Polymer-Plastics Technology and Engineering

ISSN: 0360-2559 (Print) 1525-6111 (Online) Journal homepage: http://www.tandfonline.com/loi/lpte20

A review on nanocellulose polymer

nanocomposites

Subrata Mondal

To cite this article: Subrata Mondal (2017): A review on nanocellulose polymer nanocomposites,
Polymer-Plastics Technology and Engineering, DOI: 10.1080/03602559.2017.1381253

To link to this article: http://dx.doi.org/10.1080/03602559.2017.1381253

Accepted author version posted online: 21

Sep 2017.

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 A review on nanocellulose polymer nanocomposites

Subrata Mondal

Department of Mechanical Engineering, National Institute of Technical Teachers’ Training and

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Research (NITTTR), Salt Lake City, Kolkata, West Bengal, India

Address correspondence to S. Mondal. E-mail: subratamondal@yahoo.com

ABSTRACT

Recently, nanocellulosic materials have been received significant research interest as

potential nanofiller for the reinforcements in the polymer matrices due to its renewable in nature,

readily availability, biocompatibility, inexpensive, excellent physical properties, tailorable

surface properties etc. In this review, author attempted to provide an overview of various

methods for nanocellulose reinforced polymer nanocomposites fabrications, properties of

nanocellulose based nanocomposites and their applications. The review has been emphasized for

the reinforcement of nanocellulose in various polymer matrices viz. hydrophilic, hydrophobic

matrices. Nanocellulose reinforced polymer nanocomposites have huge potential in diverse

applications which is ranges from biomedical, packaging, electronic, environmental fields etc.

Graphical Abstract

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KEYWORDS: applications, biomedical, mechanical properties, nanocellulose, polymer

nanocomposite

1. Introduction

Composites are multiphasic heterogeneous materials with improved properties as

compared with matrix phase. Matrix phase is a continuous phase while reinforcement phases are

discontinuous in nature. Individual components in the resultant composites are remained bonded

together in the mixed phases by physical or chemical means while retaining their physical

identities. In the nature, we have many interesting composite materials such as wood, bone etc.

Wood is a composite of cellulose fibrils reinforced in a lignin matrix, whereas, bone is a

composite of mainly hydroxyapatite (mineral) and collagen (protein) (Figure 1).[1] These natural

bio-composites serve as bench mark for the material scientists to design novel composite

materials with improved properties for the diverse applications.

Nanotechnology is the understanding and control of materials at the nano scale

dimensions with at least one dimension in the region up to 100 nm.[2] The unique phenomena of

nano dimensional materials could finds novel advanced material applications. Nanomaterials

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 derived from renewable resources such as cellulosic and lignocellulosic biomass could play huge

role in the nanotechnology research move.[3] Cellulose nanofibrills (which is the main

component of plant cells) provides strength, stiffness and toughness to the plant anatomy.

Typically, wood contain 40-50% of cellulose in form of nearly 2/3 nanocrystal and other 1/3

portion as amorphous.[4] Cellulose is a linear polymer of β-anhydroglucopyranoside with 1, 4 β-

glycosidic linkages in its molecular structure. Nanocellulose can be extracted from the

lignocellulosic biomass by an appropriate method or combination of more than one method.

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Extracted nanocellulose is a readily available and renewable biomaterial resource with novel

properties for the applications in advanced materials fields.[5] With the advances of

nanotechnology, material scientists are interested to extract nanocellulose from various natural

resources such as cotton, jute, ramie, bamboo, rice husk, starch, sisal etc and use them for the

advanced material applications. The shape, size, surface morphology, yield and properties of

nanocellulose would depend on source of lignocellulosic biomass, pretreatment and preparation

processes. Nanocelluloses combine the important chemical properties of cellulose with

interesting phenomena of nanoscale materials.[6–8]

Nanocomposites are interesting class of materials in which nanomaterials are reinforced

(Figure 2), and the nanomaterial has at least one dimension up to 100 nm. Polymer

nanocomposites have received great deal of interests among the scientific and industrial

communities in recent years because these materials can achieve significant improvements in

mechanical properties, dimensional stability, and solvent or gas barrier properties with respect to

the matrix polymer at very low concentration of fillers as compared with continuous phase.[9]

Nanosized cellulosic materials can be a good nanofilles for the fabrication in the polymer

nanocomposites in order to improve the overall performance (in terms of mechanical properties

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 and other functional properties viz. partial degradation, improvement of barrier properties etc.) of

nanocomposites. Cellulose nanocrystal as a reinforcing phase has been gained significant

attentions due to their low cost, biodegradability, ease of availability, high strength, renewability

and some other excellent properties due to their nano dimensions.[10] With a Young's modulus in

the range of 100-130 GPa, large specific surface area which is several hundred of m2.g-1,

nanocelluloses have the potential to reinforced various polymer matrices with very low filler

loadings to achieve targeted properties.[4,11] Thermoplastic polymer as well as thermosetting

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polymers could be used as matrix for the reinforcement of cellulosic nanofillers. Applications of

nanocellulose reinforced nanocomposites with thermoplastic and thermoset polymers as matrices

could be considered for the potential in diverse fields such as in packaging products,

construction, automotive, furniture, electronics, membranes etc.[10] This review presents polymer

nanocomposites using nanocellulose as potential reinforcing phase. Various methods of polymer

nanocomposites preparations, their properties and potential applications have been reviewed. The

paper has been concluded with few challenges of the nanocelluloses as potential filler for the

polymeric composites.

2. Background of Polymer Nanocomposites and Nanocelluloses as

Potential Nanofillers

Polymer nanocomposites are composite materials which has polymer domain as

continuous phase, whereas, reinforcing phase with at least one dimension typically less than or

equal to 100 nm.[12] Due to the presence of nano sized filler, nanocomposite possesses excellent

properties in several ways which could not be achieved by micro and macrocomposites.[13]

Nanoreinforcing materials with large specific surface areas, high aspect ratios (length by breath

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 ratio) exhibits better mechanical strength than their microsized counterparts, and required little

quantity as compared with the microfillers in order to effectively reinforce in the polymer matrix.

Therefore, some of the properties of pristine polymer e.g. density would remain unaffected in the

resultant nanocomposites.[14] Properties of nanocomposites depend on three major factors, such

as properties of polymer matrix and nanoreinforcing phase, together with interfacial interaction

between filler surface and matrix polymer. Further, for a specific nanoreinforcement phase and

matrix polymer, the properties of a polymeric nanocomposites are very much dependent on the
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dispersion and distribution of nanomaterials in the continuous matrix phase (Figure 3).[15,16]

Like other nano scale materials, nanocellulosic material has at least one dimension of

typically about 100 nm. Nanocellulose is a common name of cellulosic nanomaterials which

includes bacterial nanocellulose (BNC) produced by certain strains of bacteria, cellulose

nanofibres (CNF) and cellulose nanocrystals (CNC) extracted from the lignocellulosic

biomasses.[17,18] Nanocellulose can be prepared from lignocellulosic biomass in two stages viz.

pretreatment of raw cellulosic biomass and transformation of pretreated biomass into cellulose

nanomaterials by mechanical, chemical, enzymatic or combination of more than one method. In

the first stage, the pretreatment is used to purify the biomass to obtain individual cellulosic

fibers; whereas, the main process, transformation uses various methods such as a) mechanical, b)

chemical, c) combination of mechanical and chemical, and d) enzymatic process to disintegrate

cellulose nanocrystal from the individual cellulose fiber matrices.[19] Acid hydrolysis is the most

common chemical method for the extraction of nanocellulose from the lignocellulosic biomasses.

In acid hydrolysis process, acid attacks intermolecular and intramolecular bonds among cellulose

molecules, hemicellulose, and lignin in the biomass hierarchy structure in order to break down

the rigid structure of lingocellulosic material.[20] The morphology and dimension of

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 nanocellulose depends on source of natural resources when same preparation method would be

employed. Deepa et al. reported the dimension of nanocelluloses prepared by acid hydrolysis

method from various lignocellulosic biomasses such as banana rachis, sisal, kapok, pineapple

leaf and coir with an approximate diameter between 10–60, 20–80, 20–70, 50–150 and 40–90

nm respectively.[7] In this review, author mainly reported cellulose nanocrystal as reinforcement

phase in the polymer matrix. Cellulose nanocrystal has several excellent characteristics that

makes these nano dimensional material as an ideal for the reinforcing phase in the polymer
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matrix, as follows [19]:

i) High aspect ratio (length/width ratio) than microcellulosic materials, which

enables good stress transfer between fillers and polymer matrix, and vice versa

during the loading process;

ii) High specific contact surface area due to the nano sized dimensions, hence, low

concentration required to disperse and distribute throughout the matrix, and

achieve targeted properties;

iii) Presence of enormous hydroxyl groups on the surface of the cellulosic nanofiller

could form hydrogen bonding/participate in the chemical reaction with matrix for

the better reinforcement in the matrix;

iv) Further, presence of plenty of hydroxyl groups provides opportunity for the

functionalization of nanocellulose with appropriate molecules for effective

reinforcement of nanocellulose into the various type of matrix polymer viz.

polar/non polar.

v) Cellulose nano fillers could be considered as environmental friendly and

renewable nanofillers.

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 3. Processing of Nanocellulose and Polymer Composites

Depending on the preparation methods, polymer nanocomposite processing can be

broadly divided into two categories viz. physical methods and chemical methods. Solution

processing, melt mixing methods, electro spinning are typical examples of physical methods,

whereas, in-situ polymerization method can be considered as chemical method for the

nanocomposite preparations.[21] Nanocomposites based on cellulosic nanomaterials could be

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prepared with nonbiodegradable polymers such as polyethylene (PE), polypropylene (PP),

polyurethane, polyester, nylon as well as with biodegradable polymers such as polylactic acid

(PLA), polyvinyl alcohol (PVOH), starch, polycaprolactone (PCL), methylcellulose, soy protein

and chitosan as potential matrices.[22] Due to the presence of hydroxyl groups on the

nanocellulose surface, cellulose nanomaterials have limited dispersibility in the nonpolar

polymeric matrices. Each nanocellulose unit has three hydroxyl groups in its structure, hence,

nanocellulose has reactive surface covered with numerous active hydroxyl groups in which some

of the hydroxyl groups could form intermolecular hydrogen bonding.[18] Hydrogen bonding

between the hydroxyl groups of nanocellulose with adjacent nanocellulose causes poor

dispersion of cellulosic nanofillers in nonpolar polymeric matrices. The aggregation of

nanocellulose in the polymer matrix is increases when size of the nanocellulose decreases as a

result of increase for the specific surface area.[4] Aggregation of nanocellulose in the polymer

domain structure can be to some extent controlled by surface modification of nanocellulose with

appropriate molecules. The major chemical modifications of nanocellulose are esterification,

silylation, cationisation, fluorescent labeling, carboxylation, polymer grafting with

polar/nonpolar molecules etc. Espino-Perez et al. hydrophobically modified cellulose nanocrystal

by solvent free esterification method using carboxylic acid (CA), phenylacetic acid and

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 hydrocinnamic acid molecules. Carboxylic groups in the CA would react with hydroxyl groups

to form ester functionality. Hydrophobicity of nanocellulose could improved due to the presence

of phenolic groups attached by using phynylacetic acid on the nanofiller surfaces.[23] Bae and

Kim modified the nanocellulose by using a long hydrophobic alkyl chain via a bimolecular

nucleophilic substitution to improve the dispersion of nanofillers in the polymer matrix.[24

Solution processing is a simple approach to prepare polymer nanocomposite. Nanofillers

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are dispersed in the base polymer or pre-polymer solution by solution processing method.

Mixture of nanofillers and polymers can be agitated by physical mean such as mechanical

stirring, ultrasonic methods etc. to obtain the homogeneous mixture. Then, nanocomposites can

be prepared by casting of polymer solution and afterwards, solvent could be removed to obtain

the solid polymer nanocomposite.[21] Nanocellulose has good dispersion ability in water due to

the presence of plenty of hydroxyl functionality on the nanocellulose surface. Therefore, water

could be a good choice for the processing medium of nanocellulose/polymer composites. Water

soluble polymers as well as water dispersible polymer latex can be used as the matrices for the

nanocomposite fabrication. Finally, polymer nanocomposites could be obtained by simple

casting and solvent (water) evaporation.[4] Nanocellulose or oxidized nanocellulose reinforced

composite films of hydroxypropyl guar (HPG), carboxymethyl guar (CMG), chitosan etc. can

prepared by solution casting in order to improve the dispersion and distribution of nanofillers in

the polymer matrix.[25]

In melt mixing, nanomaterials are dispersed into the polymer matrix at melt condition,

and the polymer nanocomposites can be obtained by extrusion method.[21] Uniform dispersion

and distribution of nanocellulose in the polymer matrix is essential to improve the properties of

resultant nanocomposites. Strong interaction between nanofillers and matrix is also important to

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 prevent leaching of nanomaterials during usage and to improve the mechanical properties of the

resultant nanocomposites. In order to achieve these, surface modification of nanomaterials is

essential, specially to reinforce the nanocellulose in the nonpolar polymer matrix. Abundance of

hydroxyl groups on the nanocellulose surface provides enormous opportunity for the

modification of nanocellulose prior to the nanocellulose reinforced polymer nanocomposite

processing by melt mixing method of nonpolar polymer.[19]

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Prior to the polymerization, nanofillers could be impregnated in monomer solution, then,

polymerization can be carried out for the in situ processing of nanocellulose polymer

nanocomposite.[21] Mabrouk et al. reported polymer nanocellulose composite by in situ

polymerization in a mini-emulsion polymerization of styrene (Sty) and 2-ethyl hexylacrylate

(EHA) using methacryloxypropyl trimethoxysilane (MPMS) as a coupling agent.[26] MPMS can

react with Sty and EHA via methacrylic moiety, and formed alokoxysilane functional

copolymers. Further, most of the alokxy functions would hydrolyse and formed silanol. Presence

of silanol groups on the surface of the polymer particles increases adsorption of nanocellulose by

hydrogen bonding. Further, during the film formation process, remaining nanocelluloses are

being physically adsorbed on the polymer particle surfaces. In the final stage of film formation,

condensation reaction would takes place between the surface of silanol groups of the MPMS and

the hydroxyl groups of nanocellulose (Figure 4).[26] In situ polymerization of aniline monomers

on the surfaces of nano fibrilated cellulose to form the nanocellulose polyaniline composite is

reported by Luong et al.[27] Prior to the polymerization, monomer molecules such as aniline

hydrochloride could be absorbed on the nano fibrilated cellulose surfaces via attractive forces,

such as hydrogen bonding between the hydroxyl groups of the nanocellulose and the amine

groups of aniline, and van der Waals force to ensures good distribution and dispersion of

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 nanomaterials in the polymer matrix, and strong interfacial interaction between the two

phases.[27] In situ polymerization of phenol and nanocellulose for the nanocomposites preparation

shows the decreased of particle size of the polyphenol in the resultant nanocomposites. Covalent

bonding of cellulosic nanomaterials with polyphenol matrix provides better dispersion of

nanoreinforcement phase in the polymer matrix with improved interfacial interaction as

compared with nanocomposites prepared by physically mixing of polyphenol and nanocellulose

materials.[28] Muller et al. presented poly (3,4- ethylenedioxythiophene) (PEDOT) coated

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bacterial nanocellulose composite membrane prepared by in situ oxidative polymerization of 3,4-

ethylenedioxythiophene on the surface of nanocellulose.[29] Further, polypyrole and

nanocellulose nanocomposite electrode can be prepared by polymerization of pyrrole on the

surface of the nanocellulose.[30]

Due to its hydrophilic in nature, it is always a challenge for the nanocellulosic materials

to properly disperse and distribute in the hydrophobic polymers matrices viz. polyethylene,

polypropylene, polystyrene etc. Carrillo et al. proposed double emulsion method for the

compatibilization of aqueous dispersion of nanocellulose with nonpolar polymer matrix for an

example polystyrene. Nanocellulose could be equilibrated with organic polymer phase in a stable

water-in-oil-in-water double emulsion system. Further, proposed method eliminates solvent

exchange or drying of aqueous dispersion of nanocellulose prior to the processing.

Microstructure and properties of the composites could be tailored by controlling the ionic

strength of cellulose molecules in nanocellulose dispersion.[31] Nanocellulose surface can be

modified with appropriate molecules in order to effectively reinforce the nanomaterials in the

polymer matrix. Nanocellulose modified with toluene diisocyanate exhibits excellent dispersion

of nanocellulose in the polylactide matrix with improved interfacial interaction.[32] Ambrosio-

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 Martin et al. reported polymer nanocellulose composite which was fabricated by high energy ball

milling technique taking poly(3-hydroxybutyrate-co-3-hydroxyvalerate) as matrix and bacterial

nanocellulose as potential nanoreinforcement phase.[33]

Nanofiber mat can be prepared by electro spinning method on a grounded metallic

collector target by stretching of electrically charged polymer solution (or melt) between two

opposite electric poles. The liquid polymer is charged typically to 5–30 kV versus a ground
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target that locates at 20-30 cm distance away. Stretched polymer solution first formed a Taylor

cone at the nozzle tip, once the electric filed strength exceed the surface tension of the polymer

solution or melt, then fibers jets are formed. The discharged polymer solution (or melt) jet

undergoes a whipping process and the solvent evaporates (or melted polymer solidifies),

subsequently, the highly stretched polymer nanofibers are deposited on a grounded target.

Fabrication of nanocomposite fibers mat by electrospinning from a mixture of nanocellulose

materials and polymers is also feasible.[34–36] Sutka et al reported nanocellulose reinforced

polymer (polyvinyl alcohol) composite fiber by electro spinning technique.[37] Presence of

cellulose nanocrystal in the polymer solution would decrease the composite nanofiber diameter

as well as improves the composite nanofiber diameter distribution. Nanocellulose concentration

increases the conductivity of polymer solution, therefore, reduces the distance of electrodes that

is required for establishing a jet.[37,38] Electro spinning process ensure, complete entrapment of

cellulose nanowhisker in the polymer nanocomposite fiber matrix.[39]

4. Properties of Polymer-Nanocellulose Nanocomposites

4.1. Mechanical properties

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 To improve the mechanical properties of nanocellulose polymer nanocomposites,

nanomaerials dispersion and distribution in the polymer matrix, and interfacial interaction

between the fillers and matrix are important, so that when the load is applied, the matrix could be

able to effectively transfer it to the strong nanoreinforcement phase (Figure 5). Mechanical

properties of the nanocellulose reinforced polymer nanocomposites (Table 1) improves due to

the stiffening effect of cellulosic nanomaterials at low concentration due their large specific

surface area, which possesses better interfacial interactions between the nanocellulose and
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polymer matrix when the dispersion and distribution of nanofillers in the matrices is uniform. In

case of good dispersion, distribution and interfacial interaction between the nanocellulose and

polymer matrix, the mechanical properties of nanocomposites lies between the properties of

nanocellulose and polymer matrix (Figure 6).

Optimum concentration of nanocellulose reinforcing phases are required to improve

mechanical properties, above the threshold limit, further increase of nanomaterials decreases

mechanical properties due to the agglomeration of nanomaterials in the polymer matrix. At

optimum concentration of nanocellulosic materials with good dispersion in the polymer matrix

can promotes interlocking between reinforcing materials and matrix, making the interfacial

adhesion stronger.[48,49] The formation of a rigid cellulosic nanoreinforcing network within the

nanocomposites matrix due to percolation of the nanocellulose whiskers, improves the

mechanical properties of nanocellulose composites.[54] Improvement of mechanical properties for

the reinforcement of nanocellulose in the polymer matrix is due to the strong intra- and

intermolecular hydrogen bonds with matrix polymers due to the high aspect ratio of the

nanocellulose. Further, such high aspect ratio of nanocellulose could create huge degree of

entanglements in nanocomposite domain structure in order to further improve the mechanical

12
 properties.[27] Tensile strength and Young’s modulus of nanocomposite would increase up to

certain loading of nanofiller in the polymer matrix. With further increase of filler content,

mechanical properties are declined due to agglomeration of nanocellulose in the polymer

matrices. The aggregation of nanofillers in the nanocomposite domain structure can promote

local concentrations of stress, as a result of mechanical failure of the polymer

nanocomposites.[42,43,55] With high concentration of nanocellulose in the polymer matrix may

reduce the interaction between the nanocellulose fillers and polymer matrix as a result of non-
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uniform stress distribution in the nanocomposite materials, hence, decrease the tensile strength of

the composite films.[44] Processing of nanocellulose reinforcement in the polymer matrix also

influences the elongation of nanocomposites (Figure 7). Chitosan and nanocellulose composites

fabricated by using lactic acid have nearly 50% higher elongation than nanocomposite processed

by using acetic acid.[46]

Nanocomposite obtained by casting of a mixture of latex and nanocellulose suspension

shows significant improvement of mechanical properties in the rubbery state of polymer matrix

by incorporating 6% of nanofillers due to the hydrogen bonding which formed a rigid network,

governed by a percolation mechanism.[56,57] Polyaniline (PANI) and nanocellulose composite

film shows excellent flexibility, rigidity together with conductivity property. Storage modulus

decreases with increasing PANI concentration in the composite film (Figure 8). Composite film

containing more than 30% PANI can makes the film brittle. Improvement of mechanical

property of the composite film is possibly due to the interconnected network of cellulose

nanofillers.[58]

4.2. Thermal properties

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 Thermal property of the nanocellulose polymer nanocomposite is very important from the

application point view. Thermal properties of the nanocellulose polymer nanocomposite could be

characterized by melting temperature (Tm), glass transition temperature (Tg), crystallization

temperature and the measurement of thermal degradation property. The glass transition

temperature of nanocellulose reinforced polyvinyl alcohol (PVA) nanocomposites is increases

due to the strong hydrogen bond formation between the PVA matrices and nanocellulose. Strong

hydrogen bonding restricts the segmental mobility of polymer chains, as a result of increases of
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the Tg.[59] While, thermal degradation properties of polymer nanocellulose composites do not

provides a trend with respect to the filler concentration in the polymeric nanocomposite matrix.

In general, nanocellulose has poor thermal stability as compared with the matrix polymer for an

examples natural rubber,[60] PLA.[61] etc. However, with the incorporation of nanocellulose into

the natural rubber polymer matrix, the thermal degradation temperature of nanocomposite

increases first, and then with further increase of nanocellulose, the thermal degradation

properties declined. With low nanocellulose reinforcement phase concentration, the complex

network structure formed in the nanocomposite matrix plays an important role for the

improvement of thermal stability though the pure nanocellulose material has lower thermal

degradation properties. Decrease of thermal properties with higher nanocellulosic material

concentration is due to the poor reinforcement as a result of agglomeration of material in the

polymer domain structure. Enormous oxygen content in the nanocellulose further decreases the

thermal stability of the nanocomposites.[60] Reddy and Rhim reported slight improvement of

thermal stability in the second stage of three stages thermal degradation property of agar film

reinforced with nanocellulose.[44] Lee et al reported the similar results for the improvement of

thermal degradation properties of nanocellulose reinforced polyvinyl alcohol (PVA) based

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 nanocomposite. The thermal degradation properties of the nanocomposite films increases as the

nanocellulose filler loading increased.[41] Li et al presented significant improvement of thermal

degradation properties in the second stage for the two stages degradation properties of PVA

nanocomposites.[42] Reinforcement of nanocellulose increases the thermal stability of PVA

nanocomposites possibly due to the formation of strong hydrogen bonding between the PVA

matrix and the nanocellulose reinforcing phase.[43]

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4.3. Barrier properties

Poor permeability of nanocellulose polymer nanocomposite can be achieved by

crystalline nature of nanocellulose and ability to form a percolating network with matrix by

hydrogen bonding, which all subsequently increases the tortuosity path for the diffusing

molecules (Figure 9). When, the nanocelluloses are well dispersed and distributed, and the

interfacial interaction between nanofiller/polymer matrix is strong, the cellulose nanofiller would

reduce chain segmental mobility, thus, further decreases the penetrant diffusivity.[4] Khan et al.

shows that methyl cellulose (MC) film with 1% of nanocellulose has a 26% reduction of water

vapor permeability due to the presence of less permeable nanofillers which increase the

tortuosity in the MC-based films, leading to slower diffusion of penetrating molecules.[62]

The nanocellulose polymer nanocomposites film can be used as a barrier membrane for

the organic solvent (the property required for many industrial applications).[60] Diffusion of

solvent molecules in the nanocomposite depends on size of penetrant molecules, free volume,

polarity of the matrix and dispersed phases, segmental motion of the domain structure, tortuosity

of the moving path of penetrant molecules etc..[63] Rubber nanocellulose composites shows

decreased solvent adsorption due to the network structure formed between rubber and

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 nanocellulose. Interaction between the nanofillers and matrix increases the tortuosity of penetrant

molecules path and reduced the transport rate. Further, abundance of hydroxyl groups on the

surface of cellulosic nanofiller due to its nano dimension contributed to the tortuousity of

hydrophobic solvent which will be restricted by the hydrophilic hydroxyl groups.[60]

In a nonporous polymer film, mass transfer property would occur at the molecular

mechanism such as sorption-diffusion-desorption, therefore, the sorption is very important for

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the barrier property of the nanocomposite films. Lani et al. studied the water absorption capacity

of nanocellulose fiber reinforced PVA/starch nanocomposites. Water absorption capacity of

nanocomposite decreases due to the formation of the network structure between the

nanocellulose particles and the polymer matrix, which prevents the water molecules diffusion in

nanocomposite matrix.[40] Moisture absorption of linear PVA film decreases up to certain limit of

filler concentration in the nanocomposites due to the intermolecular hydrogen bonding which

blocks hydroxyl groups of PVA, hence, makes the film tighter and resistant for the diffusion of

water molecules. Beyond the threshold limit of filler concentration, the free hydroxyl groups of

nanocellulose starts to absorb the water molecules by hydrogen bonding, therefore, beyond the

threshold limit water absorption increases with increasing nanocellulose filler in the PVA matrix.

Nanocellulose material is hygroscopic in nature because of its abundance of hydroxyl groups in

its structure, therefore, non-hydrogen bonded hydroxyl groups in the filler surface would

absorbed significant amount of water.[43]

4.4. Biodegradability

With respect to the rapid global population growth, the solid waste disposal is becoming

an ever-increasing concern in our planet. Regarding the plastic solid waste, the research on

16
 recycling has stimulated interest in industry and academia due to their high cost and non-

degradability. One of the major problems for most of the synthetic polymers derived from the

petroleum based products is non-degradable, and hence, accumulated over the time once we

discarded after use. Biodegradable plastic could be a good alternative for the industrial and

commodity applications in a less environmentally harmful way, hence, not contributing to the

accumulation of solid plastic waste upon disposal.[64] Biodegradable plastics once discarded in

the environments, would be degradable by the enzymatic action of microorganisms and their
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long polymer chains may also be broken down by non enzymatic processes for an example

hydrolysis. The biodegradability of plastics depends on the starting raw materials and the

chemical composition, backbone structure of the polymeric materials, as well as on the

environment where they are expected to disposed.[65] Nondegradable polymer could be to some

extent degradable by the reinforcement of degradable fillers for example cellulose nanofillers.

Biodegradable epoxy nanocomposite can be fabricated by reinforcing nanocellulose in the epoxy

matrix. Nanocellulose reinforced epoxy composite with high loading of nanocellulose can be

greener as compared with commercially available biopolymer such as pure polylactide (PLA).[66]

Abraham et al. studied the biodegradation of nanocellulose reinforced natural rubber

nanocomposites.[47] Biodegradation of the nanocomposites accelerated with the increase of

nanocellulose in the rubber matrix (Figure 10), possibly due to the attraction of more microbes

in the peripheral nanocellulose fillers. The biodegradation starts with nanocellulose due to the

accumulation of microbes, and could leave holes which subsequently increase the surface area

for the biodegradation of the remaining matrix nanocomposites. Each cellulose unit has three

hydroxyl groups (unless occupied by hydrogen bonding) which are the active sites for the attack

of microbes. As expected, non-cross linked composites show a faster biodegradation than their

17
 cross linked counter part. Strong interconnected network in the crosslinked nanocellulose based

nanocomposite hinder the accessibility and activity of microorganisms as compared with the

noncrosslinked nanocomposites.[47]

4.5. Other properties

The response property of hydrogel is important for its applications in diverse fields. Nano

crystalline cellulose containing hydrogel exhibits a rapid deswelling rate due to the
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interconnected micropores formed by nanocrystal with pristine hydrogel by extensive hydrogen

bonding. Swelling ratio of nanocomposite hydrogel decreases with increasing nanocrystal due to

the stronger interaction of nanocrystal through hydrogen bond in the gels.[67] Advantage of using

nanofiller in contrast to the microfiller in the polymer matrix is the preservation of transparency

for the matrix polymers, whereas, achieving the other functional properties of the nanocomposite

materials. Transparency of the nanocellulose polymer composite would preserve when

nanofillers have homogeneous dispersion and distribution in the polymer matrix.[42]

Transparency of the nanocomposite films could be decreases with increasing nanomaterial

concentration in the polymer matrix due the possible agglomeration.[42,55] Acrylic nanocellulose

nanocomposite films preserved good transparency when prepared by in situ mini-emulsion

polymerization technique using a coupling agent, and this ensures improved dispersion and

prevent the aggregation during polymerization and film formation process.[26]

5. Applications of Polymer-Nanocellulose Composites

Synthetic polymers derived from petrochemical resources are widely used for packaging

applications because of their exceptional gas and water barrier properties, and cost effectiveness.

There has been a tremendous interest to use renewable resource based materials for the

18
 packaging applications.[68] The objective of proper food packaging is to preserve the quality,

taste and safety of the food ingredients, from the time of manufacture to the consumption from

physical, chemical, or biological abuses.[22] Packaging of foods and drinks, cosmetics and other

consumer goods are required to prevent them against physical and environmental deterioration.

Therefore, packaging material should provide appropriate barrier against oxygen, water vapor,

grease, and microorganisms. Nanocellulose has few excellent features as filler viz. nanoscale

dimensions, high crystalline nature, nontoxic and the ability to form hydrogen bonding with
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matrix of polar polymer, and all these interesting properties of cellulose nanocrystal contributed

to the excellent barrier properties of cellulose nanocrystal nanocomposite film network which is

strong for the penetrant molecules to pass through.[69] Nanocellulose reinforced carboxymethyl

guar (CMG), agar or semi-interpenetrating polymer network of poly(vinyl

alcohol)/polyacrylamide with improved gas barrier and mechanical properties can be used for the

packaging purposes. Improved properties of the composite films are possibly due to the

increased hydrogen bonding.[25,70] Reinforcement of nanocellulose together with nanoclay in the

poly(lactic acid) matrix significantly improve the water and oxygen barrier properties of the PLA

films which make nanocomposite film a promising materials for the food packageing.[71]

Nanocellulose as cellulose nanocrystal and cellulose nanofibrils can be used as

reinforcement phase in the polymer matrix for biobased films, coatings, foam etc. which offers

novel and promising properties. Cellulosic nanofibers are interesting candidate in the

development of polymeric foam, as they act as heterogeneous nucleation sites for the growth of

cells during foaming.[72–74] Vilela et al. reported nanostructured composite materials based on

poly(ionic liquid) and nanocellulose for ion exchange membrane for potential applications in fuel

cell and related applications.[75] Nanocellulose reinforced conductive polymer nanorod film

19
 facilitated the diffusion of electrolyte ions. The composite film exhibits excellent electrochemical

and electrochromic properties in electrolyte solution. Superior electrochromic performances of

nanocomposite films make them ideal in electrochromic materials.[76,77] Jiang et al. proposed

bacterial nanocellulose and Nafion composite films for proton-exchange membrane for fuel cell

(PEMFC) and direct methanol fuel cell (DMFC). Bacterial nanocellulose reinforcement

decreases water uptake, volume swelling ratio and methanol permeability, whereas, dense

structure, Young's modulus and selectivity have been improved, which makes composite
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membranes ideal for the fuel cell applications.[78] Due its large effective surface area algae

nanocellulose/polypyrrole composite provides large catalytic oxidation currents, and enables

storing of the charge.[79] Polypyrrole (PPy)-nanocellulose membranes with excellent porosity can

be prepared by oxidative chemical polymerization of pyrrole monomers on cellulose nanofibers

to design efficient and reversible electrochemically controlled ion exchange membrane for cheap

batch-wise solid phase extractions of biomolecules.[80]

Polyaniline nanocellulose composite films are excellent candidate for various electronic

fileds. The nanocomposite films with enhanced conductivity and flexibility could find promising

applications in paper based sensors, flexible electrode, electronic device and conducting

adhesives.[58,81–83] Razaq et al. proposed electrodes which was prepared from the composite of

polypyrol, nanocellulose and carbon filaments at high charge and discharge rate for the

inexpensive and environmental friendly paper based energy storage devices.[84] The free standing

paper like nanocomposite made with polypyrol nanofibers and polypyrol coated nanocellulose

with high active mass ratio and mass loading provides efficient use of pollypyrol nanomaterial

for charge storage devices with high cell capacitances, excellent rate capabilities and cycling

performance.[85] Conducting undoped poly(3,4- ethylenedioxythiophene) and bacterial

20
 nanocellulose composite membranes with an electrical conductivity and flexible membrane can

be a potential candidate for the flexible organic electronics.[29]

Cellulose nanocrystal with high specific surface area, high strength, tailorable surface

chemistry possesses significant benefit for creating reinforced hydrogel composite which

exhibits both reinforcement phase and host matrix phase desirable properties, and nanocellulose

hydrogel could find wide applications in biomedical fields.[86] Nanocellulose reinforcement in

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polymer and interpenetrating polymer network can enhance the mechanical properties.[87]

Sampath et al. presents seminterpenetrating polymer network hydrogel with improved pH

sensitivity and mechanical property, and novel hydrogel could find applications in tissue

engineering, pharmaceuticals and drug delivery.[88] Electrospun poly(ε-

caprolactone)/nanocellulose composite fiber mat can be used as scaffold for the biomedical

applications. Introduction of nanocellulose could effectively biomineralized with hydroxyapatite

for the surface modification of scaffold materials.[89]

Some of the other promising applications of nanocellulose reinforced polymer

nanocomposites could be self-healing material, anticorrosion coating etc. Surface modified

cellulose nanocrystals with scissile however reversible re-combinable dynamic covalent

mechanophore could be used as reinforcement to prepare self-healable polymer. The activation

of mechanophore on CNC surface exhibits high sensitivity to mechanical stress due to the

formation of reversible covalent bonds between the CNC surface and polymer matrix, and the

nanocomposite will have the ability to heal. These functional polymer could be applicable in the

areas where we required damaged self-reporting and self-healing properties.[90] Nanocellulose

reinforced polymer composite shows high optical transparency.[91,92] Therefore, nanocellulose

incorporated polymer composite can be used for coating applications. Ma et al. reported

21
 nanocellulose incorporated epoxy resin composite for the protective coating of mild steel. Coated

mild steel shows excellent anti-corrosion properties tested by using 3.5% NaCl solution and

studied comparatively by 30-day electrochemical impedance spectroscopy (EIS).[93]

6. Conclusions

Advances in nanotechnology have opened up new opportunities for the fabrication of

novel nanocomposites with improved properties. Nanocellulose as novel nanofiller has potential
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for tailoring the structure and properties of matrix polymers. Current development of polymer

nanocomposites based on cellulose nanocrystal as potential nanofillers in polymer matrix have

been reviewed in this paper. Research and development in polymer nanocellulose nanocomposite

is promising. However, further progress is required as there are many challenges needed to

overcome before polymeric nanocellulose nanocomposites materials can be considered for the

bulk production and applications:

a) Influence of the size, shape and surface chemistry of cellulose nanofillers on

domain structure of matrix polymer and properties of resultant polymer

nanocomposites will be interesting to explore.

b) The compatibility of nanocellulose in various polymer matrices viz.

polar/nonpolar polymers is an important aspect to consider, because the ultimate

property of resultant nanocomposite and stability of nanocellulose in polymer

domain will depends on the compatibility of nanofillers and matrix polymer.[94]

c) One of the major problems for nanocellulose and polymer nanocomposite is the

poor dispersion and distribution of nanofillers in the polymeric domain structure.

22
 d) Surface modification of nanocellulose by using appropriate molecules, hence, to

improve the interfacial interaction between the dissimilar surface of nanofiller

and polymer matrix.

Much researches and developments are still needed to consider polymer-nanocellulose

nanocomposite for bulk production and applications. This author does sincerely hope that

challenges proposed in this review paper will stimulate further researches in the field of polymer

nanocellulose nanocomposite materials for the diverse novel promising applications.

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 Table 1. Mechanical properties of nanocellulose polymer nanocomposite

Matrix polymer Concentration % Reference

of nanocellulose improvement

as compared of tensile

with matrix strength

Modulus (%

improved)
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Starch-PVC 10% 85% – [40]

(30:70 wt%)

[41]
PVA 1% ~50% 44%

[42]
PVA 6% 180% 140%

Linear PVA 7.5% 48% – [43]

Crosslinked 5% ~44% – [43]

PVA

[44]
Agar 5% ~18% ~29%

[45]
PVA 5% ~44% 450%

[46]
Chitosan in 5% ~600% ~1400%

acetic acid

[47]
Natural rubber 5% 500% ~350%

(Non-

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 crosslinked)

[47]
Natural rubber 5% 325%% ~380%

(Crosslinked)

Unsaturated 0.5% 57% – [48]

polyester

[49]
PVA 5% 28% 60%
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[50]
Cassava starch 0.5% ~110% ~180

[51]
PVA 3% ~28% ~28%

Sodium 3% ~70% – [52]

caseinate

[53]
PVA 6% 10.2 21.5%

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Figure 1. Examples of natural composites (A) Wood and (B) Bone
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Figure 2. Schematic of polymer nanocomposite and various phases
 Figure 3. Schematic showing examples of: (A) good dispersion and distribution of nanofiller and
(B) poor dispersion and distribution of nanofiller in the polymer matrix, and the interface
between nanofiller-polymer matrixes.
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 Figure 4. Nanocellulose reinforced polymer nano-composite by in situ polymerization
(Reproduced from,[26] Copyright © 2014 Elsevier B.V. All rights reserved).
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 Figure 5. Schematic representation of load transfer between nanoreinforcement phase and
polymer matrix: (A) good bonding and excellent load transfer; (B) poor bonding and void
formations
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 Figure 6. Schematic of stress-strain curves of nanocellulose, polymer matrix and polymer
nanocomposite
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 Figure 7. Stress-strain graph of chitosan nanocomposite with various nanocellulose
reinforcement processed by using (a) acetic acid and (b) lactic acid (Reproduced from[46]
Copyright © 2014 Elsevier B.V. All rights reserved).
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 Figure 8. Dynamic mechanical analysis of pure nanocellulose film, nanocellulose PANI
composite films (Reproduced from[58] Copyright © 2014 Elsevier Ltd. All rights reserved).
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 Figure 9. Schematic representation of barrier property of cellulose nanofiller polymer
nanocomposite
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 Figure 10. Scanning electron microscopy (SEM) images of natural rubber (NR)/nanocellulose
composite during the final stages of biodegradation. (A) 7.5% non-cross linked composite (B):
10% cross linked composite (C): standard cross linked matrix (without filler). (D): 10% non-
cross linked composite (Reproduced from,[47] Copyright © 2012 Elsevier Ltd. Published by
Elsevier Ltd. All rights reserved).
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