173 234, Himachal Pradesh, India
e-mail: susheel.kalia@gmail.com
S. Kalia
e-mail: susheel_kalia@yahoo.com
S. Boufi (*)
LMSE, University of Sfax, BP1171, 3000 Sfax, Tunisia
e-mail: Sami.boufi@fss.rnu.tn
S. Kango
Department of Physics and Materials Science,
Jaypee University of Information Technology,
Waknaghat 173 234, District Solan (Himachal Pradesh), India
expanding area of potential applications, including nanocomposite materials, paper and paperboard additive, biomedical
applications and as adsorbent.
Keywords Nanofibrillated cellulose . Surface modification .
Polymer grafting . Nanocomposites
Introduction
Cellulose, the most abundant component of plant biomass, is
found in nature almost exclusively in plant cell walls, but also
it is produced by some animals (e.g. tunicates), algae and few
bacteria [1, 2]. Cellulose is a semi-crystalline polysaccharide
appearing in nature in the form of fibres with width ranging
from 5 to 20 m and length in the range of 0.5 up to several
millimetres. Over the past decades, natural cellulose materials
have been used as an energy source, for building materials,
paper, textiles and clothing etc. [3]. However, there are certain
drawbacks in cellulosic materials such as incompatibility with
hydrophobic polymer which reduced their use as reinforcement in polymers [4].
For engineering applications and other cellulose-based
products, new features and functions such as uniformity and
durability are required in natural cellulose. These features can
be displayed by cellulose elementary building blocks called
cellulose microfibrils with nanosized scale, which is the base
reinforcement unit that strengthens all subsequent structures in
plant, trees etc. Thus, production of the nanofibrillated cellulose (NFC) from native cellulose and their use as reinforcement agent in polymer composite materials has gained increasing attention due to its unique features such as high
strength and stiffness, low weight and biodegradability [5].
A wide use of nanocellulose in dimensionally stable, optically transparent composites for flexible electronics or in
improved barrier membranes has been explored by many
researchers [6, 7]. Synthesis of nanofibrillated cellulose, its

properties and potential applications were described in a number of publications [810].
Cellulose nanocrystals (CNC) and nanofibrillated cellulose
constituted the two main families of nano-sized cellulose or
nanocellulose. Cellulose nanocrystals are extracted from
fibres after a complete dissolution of the non-crystalline
fractions, while the nanofibrillated cellulose results from
the application of high shearing forces of disintegration
leading to a high degree of fibrillation, which yields highly
interconnected fibrils. Nanofibrillated cellulose is one of
most promising among nano-sized cellulose material, so
in this article we have focused mainly on isolation and
surface modification of nanofibrillated cellulose using different available methods. The applications of nanofibrillated
cellulose in composite materials, drug delivery, as adsorbent
etc. are also discussed in this review.
Nanofibrillated cellulose
NFC consists of long, flexible and entangled cellulose
nanofibres and is composed of more or less individualized
cellulose microfibrils, presenting lateral dimensions in the
order of 10 to 100 nm, and length generally in the micrometre
scale, and consisting of alternating crystalline and amorphous
domains. In the literature, the term nanofibrillated cellulose, or
nanofibrillar cellulose, is also employed to designate the same
material. The terminology nanofibrillated/nanocellulose or
NFC was first used by Turbak, Snyder and Sandberg in late
1970s [11, 12]. They were the first to report the extraction
of NFC by high-pressure homogenization (HPH) of dilute
slurries of softwood cellulose fibres using a Manton Gaulin
homogenizer. As the slurry reached 80 C at 500 MPa, the
suspension turned into a translucent, high consistent gel
that they called nanofibrillated cellulose. Since then, NFC
opens the way towards intense and promising research on
nanocellulose-based materials with expanding area of potential applications, including transparent materials [13, 14],
packaging materials due to their high mechanical properties
and low gas permeability rates [1518], biomedical applications [19] and production of paper with better sheet
properties such as tensile strength [20, 21]. Cellulose
nanofibres could also be used as a rheological modifier in
foods, paints, cosmetics and pharmaceutical products [11].
NFC has been also the subject of a number of publications
focusing mainly in method of preparation and on nanocomposite applications [10, 22, 23].
In fact the term NFC should not be confused with cellulose
microfibrils which constitute the smallest discernible building
blocks of natural cellulose with lateral dimensions in the
range of 5 to 20 nm depending of the cellulose origin [24]
and length generally in micrometre scale. Actually, the
different processes adopted for release of NFC lead to a

wide distribution in the width of the nano-sized fibres
ranging from 5 up to 100 nm, depending on the energy
input to disintegrate the cellulose fibres and on the pretreatment used to facilitate the disintegration process. It
means that NFC are nanofibrils composed of bundles of
elementary fibrils separated by less ordered regions and
have the ability to create entangled networks, unlike cellulose nanocrystals being composed of elementary monocrystals. CNC looks also as stiff rod-like fibrils, while NFC are
rather flexible and exhibited strong tendency to entanglement leading to a web-like structure as water is removed
[22].
The promising potential of applications of NFC along
with its sustainable character has attracted the attention
of number of companies and starts-up to reach largescale commercial production of NFC. In 2011, Innventia
(http://www.innventia.com) opened the world's first pilot
plant for the production of nanocellulose with a capacity
of 100 kg/day, which constitutes an important step towards the
industrialization of the microfibrillar cellulose. Since that,
other investments in NFC production were launched. In
2011, UPM has started pre-commercial production of fibril
cellulose and is currently developing new fibril cellulose
applications with industrial partners (http://www.upm.com/
EN/PRODUCTS/biofibrils/Pages/default.aspx). In 2012, US
Forest Products Laboratory opens pilot plant to produce
wood-derived renewable materials, and Stora Enso (http://
www.storaenso.com) makes a ground-breaking investment
in nanotechnology at Imatra, Finland to produce and commercialize microfibrillated cellulose.
Sources for nanofibrillated cellulose

Due to the diversity of cellulose, nanocellulose can, in principle, be derived from a wide variety of sources. The primary
occurrence of cellulose is the available lignocellulosic material in forests, with wood as the most important source. Wood
should be treated by a chemical process to remove noncellulosic material, mainly lignin, before being used as a raw
material for production of NFC.
Other cellulose-containing materials include agriculture
residues, water plants, grasses and other plant materials.
Agricultural residues have received increased attention in
recent years as an alternative resource for the extraction of
cellulose fibres due to their large amount all over the world
and annual renewability especially for countries that do not
have forests. Comparatively to the wood, non-woody plants
have generally lower lignin contents [25] and offer several
advantages, including short growth cycles with moderate
irrigation requirements, environmental benefits owing to
their renewable nature and low energy consumption for
the extraction of the cellulose fibres. However, despite

the abundance of non-woody plant, their use as a raw
material for chemical pulping is still limited because of
the high labour cost of collection of nonwoody plant,
namely in developed countries, and of the high silica
content, namely for cereal straw, making the pulping
process more difficult than woody fibres. The high silica
content hampers to use the classical soda pulping technology,
as the recycling of black liquor with a recovery boiler is harder
to implement.
The morphology of the nanofibrillated cellulose from the
annual plants depends from their origin. An example of
nanofibrillated cellulose from several annual plants is shown
in Fig. 1 [26]. A wide variety of non-woody plant have been
studied for the extraction of NFC, including cotton [27], ramie
[28], sisal [29], flax [30], abaca [26], wheat straw [31, 32],
potato tubers [33], sugar beet pulp [34], banana rachis [35],
bagasse [36], palm tree [37] etc.
Isolation of nanofibrillated cellulose

NFC is produced by delaminating cellulosic fibres under an
intense high mechanical sharing action in order to release the
NFC and to overcome interfibrillar hydrogen bonds into both
crystalline and amorphous domains. Although HPH and
Fig. 1 AFM images of the NFC
from several annual plant, namely
abaca, hemp, flax and sisal.
Reprinted from [26], Copyright
2013, with permission from
Elsevier
microfluidization are the main methods currently used, other

approaches were also reported in the literature.
High-pressure homogenization (HPH)
This is the widely used method for large-scale operations as
well as lab scale production of NFC. HPH technique was
introduced in early 1980s to produce fine emulsion based
on the availability of devices that are able to generate high
pressure in liquids as high as 5001,000 MPa. The process has been extensively used by the dairy and food
industry, mainly to stabilize food emulsion and to disrupt
lipid globules in liquid food. Different manufactures of
HPH exist for producing lab scale or industrial equipment
such as Microfluidics (http://www.microfluidicscorp.com),
Avestin (http://www.avestin.com/company.html), Niro Soavi
(www.nirosoavi.com/) and Stansted fluid power (http://www.
stanstedfluidpower.com).
Homogenization involves the forcing of the suspension by
a piston under pressure through a very narrow channel or
orifice under pressure operating between 100 up to 2,
000 MPa (Fig. 2). The width of the homogenization gap,
depending on the viscosity of the suspension and the applied
pressure, ranges from approximately 5 to 20 m. The
resulting high streaming velocity of the suspension causes
an increase in the dynamic pressure which is compensated
Fig. 2 a, b Scheme illustration

of the principle of
homogenization and c example of
lab scale homogenizer (GEA Niro
Soavi)
by a reduction in the static pressure below the vapour pressure

of the aqueous phase. This leads to the formation of gas
bubbles that collapse immediately when the liquid leaves the
homogenization gap being again under normal air pressure
of 100 kPa. This phenomenon of formation and implosion
of the gas bubbles results in cavitation and shockwaves that
bring the disruption of the cellulose wall [38, 39]. The size
reduction of cellulose fibres is also promoted by the large
pressure drop, the high shear forces, the turbulent flow and
the collision of the particles against each other. The extent
of the cellulose fibrillation depends on the number of
homogenization cycles and to the applied pressure. The
higher the pressure, the higher is the efficiency of disruption per pass through the machine. Based on the literature
data, high-pressure homogenization is the most widely used
method for the preparation of NFC [40].
high pressure (150210 MPa). As a result, product stream

accelerates to the high velocity and creating shear rate within
the product exceeding 106 s1 with intense particle collisions
and cavitation forces results in disintegration of the cellulose
fibres to elementary building blocks. Unlike in the homogenizer which operates at a constant processing volume, the
microfluidizer operates at a constant shear rate, which reduces
the likelihood of clogs. Furthermore, fixed geometry of the
interaction chamber ensures reproducibility, especially when
samples are processed multiple times. It is necessary to repeat
the mechanical treatment and use different sized chambers
in order to increase the degree of fibrillation. Like highpressure homogenization, the microfluidization process has
been widely used for the production of NFC [4244].
Microfluidization
In micro-grinding, dilute slurries of cellulosic fibres (consistency of ~2 %) are forced through a gap between two specially
modified grooved discsone static, other revolving at about
1,500 rpm (Fig. 3). These discs have bursts and grooves that
contact the fibres to disintegrate them into the sub-structural
components [4547]. Contact with the hard surfaces and
repeated cyclic stresses result in the defibrillation of the fibres.
Typically, the materials used for the discs in the micro-grinder
are non-porous resins containing silicon carbide. The discs
can be produced using different grit classes and different
Microfluidizer system is currently used in technology for

miniaturization from macro- to micro/nano-structure dimensions [41]. This technology has been traditionally used in the
pharmaceutical industry to make liposomal products and pharmaceutical emulsions and by the dairy and food industry to
produce homogenized milk and flavour emulsions. In the
microfluidizer, suspension is forced through a defined fixed
geometry narrow channel being either Y-type or Z-type under
Grinding
Fig. 3 MKCA 6-2 from Masuko Sangyo Ltd
groove configurations to alter flow patterns during processing.

The extent of fibrillation is dependent upon the distance
between the discs, the morphology of the disc channels
and the number of passes through the grinder. Like a
homogenizer, many passes are necessary (anywhere from
three to ten passes) and are required to generate adequate
liberation of fibrillated cellulosic structures though refining
pre-treatment is not necessary. Disc maintenance and replacement can be a drawback since wood pulp fibres can wear
down the grooves and grit. However, a main advantage of
processing with the micro-grinder is that other processing
techniques like mechanical and fibre shortening pretreatments are not required.
Recently, the use of ultrasound irradiation as an alternative

to mechanical disintegration for the release of cellulose
microfibrils is the subject of numerous research works.
Chemical pre-treatments and high-intensity ultrasonication
improved the yield of nanofibrillated fraction cellulose
nanofibres with 520 nm in width and several microns in
length [5155]. The main advantages and disadvantages of
each preparation method are reported in Table 1 (http://www.
microfluidicscorp.com) [18, 24, 4042, 4467].
Ultrasound-assisted fibrillation
Two problems were often encountered when manufacturing of

nanofibrillated cellulose from pulp, namely (a) clogging of the
pulp, when the pulp is pumped through high-pressure
fluidizers/homogenizers, and (b) high energy consumptions
associated with the fibre delamination which often involves
multiples passes through the disintegration device until efficient delamination of the cell wall is observed. This high
energy inputs is necessary in order to release the NFC and to
overcome interfibrillar hydrogen bonds into both crystalline
and amorphous domains [68]. Therefore, one of the most
important challenges to produce NFC on an industrial scale
is to decrease the energy demand and facilitate the process of
production. Pre-treatments were sometimes used to address
this problem. In this section, we have discussed some of the
most efficient pre-treatments of fibres to facilitate the cell wall
delamination and the release of nanosized fibrils.
Ultrasonication is the application of sound energy to physical

and chemical systems. In liquids, sonication produces bubbles
that grows and implodes hot spots that cause acoustic cavitation, formation, growth and implosive collapse of bubbles to
produce hot spots [48]. The energy provided by cavitation
during ultrasound irradiation might be controlled to be within
10100 kJ/mol, which is within the hydrogen bond energy
scale. Thus, the ultrasonic impact can gradually disintegrate
the micron-sized cellulose fibres into nanofibres. Basic technology of ultrasonication was developed over more than
50 years ago, and its use in size reduction at the nanoscale
level is widely adopted. Only few applications about this
technique for the production of nanocellulose were reported
in the literature. Cheng et al. [49] used high-intensity
ultrasonication with a batch process to isolate fibrils from
several cellulose sources. The results showed that a mixture
of microscale and nanoscale fibrils was obtained with diameters ranging from about 30 nm to several micrometres. However, because of the complicated multilayered structure of
plant fibres and the interfibrillar hydrogen bonds, the fibres
obtained by these methods are aggregated nanofibres with a
wide distribution in width [50].
Pre-treatment of fibres to facilitate the release

of nanofibrillated cellulose
Refining by mechanical treatments

Mechanical refining is widely used prior to homogenization
process in order to facilitate to defibrillation and reduce the
energy input [6972]. Disc refiners, PFI mills and Valley
beaters were reported prior to the production of NFC
[7375]. During this process, the dilute fibre suspension is
10
Table 1 Summary of the different technologies used to extract nanofibrillated cellulose (http://www.microfluidicscorp.com) [18, 24, 4042, 4467]
Technology
Advantages
Disadvantages
High-pressure
homogenization
It is a mechanical process that is quick and effective

It is a continuous process
The results obtained in laboratory are perfectly reproducible
in industrial scale
You can vary pressure in order to find the right degree of cell
delimitation
Ease of scale up
Less risk of clogging
Uniform particle size reduction
Fewer repeat passes to ensure optimum sample processing
High power output
High number of homogenization cycle

High energy consumption
Microfluidization
Ultrasonication
High efficiency for cell delamination
Micro-grinding
Less energy consumption
Increase in temperature of the suspension during processing
Unsuitable for industrial scale
Heat generated by the ultrasound process must be dissipated

High noise levels (most systems require hearing protection and
sonic enclosures)
Useful only to a lab scale level, pre-treatment is necessary to
release NFC
Reduction in the crystalline degree of NFC, disk maintenance
and replacement
Fewer passes are needed to obtain NFC
forced through a gap between rotor and stator discs. These

discs have surfaces fitted with bars and grooves against
which the fibres are subjected to repeated cyclic stresses.
This mechanical treatment brings about irreversible
changes in morphology and size of fibres [76]. Actually,
under the effect of the intense mechanical shearing action
in the disc refiner, the cellulose fibres are subjected to
repeated loading action of the refiner bars, leading to a
progressive peeling off of the external cell wall layers,
namely the primary (P) and first secondary (S1), making
the subjacent thicker secondary cell wall layers [77]
more exposed to fibrillation during the homogenization
process. However, mechanical refining brings about a damage
of the microfibril structure by reducing molar mass and degree
of crystallinity [63].
(Fig. 4) [63]. The TEMPO-mediated oxidation could be carried

at basic condition with pH around 11 and low temperature
(4 C) or under acid condition with pH around 4.55.0 and
temperature 5060 C. Former condition leaves a fraction of
the aldehyde groups (<0.08 mmol/g) in the oxidized cellulose,
while no residual aldehyde groups are likely to remain in the
oxidized fibres and the extent de-polymerization side reactions
or discoloration of the fibres were reduced [84].
TEMPO-mediated oxidation
Another more promising route towards making easier the
extraction of NFC relies on chemical treatments involving
the addition of negatively charged entities at the microfibrils
surface. Saito et al. were the first to report that 2,2,6,6tetramethylpiperidine-1-oxyl (TEMPO)-mediated oxidation
of cellulose fibres facilitated the release of NFC and allowed
for low energy mechanical disintegration of the oxidized fibres
in aqueous suspensions [62, 7882]. TEMPO is a highly stable
nitroxyl radical which is used extensively in the selective
oxidation of primary alcohols to corresponding aldehydes
and carboxylic acids. In aqueous environment, TEMPO catalyzed the conversion of carbohydrate primary alcohols to
carboxylate (COO-) functionalities in the presence of a primary
oxidizing agent, e.g. sodium hypochlorite (NaOCl) [83]
Fig. 4 Proposed mechanism for the oxidation of anhydroglucose to

6-carboxycellulose moieties via TEMPO/NaOCl/NaBr system in alkaline
media. Numbers represent two levels of oxidation: (1) CH2OH
CHO and (2) CHOCO2H. Reprinted from [63], Copyright 2003,
with permission from Springer
Compared to the energy consumption using high-pressure

homogenizer, TEMPO-mediated oxidation pre-treatment was
shown to dramatically decrease the consumption by a factor
more than 100 [81]. Several hypotheses were postulated to
account for this huge change in the delamination process,
namely (a) the oxidation generates negative charges that bring
forth repulsive forces between microfibrils within the cell wall
[10], contributing to loosen the microfibrils cohesion held by
hydrogen bonding; (b) the oxidation favours the hydration
and swelling of the fibres, making them more flexible and
crystalline zone more accessible; (c) oxidation loosens the
primary and S1 cell wall making S2 layer more accessible
and more prone to fibrillation during the homogenization
process; (d) finally, the oxidation results in chain scission
in amorphous zone, creating defaults within the fibre cell
wall, which facilitates the mechanical fibrillation.
Level of oxidation is critical in reducing the energy input
and improved the yield of nanofibrillation as well as the transparency degree of the NFC suspension (Fig. 5a). A carboxyl
Fig. 5 a Appearance of NFC

gel at 1.5 wt.% from TEMPOmediated oxidation of Eucalyptus
fibres after ten passes at 600 MPa,
at different carboxyl contents,
and b their corresponding
transmittance behaviour;
I 300 mol g1, II 500 mol g1
and III 1,000 mol g1
11
content of about 300 mol/g is necessary to observe a worth

change in the number of passes necessary to release the NFC
and to prevent the clogging of the homogenizer. Furthermore,
over a carboxyl content of 500 mol/g, non-significant change
in the ease of nanofibrillation could be observed [65, 66].
Moreover, higher the carboxyl content better is the optical
transparency of the ensuing NFC suspension (Fig. 5b).
Change of degree of oxidation has been found to show an
obvious effect on the size of NFC. Preparation of NFC from
the date palm tree was controlled and optimized by monitoring
the oxidation time (degree of oxidation) of the pristine cellulose and the number of cycles through the homogenizer. The
oxidation was monitored by TEMPO-mediated oxidation. A
significant reduction in NFC length was occurred during the
TEMPO-mediated oxidation. Reduction of NFC size with
increase in oxidation time was confirmed by UVvis spectroscopy and measurement of the degree of polymerization
[85]. Effect of TEMPO oxidation conditions and mechanical
fibrillation treatments on the lengths and average degrees of
12
polymerization was determined by viscosity measurement

(DPv) of the TEMPO-oxidized cellulose nanofibrils. DPv
values and average lengths of TEMPO-oxidized cellulose
nanofibrils were decreased with increasing addition of NaClO
in the TEMPO-mediated oxidation stage [86]. Recently it
was shown that by surpassing a carboxyl content of
3 mmol/g, a spontaneous disintegration of the fibres into
nanofibres might be achieved almost in the absence of
mechanical energy input [87].
extraction of cellulose nanofibrils from biomass [95]. The

process was used either alone or in combination with high
pressure.
The advantages of steam explosion include a significantly
lower environmental impact, low energy consumption, lower
capital investment and use of less hazardous chemicals. Process should be repeated several times until efficient release of
the cellulose microfibrils takes place [96].
Delignification using NaClO2/acetic acid
Enzymatic pre-treatments
Enzyme pre-treatment, an environmentally friendly alternative to chemical pre-treatment, was also reported to reduce the
processing cost, by lowering the number of passes through the
homogenizer. Few researchers have investigated the effect of
the enzyme pre-treatment on the ease of the release of NFC
[63, 8891]. A recent patent revealed an energy efficient
process to produce NFC based on alternating enzymatic
treatment with mechanical treatments, followed by a high
shear mechanical defibrillation, such as homogenization,
grinding or microfluidization [92]. The most widely used
enzyme is commercial cellulase, which encompasses of
three groups endoglucanases, cellobiohydrolases or
exoglucanases, and glucosidases as illustrated in Fig. 6.
The cell walls become softened by the enzymatic breakages
of the cellulose networks prior to the mechanical disintegration, thus promoting the cell wall delamination and the
release of NFC [93].
Steam explosion
The steam explosion process is based on short time vapour
phase cooking at temperatures in the range of 180 to 210 C,
followed by explosive decompression, and sudden release of
pressure, during which the flash evaporation of water exerts a
thermomechanical force causing the rupture of material. This
effect results in a substantial breakdown of lignocellulosic
structure, hydrolysis of the hemicellulose fraction, depolymerization of the lignin components and defibrillization [94]. To
date, steam exploded fibre has been used mainly as a pulping
process for the extraction of cellulose fibres from biomass.
However, this approach was successfully extended to the
Fig. 6 Types of cellulases:

a endoglucanases without
cellulose-binding domain;
b endoglucanases with
cellulose-binding domain;
c, d cellobiohydrolases and
e glucosidases. Reprinted from
[93], open access 2008
When the delignification process was carried out using NaClO2/

acetic acid pulping process, higher yield in nanofibrillated
fraction was obtained, compared to the conventional kraft or
NaOH pulping process. This improvement was explained by
the difference in the chemical composition of the delignified
fibres, specifically the hemicellulose content. The correlation
between the hemicellulose content and the nanofibrillation
efficiency was confirmed by the work of Iwamoto et al.
and Chaker et al. [13, 97]. It was shown that the higher the
hemicellulose content in the fibres, the better is the yield of
the nanofibrillated material. This correlation between the
extent of fibrillation and the hemicellulose content was
explained by considering the molecular organization of cellulose microfibrils and hemicellulose within the cell wall.
Referring to the lamella model, hemicellulose is believed to
be tightly bounded to the cellulose microfibrils via multiple
hydrogen bonds and physically span the gap between them.
Given its structural properties, namely amorphous character,
macromolecular ramification and high hydrophilicity, hemicellulose will act as a physical barrier to keep the cellulose
microfibrils apart from each other, consequently preventing
their aggregation.
All of the above cited fibre treatments carried out prior to
the disintegration process were reported to facilitate the
delamination of the cell wall and the liberation of the cellulose microfibrils. This means that lower energy demand is
needed to achieve high extent of cellulose nanofibrillation.
However, the question to what extent these pre-treatments
affect the energy consumption still a matter of debate. To
our knowledge, the quantitative correlation between the
carboxyl content and the mode of disintegration was tackled
only by two publications [71, 87].
13
Fig. 7 Ring-opening
polymerization of -CL from
NFC, using benzyl alcohol as
co-initiator. Reprinted from [103],
Copyright 2008, with permission
from Elsevier
Surface modification of nanofibrillated cellulose

Surface modification of nanofibrillated cellulose is crucial in
order to improve compatibility and homogeneous dispersion
within polymer matrices [98]. Different methods such as
esterification, cationisation, silylation, polymer grafting and
TEMPO oxidation have been reported for the surface modification of nano-sized cellulose [99102].
Polymer grafting
Surface modification of nanofibrillated cellulose was carried
out by grafting poly(e-caprolactone) via ring-opening polymerization as illustrated in Fig. 7 [103]. A two-step method for
grafting polyacrylic acid (PAA) onto henequen cellulosic
microfibres was also reported [104]. They initially treated
the cellulose microfibres with an epoxide that contains a
terminal double bond followed by grafting of the PAA onto
the cellulosic fibrils using a solution polymerization reaction
initiated with potassium persulfate. The best conditions for the
grafting reaction were found with 0.4 % initiator with respect

to the weight of fibre. Xiao et al. [105] reported the surfaceinitiated atom transfer radical polymerization of butyl acrylate
on NFC using two catalyst systems, CuIBr/2,2-bipyridine and
CuIBr/pentamethyl-diethylenetriamine to create controllable
hydrophobic chains on NFC. Li et al. [106] also reported the
grafting of poly(butyl acrylate) (PBuA) on NFC by atom
transfer radical polymerization of butyl acrylate on the surface
of 2-bromoisobutyryl-functionalized NFC.
In case of cerium-induced grafting of glycidyl methacrylate
on the cellulose microfibrils, mechanism of ceric ion reaction
involves the formation of a chelate complex that decomposes
to generate free radicals on the cellulose backbone. In the
presence of glycidyl methacrylate (GMA) monomers, these
free radicals resulted in graft polymerization on the surface of
fibres, as shown in Fig. 8 [107]. This mechanism was proposed by Mishra et al. [108].
Effects of monomer type and concentration, initiator concentration and polymerization time were studied during free
radical graft copolymerization of nanofibrillated cellulose with
Fig. 8 Oxidation of 1,2-glycol groups followed by grafting of glycidyl methacrylate. Reprinted from [107], Copyright 2007, with permission from Springer
14
the surface of cellulose nanofibres by use of coupling agents

such as silane reagents.
Surface modification of nanofibrillated cellulose was
performed with three different coupling agents: 3aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane
and a titanate coupling agent [115]. Modification with silane
coupling agents involves hydrolysis and condensation of
triethoxysilanes which forms SiOH bearing oligomers.
The oligomers can form hydrogen bonds with OH groups
of cellulose at room temperature, and a condensation reaction
takes place to give SiOC bonds. The mechanism of titanate
coupling is quite different from the silanes. It was proposed
that the coupling occurs by alcoholysis, surface chelation or
coordination exchange [116]. If hydroxyl groups are present on
the surface of the substrate, then the monoalkoxy- and
neoalkoxy-type titanium-derived coupling agents react with
the hydroxyl groups to form a monomolecular layer. The
reaction mechanism of titanate coupling agent and cellulose
is shown in Fig. 9.
Cellulose microfibrils resulting from the homogenization
of parenchymal cell walls by using isopropyl dimethyl
chlorosilane were modified [117]. It was reported that
acrylic monomers such as glycidyl methacrylate, ethyl acrylate,

methyl methacrylate, butyl acrylate and 2-hydroxyethyl methacrylate. The monomer conversion (C), graft yield (G), graft
efficiency (G E), weight fraction (W G), weight average molar
mass and polydispersity of the grafted polymer are displayed in
Table 2 [109].
NFC was covalently grafted with poly(-caprolactone)
(PCL) via ring-opening polymerization of -caprolactone
(-CL) in order to improve the dispersibility of the hydrophilic
NFC in the nonpolar matrix and the interfacial adhesion in the
composite material. The reaction mixture was then dispersed in
tetrahydrofuran (THF) to separate the PCL-grafted NFC from
poly(-caprolactone) in the solution by filtration [110]. Only
few studies have focused on graft copolymerization onto NFC,
and most of the studies were reported on grafting of polymers
to the surface of other cellulose nanofillers [111114].
Coupling agents
Use of coupling agents is another important technique for
surface functionalization of nanofibrillated cellulose. Many
reactions have already been performed in order to modify
Table 2 Polymerization parameters and gravimetrically determined conversion (C), graft yield (G), graft efficiency (G E) and weight fraction of polymer
(W G) in each product (reprinted from [109], Copyright 2011, with permission from Elsevier)
Sample
n (M)/m (NFC)a
(mmol/g)
[CAN]
(mmol/dm3)
t (min)
C b (%)
G b (%)
G Eb (%)
W Gb (%)
M w,G (kg/mol)
PDG
NFC-PGMA 3
38
60
85
321
96
76
NFC-PGMA 4
NFC-PGMA 5
NFC-PGMA 6
NFC-PEA 4
NFC-PEA 5
NFC-PEA 6
NFC-PEA 7
NFC-PMMA 1
NFC-PMMA 2
NFC-PMMA 3
NFC-PMMA 4
NFC-PBuA 1
NFC-PBuA 2
NFC-PBuA 3
NFC-PBuA 4
NFC-PHEMA 1
NFC-PHEMA 2
NFC-PHEMA 3
20
40
40
20
40
40
40
40
21
40
40
41
20
40
40
40
21
40
2
4
2
2
2
4
2
2
2
4
2
2
2
4
2
2
2
4
60
60
90
60
60
60
90
60
60
60
90
60
60
60
90
60
60
60
54
78
77
82
70
74
74
35
36
35
41
81
81
81
86
10
14
11
146
434
439
95
230
251
255
78
56
94
98
369
177
345
392
33
19
37
96
97
99
81
84
85
56
75
67
60
86
85
83
89
63
51
64
59
81
81
49
70
72
72
44
36
48
49
79
64
78
80
25
16
27
33c
40c
391c
127c
256d
121d
194d
239d
3,480d
1,420d
1,890d
1,770d
1.5
4.9
1.9
2.6
2.0
1.5
1.7
1.9
1.2
1.8
1.4
1.7
NFC-PHEMA 4
40
90
29
27
18
21
Quantity of monomer per gram of dry NFC
Determined gravimetrically
Determined by MALLS
Determined by GPC
15
Fig. 9 The reaction mechanism of titanate coupling agent on the cellulose surface. Reprinted from [115], Copyright 2008, with permission from Elsevier
microfibrils retained their morphology under mild silylation

conditions and could be dispersed into organic solvents in a
non-flocculating manner. NFC was hydrophobized via partial
surface silylation using the same silylation agent and found
that partial solubilization of NFC and loss of nanostructure
could occur when silylation conditions were too harsh. In
silylation procedure, chlorodimethyl isopropylsilane reacts
with surface hydroxyl groups of the NFC material, resulting
in a hydrophobication of the surface [73].
Surface treatment of NFC was carried out using a silane, 3aminopropyltriethoxysilane. The silane was pre-hydrolyzed in
a double molar concentration of water for 2 h and then added
to the NFC acetone suspension. The suspension was stirred
for 3 h, filtered and then dried at room temperature for 1 day
followed by further curing at 120 C for 2 h in air. Original and
modified NFC was then combined with a cellulose acetate
matrix by film casting from an acetone suspension, and thermal stability of composites with treated NFC was found to be
better than the untreated NFC [118].
Other chemical methods
There are certain other methods adopted by the researchers to
modify the surface of cellulose nanofibres. These methods
include acetylation, cationic modification, alkali treatment
etc. Acetylation is a type of chemical modification in which
acetyl groups reacts with the surface hydroxyl groups on the
cellulose, thereby making the hydrophilic surface of cellulose
to be more hydrophobic. Sassi and Chanzy reported that the
acetylation of cellulose depends on the accessibility and susceptibility of OH groups in the amorphous and crystalline
regions within the cellulose polymer chain [119]. Surface
modification of NFC by adding of acetyl moieties on the
cellulose surface using a large excess of acetic anhydride
was studied and shown in Fig. 10 [120].
Gaseous acetylation of microcrystalline cellulose was
carried out to modify its chemical and physical properties
and at the same time to preserve the morphology of cellulose microfibrils [121]. Acetylation of NFC was carried out
to decrease the hydrophilicity of cellulose nanofibres and
further to improve the chemical affinity between NFC and

non-polar environments. It has been found that degree of
substitution increased rapidly during the first 60 min, suggesting that the reaction occurred primarily on easily accessible surface hydroxyl groups, whereas reaction rate gradually
slowed down up to 180 min with a degree of substitution
ranging from 0.37 to 0.41. This was due to the modification of
less accessible surface OH groups on nanofibres as well as
steric hindrance induced by grafted acetyl groups on the fibre
surface [122]. Heterogeneous acetylation of NFC was carried
out to modify the physical properties and at the same time to
preserve the morphology of cellulose fibrils [123]. Cellulose
nanofibres with hydrophobic surface characteristics were synthesized using chemical modification technique. Kenaf fibres
were modified using acetic anhydride as acetylating agent and
pyridine as catalyst. Cellulose nanofibres were then isolated
from the acetylated kenaf using mechanical isolation methods.
It was reported that when kenaf fibres were treated with
acetylating reagents, the chemicals get penetrated deep into
the cell wall resulting in acetylation of OH groups on the
surface as well as bulk. The use of pyridine will swell and
open the cellulose fibre cell walls, thus increasing the number
of accessible reactive hydroxyl sites. Swelling effect of pyridine is expected to favour the penetration of acetic anhydride
and acetic acid into the swelled fibres, which rupture the cell
wall structure and thereby enhancing the rate of acetylation
[124]. Cellulose nanofibres with acetyl groups on the surfaces
were then isolated from the cell wall by mechanical treatments [125]. Modification of NFC water suspensions was
performed using two cationic methacrylate polymers:
poly([2 (methacryloyloxy)ethyl] trimethyl ammonium iodide)
and poly[(stearyl methacrylate)-stat-([2-(methacryloyloxy)ethyl]
trimethyl ammonium iodide)] [126].
Cationic modification of cellulose nanofibrils films was
carried out by adsorption of n-hexadecyl trimethyl ammonium bromide (cetyltrimethylammonium bromide, CTAB), a
cationic surfactant directly on the film surfaces [127]. The
surface adsorption was carried out using two concentrations
of CTAB solution: four critical micelle concentration (CMC)
(T2 and T3) and 0.93 CMC (T4 and T5), but with the same
16
Fig. 10 Acetylation of NFC with acetic anhydride (AA). Reprinted from [120], Copyright 2010, with permission from American Chemical Society
total amounts. Figure 11 shows the high-resolution transmission electron microscopy (HRTEM) image from a single
surface-modified and unmodified nanofibril. In Fig. 11b,
black dots (CTAB molecules) were encountered along the
nanofibril structure which means that the CTAB molecules
are adsorbed on the nanofibril surfaces. Such black dots
were not encountered on the unmodified TEMPO-mediated
cellulose nanofibrils (Fig. 11a). Transparent and high gas
barrier films were synthesized from TEMPO-oxidized cellulose nanofibres. These films were found to be flexible and have
high tensile strength and low coefficient of thermal expansion.
The unique characteristics of these films are promising for
potential applications in some high-tech materials [14].
Alkali treatment of NFC was carried out by immersing the
dry sheets of NFC in NaOH aqueous solutions of 5 and
20 wt.% concentrations, kept at reduced pressure of 0.01 MPa
for 2 h and at ambient pressure for an additional 10 h. It was
found that sheets treated with 5 wt.% alkali solution showed no
variations in dimensions compared to the untreated ones,
whereas 20 wt.% NaOH solution treatment resulted in a visible
contraction in diameter of about 17 % for NFC as compared
to untreated sheets. Thicknesses of the sheets were slightly
enhanced by the alkali treatment. In case of crystalline
structure, diffraction pattern of the 20 wt.% alkali solutiontreated NFC samples was characteristic of cellulose II, and
5 wt.% NaOH solution-treated sheets showed the same
cellulose I profile as the untreated sheets [128].
Synthesis of amino functionalized NFC using click
chemistry was reported in aqueous reaction conditions [129].
Firstly, the reactive azide groups were introduced on the surface
of NFC by the etherification of 1-azido-2,3-epoxypropane in
alkaline water/isopropanol mixture at ambient temperature
followed by reaction with propargyl amine utilizing copper
Fig. 11 HRTEM of a single

nanofibril and b CTAB-modified
nanofibril. Note that the a and
b were taken at the same
magnification, i.e. 100,000. The
contrast of the images has been
modified for better visualization.
Springer
catalyzed azide-alkyne cyclo-addition (CuAAC), leading to

pH-responsive 1,2,3-triazole-4-methanamine decorated NFC.
Further, etherification reaction of 1-azido- 2,3-epoxypropane
was carried out with the surface hydroxyl groups of NFC under
alkaline conditions. The azide functionalized NFC was used
to introduce amine groups using the CuAAC reaction as
illustrated in Fig. 12a.
Surface of oxidized cellulose microfibrils was modified
using amine-terminated molecules [130]. Firstly, native cellulose was oxidized with catalytic amounts of radical TEMPO,
sodium hypochlorite and sodium bromide in water. The
primary alcohol moieties were selectively oxidized into
carboxyl groups. Then coupling of amines derivatives onto
oxidized cellulose was carried out by a peptidic reaction
using carbodiimide as catalyst and hydroxysuccinimide as
an amidation agent. The reaction of amine grafting onto
oxidized cellulose is shown in Fig. 13.
A positive charge was introduced to NFC surface through
grafting of hexamethylene diisocyanate, followed by reaction
with two different diamines, bis-(3-aminopropyl) amine and
3-(diethylamino) propylamine. Authors also reported the surface modification of NFC by introducing succinic and maleic
acid groups directly onto the NFC surface as a monolayer by a
reaction between the corresponding anhydrides and surface
hydroxyl groups of the NFC [107].
Effect of surface modification on some properties

of nanofibrillated cellulose
Surface modification by using various chemical treatments has
pronounced effect on some properties of NFC. Morphology of
the untreated and titanate treated sample was compared, and
17
Fig. 12 Schematic representation

of the reaction of azide
functionalized NFC with a
propargyl amine and b
5-(dimethylamino)-N-(2-propyl)1-naphthalene sulphonamide.
Springer
treated fibres appear much smoother than the untreated fibres,

indicating that the treatment has altered the surface morphology of the NFC [115].
AFM studies of unmodified NFC and acrylic monomergrafted NFC was carried out and as shown in Fig. 14 [109].
Unmodified NFC (Fig. 14a) consisted of fibrils that were
clearly less than 50 nm in diameter, but thicker fibril aggregate
bundles were also present. Comparison of the images reveals
that the nanoscale fibrillar structure is retained during the graft
copolymerization process. The grafted NFC samples showed
a rougher surface than those of the unmodified NFC. The
fibrils of the grafted NFC were also somewhat thicker than
those of the unmodified sample, and this may be because of
the large amount of grafted polymer. In NFC-g-poly(glycidyl
methacrylate) (PGMA), polymer was clearly visible as a
Fig. 13 Reaction of amine
grafting onto oxidized cellulose.
Springer
granular structure on the nanofibrils, where weight fraction

of the grafted PGMA was high (80 %) (Fig. 14b), whereas in
NFC-g-PHEMA, presence of polymer was seen as a rough
surface of cellulose fibrils in case of low weight fraction
(21 %) (Fig. 14c). The polymer content was 70 % in the
NFC-g-PEA sample (M w =40 kg/mol, Fig. 14d, e) and 80 %
in the NFC-g-PBuA (1,770 kg/mol, Fig. 14f, g). Stenstad et al.
[107] reported that surface of NFC modified with GMA
(20 lmol GMA/mg NFC) displays a more barbed nature while
the surface of unmodified microfibrils appears fairly smooth.
Hydrophobicity of acetylated nanofibres increased as compared to the non-acetylated nanofibres [125]. The acetylated
nanofibres formed stable suspension in both acetone and
ethanol, while the non-acetylated nanofibres showed a slow
sedimentation in used solvents. Lonnberg et al. [103] also
18
Fig. 14 AFM topographic images

(55 m) of a unmodified NFC,
b NFC-g-PGMA, c NFC-gPHEMA, d NFC-g-PEA and
e NFC-g-PBuA. Phase images
of f NFC-g-PEA and g NFC-gPBuA. Reprinted from [109],
Copyright 2011, with permission
from Elsevier
found that dispersibility of NFC in nonpolar solvent is greatly

improved after grafting with PCL.
The impact of acetyl content on the dispersion stability of
NFC was studied by Tingaut et al. [120] and found that
resulting powdered nanofibres were easily redispersed in
chloroform, a PLA solvent of low polarity, leading to very
stable suspensions as shown in Fig. 15. The unmodified NFC
could not be dispersed, as a result of strong hornification
during drying, and suspensions of acetylated NFC showed
varying degrees of stability, which were dependent on %
acetylation (Ac). Stable suspensions were observed for acetylated NFC with more than 1.5 % of Ac and quality of the
suspensions being similar to the one described in Fig. 15a.
However, a total flocculation was observed for an NFC with
1.5 % of Ac, which was associated with an incomplete acetylation of the nanofibres surface.
NFC grafted with PGMA and poly(methyl methacrylate)
(PMMA) was observed immediately after synthesis and found
still dispersed in water as a milky mixture [109]. The solid
substance had nevertheless formed visible particles, which
descended to the bottom relatively quickly. These products
formed a stable dispersion in acetone and THF, similarly to
unmodified NFC in water. Products containing PEA and
PBuA were much more hydrophobic and precipitated from
water as considerably larger particles. When the solvent was
replaced by a less polar one, the particles were better dispersed.
In the least polar solvent (toluene), modified NFC seemed to
swell and become translucent. Grafting with PHEMA did not
change the appearance of water suspension, and the product

was well dispersed both in water and methanol. When
dried, the well-dispersed products formed a fragmented film
or a solid mass, whereas granular products retained their
form (Fig. 16).
Fig. 15 Suspensions in chloroform of acetylated NFC (0.07 % (w/w))

with acetyl contents of 0 (unmodified NFC), 1.5, 4.5, 8.5, 13 and 17 %. a,
b Solvent exchanged and dried samples, respectively. Photographs were
taken 24 h after sonication. Reprinted from [120], Copyright 2010, with
permission from American Chemical Society
Fig. 16 Water droplet on the surface of unmodified NFC (1) and products grafted with PGMA (2), PEA (3), PMMA (4), PBuA (5) and
PHEMA (6). Reprinted from [109], Copyright 2011, with permission
from Elsevier
Water contact angle for a drop of water on the surface of

treated NFC was measured by Lu et al. [115]. They observed
that untreated NFC film was very hydrophilic due to the OHrich molecular structure, which gives a contact angle of 15.
The silane treatment of NFC increases the value of water
contact angle to 90 and 64 for aminosilane-treated NFC
(ANFC) and GNFC, respectively. It was observed that titanate
treatment completely changes the hydrophilic surface of NFC
to the hydrophobic one. The water contact angle increases
from 15 to 110, which was more hydrophobic than the
silane-treated NFC. This is possible due to much less polarity
of the alkyl chain of the titanate modifier.
Fig. 17 TGA thermograms for
acetylated NFC with acetyl
contents of 0 (unmodified NFC),
1.5, 4.5, 8.5, 13 and 17 %.
Elsevier
19
The impact of chemical modification on the crystal structure of fibre using wide-angle X-ray diffraction (WAXD)
analysis was evaluated by Tingaut et al. [120]. It was observed
that more than 4.5 % of Ac promoted significant changes in
the NFC crystalline structure (WAXD experiments) and
prevented hornication upon drying. This was possible because
grafted acetyl groups allowed reduced hydrogen bonding
between cellulose microfibrils.
The impact of acetyl content on the thermal properties
of NFC was evaluated by TGA [115]. The thermograms of
acetylated NFC with %Ac ranging from 0 to 17 % are
presented in Fig. 17, where the 5 % weight loss temperatures (T 5 wt.%) are listed. At 5 % weight loss, a T5 wt.%
of 290 C was measured for the unmodified NFC but was
systematically shifted to higher temperatures for acetylated
samples. T5 wt.% increased gradually with the acetyl content, up to 10.5 %, for which a temperature of 345 C was
measured.
Applications of nanofibrillated cellulose

Nanofibrillated cellulose-based nanocomposite materials
There are many methods for the reinforcement of original and
modified nanofibrillated cellulose in polymer matrices such as
solvent casting, melt mixing, mixing the NFC suspension in
water with polymer latex or aqueous suspension, in situ polymerization and electrospinning. Properties of nanocomposite
depend on the nature of polymer matrix, interaction between
20
polymer matrix and cellulose nanofibrils and structure of large

interphase elements [131].
Solvent casting and melt mixing
Solvent casting and melt mixing methods were extensively
studied around the world for fabrication of nanofibrillated
cellulose-based polymer composites. Favier et al. [132] were
the first to report the use of nanocellulose as reinforcing
fillers in poly(styrene-co-butyl acrylate)-based nanocomposites. Since then, numerous nanocomposite materials were
developed by incorporating nanocellulose into a wide range
of polymeric matrices such as polyethylene or polypropylene
(non-biodegradable polymers), PLA, polyvinyl alcohol, starch,
PCL, polyhydroxybutyrate, polymethymethacrylate etc. [10,
133137]. The properties of these cellulosic nanocomposites
depend on the types and characteristics of nanocellulose and
polymeric matrices (which could be both natural and synthetic
polymers) [138].
The PLA nanocomposites reinforced with cellulose microfibrils were synthesized by mixing the microfibrils with PLA
in an organic solvent and then roller-mixed to attain uniform
dispersion of the cellulose fibrils. NFC reinforcement increased the Youngs modulus and tensile strength of PLA
by 40 and 25 %, respectively, without a reduction of yield
strain at a fibre content of 10 wt.% [139]. PLA nanocomposites were also fabricated using cellulose microfibrils as
reinforcement by mixing the microfibrils with PLA in an
organic solvent with various fibre contents up to 20 wt.%,
followed by drying, kneading and hot pressing into sheets.
Thermal and mechanical properties of composites were
studied, and tensile modulus and strength of neat PLA
were found to be improved in both amorphous and crystallized states with an increase of NFC content. The
addition of 20 wt.% of NFC in PLA improved the storage
modulus of crystallized PLA at a high temperature
(120 C) from 293 to 1,034 MPa [140].
Cellulose nanofibre-reinforced (CNF) PLA composites were
developed by twin screw extrusion [141]. Nanocomposites were
synthesized by premixing a master batch with high concentration of CNFs in PLA and diluting to final concentrations (1, 3,
5 wt.%) during the extrusion. Effect of nanofibre content (1, 3,
5 wt.%) on the composites mechanical and thermal properties
was evaluated, and it was found that tensile modulus increased
from 2.9 to 3.6 GPa and tensile strength increased from 58 to
71 MPa for nanocomposites with 5 wt.% of CNF. The dynamic
mechanical properties carried out using the dynamic mechanical
analyzer (DMA) were also positive: the storage modulus being
more significant in high-temperature region (70 C) and increased for all nanocomposites in comparison to neat PLA.
Reinforcement of cellulose nanofibres shifted the tan peak
towards higher temperatures. The tan peak of the PLA shifted
from 70 to 76 C for composites with 5 wt.% CNF loading.
Environmentally friendly green composites were fabricated

from starch-based, dispersion-type biodegradable resin and
cellulose nanofibres by blending them using a home-use mixer
and a stirrer [142]. The mixture was dried in air or vacuum, and
composites were then hot-pressed at 140 C and 1050 MPa.
Flexural strength and flexural modulus of composites were
increased with increase in moulding pressure.
Synthesis of CNF polyvinyl acetate (PVAc) composites
was carried out using the twin screw extrusion technique,
and influence of CNF content on nanocomposites morphology, tensile and viscoelastic properties was studied.
The tensile strength and modulus of PVAc were improved
by 20 and 59 %, respectively, with increased CNF content
(10 wt.% CNFs) as compared to the matrix. The fractured
surfaces of the nanocomposites after the tensile tests
showed the bridging of CNFs inside the micro-cracks
which indicates good stress transfer and limited plastic
deformation. The DMA study showed a slight increase
in the storage modulus as well as positive shift and
broadening of the tan delta peak of PVAc with increased
CNF content. The creep study showed that CNFs improved
the elasticity of PVAc and strongly restricted the viscous flow
of PVAc chains, thus enhancing the creep resistance of PVAc
effectively [143].
Nanocomposite films of NFC and melamine formaldehyde
(MF) resin were produced as a potential material for use in
loudspeaker membranes, where a high Youngs modulus and
low density are required. The MF-NFC nanocomposites
showed average Youngs modulus as high as 16.6 GPa and
average tensile strength as high as 142 MPa, while density
was higher than for a conventional paper prepared from pulp
fibres. Combination of these properties including high
mechanical damping attainable with NFC films and composites
shows that these materials have potential to be used as loudspeaker membranes [2].
Nanocomposites of swede root NFC were fabricated using
four types of acrylic and two types of epoxy resins. All the
composites were significantly stiffer and stronger than the
unmodified resins [144].
Seydibeyoglu and Oksman [145] synthesized PU-NFC
composite materials using a film stacking method in which
PU films and non-woven cellulose fibril mats were stacked and
compression moulded. NFC reinforcement improved thermal
and mechanical properties of pure PU. Nanocomposites with
16.5 wt.% fibril content had tensile strength and E-modulus
values nearly five times and 30 times higher, respectively, than
the corresponding values for matrix polymer.
PLA bionanocomposites with tunable properties were prepared using the unmodified and acetylated NFC (with %Ac
ranging from 0 to 17 %), with NFC contents from 2.5 to
17 wt.%. An increase in PLA glass transition temperature was
observed by using 8.5 % acetylated NFC at 17 wt.%, indicating
an improved compatibility at the fibrematrix interface. These
findings suggest that final properties of nanocomposite materials can be controlled by adjusting the %Ac of NFC [120].
The untreated and silane-treated NFC were successfully
incorporated into epoxy resin system by using acetone as
solvent. The better dispersion of NFC and stronger adhesion
between microfibrils and matrix were confirmed by ESEM,
which resulted in better mechanical properties of composite
materials. At a 3.7 wt.% addition of NFC, the storage modulus
at 30 C increased about 20 %, with the ANFC having a
modulus increase of greater than 25 %. At 130 C, modulus
increase was more substantial with ANFC, increasing the
modulus from 10 MPa to over 65 MPa [115].
Synthesis of nanocomposites of alkali-treated NFC and
phenolic resin was reported, and their mechanical properties
were compared with their pulp fibre-based microcomposite
counterparts. Tensile tests showed that strong alkali-treated
NFC nanocomposites with resin content around 20 wt.%
achieved strain at fracture values two times higher than those
of untreated NFC nanocomposites and five times higher than
those of untreated pulp microcomposites. The improvement in
work of fracture of alkali-treated NFC nanocomposites was
attributed to the ductility of the nanofibres caused by transformations in the amorphous regions along the cellulose microfibrils [128]. Polylactide/NFC composites were prepared by
compression moulding of wet-comingled NFC and PLA latex
or powder, twin screw extrusion of the wet-comingled compounds and solvent mixing of PLA with NFC or acetylated
NFC. Optical microscopy and transmission electron microscopy were used to investigate the morphology of composites.
Acetylation of NFC decreased the hydrophilicity of NFC and
improved chemical affinity with the PLA matrix. Solvent
casting resulted in a more uniform dispersion of NFC fibres
and compression moulding of wet comingled NFC and PLA
latex or powder compounds resulted in a cellular NFC network, whereas in case of acetylated NFC, somewhat lower
aggregate diameters were observed [146].
In situ polymerization
In this approach, a pre-polymer or monomer is polymerized in
the presence of nanofibrillated cellulose thus allowing better
dispersion of the NFC with superior mechanical and other
properties.
UV photopolymerization was used for the synthesis of in
situ polymerized bionanocomposite hydrogels. The swelling
behaviour, mechanical properties, morphology and biocompatibility of synthesized polymer nanocomposites based on
nanofibrillated cellulose were studied. All synthesized composite hydrogels reinforced with NFC showed lower swelling, increases mechanical properties, a porous and homogeneous structure and resulted biocompatible as compared to
neat hydrogel [147]. NFC/PANi composite paper was fabricated through in situ polymerization of aniline monomers on
21
nanocellulose fibrils followed by vacuum filtration or solvent evaporation of casting (Fig. 18). NFC/PANi composite
paper-based materials were found to exhibit good mechanical properties and high conductivity. The NFC/PANi composite paper exhibits a percolation threshold of electrical
conductivity of 4.57 vol.% of PANi content, at which the
corresponding conductivity was measured to be 2.6
105S cm1, which is well above the antistatic criterion of
108S cm1. Remarkably, at the percolation threshold, the
mechanical strength of the NFC/PANi composite paper is as
same as that of neat NFC. These materials may find potential applications in flexible electrodes, antistatic coatings and
electrical conductors [148].
An electrically conducting nanocellulose polypyrrole composite based on nanofibrillated cellulose from wood was fabricated through in situ polymerization. On the basis of experimental, it was reported results that synthesized nanocellulose
composites may significantly facilitate industrial manufacturing of highly porous, electroactive conductive paper materials
for applications including ion-exchange and paper-based
energy storage devices [149].
Electrospinning
Electrospinning is an efficient technique for the fabrication of
polymer nanocomposite fibres. Only few investigations are
available for reinforcement of e-spun fibres. Nanofibrillated
cellulose was introduced into polyethylene oxide (PEO) fibres
by an e-spinning procedure in order to improve their
mechanical properties. Effect of NFC was investigated
with respect to e-spinning process parameters as well as
morphological and mechanical properties of the fibres. The
morphological investigations showed that reinforcing fibres
with circular cross-sections results in homogeneous dispersion within the polymer matrix. Modulus of elasticity was
increased from about 3866 MPa for PEO fibres having
no or little content of NFC to 240470 MPa for highly
filled fibres as has been observed [150].
Electrospun nanofibres of poly(vinyl alcohol) reinforced
with cellulose nanofibrils were prepared by electrospinning,
and tensile strength and Youngs modulus of reinforced composites were found to be increased by ca. 240 % by addition of
only 6.6 wt.% of cellulose nanofibres without major changes
in elongation at break. This may be attributed to the good
interaction between PVA and cellulose nanofibres during the
compounding step [151]. A dispersion of cellulose nanofibril
with PEO dissolved in water was used to obtain composite
nanofibres by electrospinning techniques. Various parameters
like target-source distance, voltage, flow rate and concentration of PEO solution were found to be 15 cm, 2225 kV,
13 ml/min and 5 wt.% [152]. Nanocomposite fibres were
electrospun into non-woven fabrics at elevated temperature from
poly(lactic acid) in dimethylformamide solutions containing
22
Fig. 18 a Schematic showing the

preparation of NFC/PANi
composite paper through in situ
polymerization of aniline
monomers on nanocellulose
fibrils, following by vacuum
filtration or solvent evaporation
of casting, b photographs of
NFC, PANi and NFC/PANi
composite suspensions containing
580 wt.% of PANi with solid
contents of ca. 1 mg ml1.
Elsevier
suspended cellulose nanofibrils. Water contact angle of the

electrospun non-woven fabrics was found to decrease with
increase in cellulose nanofibril content. Incorporation of
cellulose nanofibrils to poly(lactic acid) results in enhanced
strength and decreased elongation of the electrospun nonwoven fabrics [153].
Biomedical applications
In recent years, cellulosic nanofibres were successfully used
by many researchers for biomedical applications. Valo et al.
[154] have studied the application of cellulosic nanofibres in
drug delivery. Hydrophobin coupled with two cellulose
binding domains was used in order to facilitate drug nanoparticle binding to nanofibrillar cellulose. Cellulose nanofibrillar
matrix provides protection for the nanoparticles during the
formulation process and storage. Nanoparticles around
100 nm could be stored in a suspension with cellulose
nanofibrils for more than 10 months when the specific
cellulose binding domain was fused to the hydrophobin. It
was also found that freeze-dried particles in the cellulose
nanofibrils matrix were preserved without major changes
in their morphology.
Nanofibrillated cellulose composite hydrogel was developed
for the replacement of the nucleus pulposus. It was reported
that composite hydrogels reinforced with cellulosic
nanofibres may be viable as nucleus pulposus implants due
to their adequate swelling ratio, which may restore the
annulus fibrosus loading, and their increased mechanical
properties, which could possibly restore the height of the
intervertebral discs [147]. Biocomposite hydrogels with

carboxymethylated, nanofibrillated cellulose powder were
also prepared by UV polymerization of N-vinyl-2-pyrrolidone with Tween 20 trimethacrylate as a cross-linking agent
for replacement of the native, human nucleus pulposus in
intervertebral discs. Nanofibrillated cellulose powder was
prepared after solvent exchange and centrifugation by drying
the suspension at 60 C and ambient pressure under subsequent stirring with a glass bar [155]. Cellulosic nanofibres
were used as a material for the development of nanocomposite scaffolds for use in artificial ligaments or tendon
substitutes. Nanocomposites were prepared with mechanical
properties similar or better than the natural ligaments and
tendons. The nanocomposites were found to exhibit excellent
cytocompatibility required for biomedical applications.
Collagen-based implantable scaffolds reinforced with the cellulosic nanofibres were also prepared. Cellulosic nanofibres
reinforcement resulted in better mechanical performance and
dimensional stability without affecting the biocompatibility
and non-toxicity of collagen [156, 157].
Cellulosic nanofibres were prepared from native cellulose
by TEMPO-mediated oxidation and individually dispersed
in water by mechanical disintegration. These cellulosic
nanofibres were found to exhibit characteristic biological
activities when administered to mice and may have potential
applications to biomedical fields for human health. TEMPOoxidized cellulosic nanofibres were orally administered with
glucose and glyceryl trioleate to mice, and blood levels of
metabolic variables were followed over time. Blood glucose,
insulin, glucose-dependent insulinotropic polypeptide and
23
triglycerides were significantly decreased, especially 10 min

after the administration cellulosic nanofibres [158]. Cellulose
nanocomposites reinforced with NFC isolated from pineapple leaf fibres were designed of prosthetic heart valves as
well as vascular grafts [159].
Nanofibrillated cellulose as adsorbent for removal of heavy
metal ions and CO2 capture
Given the high surface area of the nanofibrillated cellulose,
adsorbent based on modified NFC might afford an interesting
alternative to conventional adsorbent like activated carbon,
ion exchange resins or zeolite. This new area of potential use
of NFC in the field of water treatment was explored by several
recent publications that showed the possibility to prepare
adsorbent based on modified nanofibrillated cellulose for
removing heavy metal ions but also organic pollutants. The
possibility to implement wide possibility of surface modification on the cellulose surface opens the way towards the
insertion of specific groups, such as carboxyl, amine, ammonium and thiol likely to interact with metallic cations or
organic compound. Adsorption is the most effective and versatile method for the removal of heavy metals as other
methods have high operating cost and generates solid waste
which poses disposal challenges [160163]. Stephen et al.
[164] used oxolane-2,5-dione-modified cellulose nanofibres
for adsorption of cadmium and lead ions from model wastewater samples for the first time. They studied adsorption
kinetics using different concentration for lead and cadmium:
20, 50, 100, 150 and 200 mg L1 at an adsorbent concentration
of 2 g L1. The order in adsorption behaviour was Cd>Pb.
This could be explained by the chelation and entrapment of
cadmium on the ligand as well as the pores on the surface of
functionalized cellulose. The maximum adsorption (q max)
demonstrates the higher capacity of cellulose-g-oxolane-2,
5-dionenanofibres for Pb and Cd removal as compared
with oxolane-2,5-dione functionalized raw cellulose fibres
(Table 3). The adsorption capacities for functionalized
cellulose nanofibres were 1.0 and 2.91 mmol g1 for Pb

and Cd, respectively, in comparison to 0.002 mmol g1 of
raw cellulose. Moreover, Table 3 shows that metal uptake
data agree strongly with Freundlich adsorption isotherm
model with correlation coefficient (r 2) of 0.99.
Amine-based nanofibrillated cellulose adsorbent was
developed for CO2 capture from air through freezedrying an aqueous suspension of nanofibrillated cellulose
and N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane.
CO2 adsorption was carried out for 12 h of experiments at an
air flow rate of 1 L/min at 25 C, 40 % relative humidity and
CO2 concentration of 506 ppm. The CO2 outlet concentration
as a function of the adsorption time of aminosilanemodified nanofibrillated cellulose aerogel is shown in
Fig. 19. After 12 h of experiment, CO2 uptake rate became
small (0.67 mol/g/min), and the CO2 outlet concentration
reached 97 % of the inlet concentration. CO2 adsorption
was found to be 1.39 mmol CO2/g [165].
NFC as an adsorbent for dissolved organic compounds
Highly porous cellulose organogels were prepared from
nanofibrillated cellulose hydrogels, and their adsorption
properties towards a wide range of organic pollutants
including aromatic compounds, herbicide and pesticides
were investigated by Maatar et al. [166]. It was shown
that by functionalizing the native cellulose nanofibrils of
the organogel with the hydrophobic hydrocarbon chains,
the adsorption capacity is meaningfully boosted, making
possible to use the modified organogel as an adsorbent for
organic compounds (Table 4). Adsorption capacity ranging
from 50 up to 500 mol/g was reached for the modified
NFC organogel. It was proposed that the adsorption process is the result of the diffusion of the organic solute
Table 3 Langmuir and Freundlich isotherm constants for Cd and Pb onto

functionalized cellulose, nano and raw fibres (reprinted from [164],
Copyright 2011, with permission from Elsevier)
Langmuir
Freundlich
Metal q max
(mmol g1)
ion
K L (L mmol1) r 2
K f (mmol g1) n
Cd
Pb
r2
0.59a
0.001
0.989 2.91
1.93 0.988
0.13b
0.02
0.998 0.002
0.39 0.979
1.21a
0.002
0.995 1.0
1.23 0.997
0.24b
0.01
0.986 0.002
0.43 0.942
Cellulose-g-oxolane-2,5-dione nanofibres
Raw cellulose-g-oxolane-2,5-dione
Fig. 19 CO2 outlet concentration during humid CO2 adsorption on

aminosilane modified nanofibrillated cellulose aerogel (solid line) and
fractional uptake of the CO2 capacity (dashed line). Reprinted from
[165], Copyright 2011, with permission from American Chemical Society
24
Table 4 Physical characteristics of the different solutes and their maximum adsorbed amount on both the unmodified and modified
nanofibrillated aerogel. Reprinted from [166], Copyright 2013, with permission from Elsevier
Maximum adsorption capacity on the unmodified cellulose aerogel
Maximum adsorption capacity on the modified cellulose aerogel
Fig. 20 FE-SEM of ultra-thin layer of paper prepared in presence of

added NFC
inside the grafted hydrocarbon chains acting as a reservoir

on which the organic compounds would be accumulated.
The results showed that the modified cellulose organogels
could be easily regenerated and reused without any loss of
the adsorption capacity, which constitutes one of the main
advantages of this category of the adsorbents derived from
a renewable resource.
NFC as a strength additive for paper and paperboard
The use of nanofibrillated cellulose as a reinforcing additive to
improve physical and mechanical properties of paper has
recently arouse much interest, and promising potential in the
field of paper technology and packaging is expected in the
near future [68, 167169]. In fact, owing to the large specific
surface area and high aspect ratio, NFC and their strong
affinity with cellulosic pulp, along with their ability to form
a 3D network, constitute so many benefits for the improvement of paper strength when NFC was added to the pulp
slurry. Taipale et al. [169] showed that the addition of NFC
decreased the drainage rate of pulp suspension and increased
the strength of paper, especially if a cationic polyelectrolyte is
used as a retention aid. However, by optimum selection of
materials and process conditions, an enhancement of the
Fig. 21 Schematic illustration of

the mechanism of paper
strengthening in presence of
added NFC. Reprinted from
[170], Copyright 2013, with
permission from Springer
25
strength properties could be achieved without simultaneously

deteriorating the drainage. The effect of the NFC addition on
the paper strength was also confirmed by Gonzalez et al. [167,
170] who undertaken a deep investigation on how the NFC
addition might improve the mechanical strength of paper and
reduce the energy demand during the refining process.
In a recent work carried out by Gonzalez et al. [170], it was
shown that combination of the enzymatic treatment of the
pulp (biobeating) and NFC addition can be considered as a
promising alternative to traditional beating as a way of
improving mechanical properties of the final paper without
simultaneously reducing drainage rate at undesirable levels.
The addition of NFC to the enzyme-treated pulp significantly
increased mechanical properties of paper; porosity was reduced, whereas opacity remained unmodified. The hypothesis
of NFC acting as an adhesion promoter of cellulose fibres was
clearly confirmed by field emission scanning electron microscopy (FE-SEM) observation (Fig. 20). A schematic illustration of the strengthening mechanism of NFC for paper was
also proposed (Fig. 21). It was found that enzymatic treatment
improved the mechanical properties of fibres without modifying drainability. After biobeating, NFC was added to the
enzyme-treated pulps. Mechanical properties were enhanced,
obtaining length at break values similar to those observed in
commercial printing/writing paper. Opacity remained constant, whereas porosity was gradually reduced as more amount
of NFC was added. The presence of NFC also reduced
drainability, although it remained at suitable levels for the
papermaking industry. The results suggest that the combination of biobeating and NFC addition can be considered as an
alternative to mechanical beating.
Conclusions
Nanofibrillated cellulose has exciting potential as reinforcements
in polymer matrices for the development of bionanocomposites.
26
TEMPO-mediated oxidation pre-treatment was shown to dramatically decrease the energy consumption and size of
nanofibrillated cellulose. Enzyme pre-treatment can reduce the
processing cost by lowering the number of passes through the
homogenizer. Hydrophilic nature of nanofibrillated cellulose can
be tailored by various methods such as esterification, silylation,
polymer grafting etc.
In fact all of the chemical modification likely to be undertaken on cellulose fibres might be implemented on the NFC
surface. These wide possibilities of surface modification
open the horizon towards more possible use of NFC in
advanced and new functional materials. Developing
greener approach of surface modification of NFC will
certainly constitute a promising strategy within the context
of new sustainable and environmental-friendly products
derived from renewable resources.
Due to the improved properties, in applications
nanofibrillated cellulose composites are being developed for
use in engineering and medical fields. Transparent nanocomposite material with enhanced stiffness and strength could be
obtained with the incorporation of NFC in a polymer matrix.
Water-soluble harmful organic pollutants can be removed
with the help of nanofibrillated membranes, and paper and
paperboard with improved strength and reduced energy
consumption can be produced by the addition of NFC to
the pulp. The main challenge in the scale-up of commercial production of NFC will be tributary on the energy
requirement for the disintegration process and how efficient will be the fibres pre-treatment to make easier the
cell wall breakup.
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14251435
Susheel Kalia is Visiting Researcher in the Department of

Civil, Chemical, Environmental andMaterials Engineering
at the University of Bologna,
Italy. He has more than 60 research papers in international
journals along with over 80
publications in conferences
and several book chapters. Additionally, he has edited a
number of books. Presently,
his research is in the field of
biocomposites, nanocomposites, conducting polymers, cellulose nanofibers, nano-hybrid materials, hydrogels and cryogenics.
Sami Boufi is presently a Professor in the Department of Chemistry of the University of Sfax in
Tunisia. He got his PhD in the
Sciences of Polymeric Materials
from the Grenoble Institute of
Technology, France in 1993. His
research activities include composites and nanocomposites
based on natural fillers and
nanofillers, chemical modification of cellulose, colloidal chemistry with special focus on
nanocellulose and polysaccharide
based nanoparticles.
31
Annamaria Celli received her
PhD in Materials Engineering from
the University of Bologna. She was
employed as a researcher at the
Giulio Natta Research Center of
Himont/Basell in Ferrara and then,
she rejoined the University of Bologna as an assistant professor in the
Polymer Group of DICAM. Her
research focus is within the fields
of relationships between macromolecular structure and properties,
preparation of novel polymers, composites and nanocomposites, mainly
in the field of renewable materials.
Sarita Kango received her

Masters degree in Chemistry
from Panjab University Chandigarh in 2010 and M.Phil
from Sho oli ni U niv ersit y,
Solan in 2011. Currently she
is Research Fellow in the Dept.
of Physics and Materials Science at Jaypee University of
Information Technology, Solan
(India). Her areas of interest
are natural fibers, polymer
grafting, semiconductor and
magnetic nanoparticles and
nanocomposites

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Colloid Polym Sci (2014) 292:531