A Review of Nanocellulose Polymer Composites Characteristics and Challenges

Hon-Meng Ng1, Lee Tin Sin1, Soo-Tueen Bee1, Tiam-Ting Tee1, A. R. Rahmat2
1
Department of Chemical Engineering, Lee Kong Faculty of Engineering and Science,
Universiti Tunku Abdul Rahman, Jalan Sungai Long, Bandar Sungai Long, Cheras,
Kajang, Selangor, Malaysia, 2Department of Polymer Engineering, Faculty of Chemical
Engineering, Universiti Teknologi Malaysia, UTM Skudai, Johor

Corresponding author: Lee Tin Sin, E-mail: direct.tinsin@gmail.com

Abstract

The nano-size cellulose has emerged in the last two decades as an efficient strategy to

improve the structural and functional properties of polymer composite. This review

focuses to explore the unique mechanical-thermal properties of cellulose-based

nanocomposites particularly on the various reinforcing mechanisms of nanocellulose. The

promising reinforcing capabilities of nano-cellulose (NC) mainly lie in their intrinsic

chemical natures, aspect ratio and degree of crystallinity. In this paper, the potential

factors of deteriorating the aspect ratio and crystallinity have been systematically

reviewed. Some relevent suggestions/solutions were also widely exploited towards

tailoring the generating problems.

GRAPHICAL ABSTRACT:

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KEYWORDS: Nanocellulose; Polymer composites: Mechanical properties

Abbreviations:

Reinforcements

NC nanocellulose

NFC nanofibrillated cellulose

NCF nanocellulose fiber

CNC cellulose nanocrystal

CNW cellulose nanowhisker

Polymers

PCL polycaprolactone

PLA poly(lactic acid)

2
PE polyethylene

PP polypropylene

PVA poly(vinyl acetate)

PVOH polyvinyl alcohol

TPS thermoplastic starch

CAB cellulose acetate butyrate

Techniques

DMA dynamic mechanical analysis

DSC differential scanning calorimetry

TGA thermogravimetric analysis

1. INTRODUCTION

Plastic composites have been applied for variety applications in industry and commercial

which require extraordinary performance. Most of the polymer composites products

normally found in the market have outstanding mechanical and thermal properties,

considering mechanical deformative/creep resistance and thermal stability/heat resistance

have been related as important criterions for the implementation of structural products [1].

Although the traditional recalcitrant polyolefins (e.g. PE, PP) have been widely used, it is

unable to meet the sustainable demands due to limited non-renewable petroleum supplies,

hence driving more researches search for alternatives when impending depletion of

crude-oil [2,3]. The unconventional polymers such as thermoplastic with biodegradable

backbone, polymers derived from non-renewable petroleum or renewable natural

resources have gained more acceptances in structural applications. However, majority of

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these polymers are imperfect in either mechanical or thermal properties [4]. For instance,

the biopolymer PLA has outstanding mechanical properties but accompanied by

disadvantages of brittleness and poor thermal stability, whereas starch-based products

mainly suffer from weak mechanical properties [5,6]. For the polymers which is desirably

utilized for specific application (i.e. biodegradable purpose), the inherently uncompetitive

mechanical and/or thermal performances often limiting their applications [4,7]. Among

numerous attempts have been made to enhance mechanical-thermal performance, the

blending of polymers with reinforcing fillers has been recognized as one of the most

efficient techniques to offer unique opportunities for property modifications by varying

amounts of fillers [8,9]. More importantly, the blending process is lower cost as compared

to the cost of development of new synthetic polymeric materials [5].

Many types of reinforcing fillers with various sizes and forms have been studied to

produce new desirable hybrid materials for a variety of applications, especially nanosize-

fillers have been shown to be effective reinforcing agents [10]. Apart from the

reinforcement capabilities, many fundamental criterions still have been existed to affect

the selection of sources as reinforcing material when considering the long-term

application or sustainable usage of fillers. One of the most important factors is regarded

as biocompatibility, but manyresources used to prepare reinforcing filler are inorganic.

These substances include mineral, metal-oxide, clay and graphene resources. The

continuous long-term usage of these non-renewable resources to derive fillers also has

been always questioned as they would be exhaustable in one day future, while the rising

cost of such limited raw feedstock definitely increasing production cost. From the view

4
point of sustainable production, the renewable natural plants undoubtedly serve as

promising feedstock based on their nearly inexhaustible supplies from abundant forest

resources, crops processing by-products and etc [11-13]. In a dissimilar manner, the

reinforcing agents derived from natural plant with those of organic nature are more

environmental benign. Additionally, the good environmental protection also can be

offered since plant sequesters carbon by absorbing carbon dioxide during plant growth,

reducing the greenhouse gas concentration [14]. Thus, it is safe to term the plant-based

filler as green reinforcing agent. Without relating to greenhouse gas, the term of “green”

also generally refers to products that are less detrimental to human health than traditional

equivalents. Unlike harmless plant-reinforcement, there is always concern on the health

risks and safety problems caused by traditional reinforcing particles such as nano-clay,

nano-aluminum oxide particles, silica, mica and carbon blacks [15–18].

The above acute conditions inevitably create an opportunity for plant’s cellulose fiber to

become sustainable materials of choice for 21st Century [19–21]. In this cellulosic century,

it is non-surprising that more and more types of plant resources have been exploited to be

processed into cellulosic filler, while the hierarchical and multi-level organization of

plant-fiber structure making the different types of cellulosic fillers are possible depending

on processing techniques [14,22]. Moreover, these cellulosic fillers could be either derived

in macro, micro or nano scale, involving pulp fiber, cellulose fiber, microfiber, nanofiber

and nanocellulose (NC). Nano-size fillers prepared from nanotechnology, however, are

found to be more preferable in many applications, mainly due to aspect ratio and degree

of crystallinity is far superior to a macro/microsized pulp fiber [23,24]. Owing to their high

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surface area-to-volume ratios by high aspect ratio, the lower concentrations of nanofillers

are needed to achieve reinforcing effects [23]. Due to higher degree of crystallinity by

lower amount structural defects, the rigid individual nanocellulose is more thermally

stable and higher mechanical strength than macro/micro fibers, approaching the

properties of a perfect cellulose crystal [7,25,26]. The large difference in cellulose fibers

between micro- and nano-size can be purely ascribed to NC has been purified from non-

cellulosic materials like lignin, hemicellulose and other thermally labile constituents [25].

This highly purified NC also has higher capacity to serve as nucleating agents than

cellulose fibers due to the improved surface topography [20].

The emerging of organic cellulose filler derived from biological origins opening more

opportunities for creating a biocomposites pioneer with expectation to substitute the

conventional non-organic/eco-friendly composites towards overcoming globally alarming

plastic wastes [12,13]. By expanding the concept of biocomposites to the nanostructured

hybrid materials, the term of ‘bionanocomposites’ can be used for designating composites

materials made from bio-based nanofillers (i.e. NCs) and biodegradable polymers (e.g.

PVOH, PVA) or biopolymers (e.g., PLA, PHA) which derived from renewable natural

resources [27,28]. Even for non-biobased resins reinforced by NCs, the

‘bionanocomposites’ is also suitable considering plant-based filler can compensate for

such non-biodegradable drawbacks as well as add advantages (like biodegradable

behavior) to matrix with desired to trigger biodegradability [22,29]. However, the

production of 100% bio-based composites as a complete substitute for petroleum-based

products is still a challenge unless the utilization of biodegradable plastic or bio-resins as

6
based matrix [12]. In this concern, the nanocellulose has inspired the exploration of more

biodegradable plastics to develop fully bio-based nanocomposites without counteracting

their superiority of biodegradability instead of their weak properties could be solved. In

particular, since most of the biodegradable-polymers are hydrophilic polymer (e.g. PCL,

TPS), the beneficial interaction between matrix-NCs is easily achieved in polymer of

having chemical similarity to hydrophilic NCs, contributing to improved properties [30,31].

Similarly, the effective utilization of renewable-resource-based polymers also have been

encouraged, involving natural polymer derived from plant-oil, protein, starches and

microbes [12]. Since these bio-based polymers reinforced by NC desired to reach the

properties of fossil-derived polymers, the cost of the expensive petroleum-resources and

energy consumed to derive petro-based plastic could be saved, making the cellulose-

composite is relatively cheaper price [11,17].

This paper focuses on the unexplored review on mechanical-thermal properties of

cellulose-based nanocomposites by setting out in-depth inspection on the possible

reinforcing potentials of cellulosic nanosize-fillers based on to recent literatures.

Although the use of natural NCs to reinforce plastics has offered many advantages, one

should be alert that the composite properties do not always meet the material

requirements of various applications involved in mechanical-thermal properties. Thus,

before these cellulosic nanofillers could reach their best application potential, several

issues of inhibiting the reinforcing potentials of NCs and even mechanical-thermal

properties’ improvement are presently exploited while these problems are discussed in a

greater detail associated with some possible suggestions/solutions. Such additional

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information is meaningful for the future research in related area with desired to avoid the

repeating problems of researches in the past by possible advancement of several

prosessing or techniques raised in the future. As realized by very high potentials of

cellulosic nanomaterials to reinforce wide range of polymer matrices (thermoplastic and

thermoset) and to meet almost all the requirements for being “green”, the main goal of

this review is devoted to facilitate the more commercial development of green cellulosic-

nanocomposite materials. More importantly, the behind motivation is heavily promoting

the more extensive development of industrial crop or plant industry with its purpose in

reducing the greenhouse gas CO2 and increasing new sources of economic growth.

2. PLANT-DERIVED NANOCELLULOSE

The nanosize cellulose is available to be extracted from various plant sourceswhich

covering the wood of forest resources (soft wood, hard wood, recycled newspaper and

magazine fiber), non-wood lignocellulose (e.g. sisal, coir, hemp, flax, jute, ramie, kenaf,

cotton and algae) and agricultural residues/by-products (e.g. corncob, risk husk,

sugarcane bagasse, banana, crop straw and etc.) [1,32-36]. By comparing to the

nanocellulose extraction process such as bacterial/microbial (e.g. Gluconaceto-bacter

xylinus) and animal sources (e.g. mantles of tunicate, silk, wool), it is not difficult to

realize that the derivation procedure of nanocellulose from plant is more complex [22,34,37].

It is preferable to extract the nanocellulose from pure cellulose source itself as compare to

plant cell wall due to plant cell wall is very heterogeneous in structure while very likely

to be interrupted by many other kinds of non-cellulosic components [32,38,39]. Hence, it is

8
important to understand the physical and morphological structure of plant cell walls

primarily prior to further extract the nanocellulose from plant in order to produce highly

efficient at low cost output.

As shown by enlarging views of Figure 1, the native cellulose is the main building

molecules for nanocellulose. This means that this semicrystalline fibrillar structure is

indeed the main source of constituting the plant cell wall [22,36]. Generally, the cellulose

molecule is a linear syndiotactic polysaccharide, which consisting of both D-glucose

units (a simple sugar) and -d-anhydroglucopyranose units (AGU) [40–42]. Two AGU

linked by unbranched -(1→4)-glycosidic bonds are then available to form a repeat unit

in long-chain cellulose, such dimer of glucose is known as cellobiose as specified in

Figure 1 [40-42]. Depending on numbers of cellobiose, cellulose molecule with a

nonbranched chain could be formed in variable length, and even different molecular

weight and chemical formula (C6nH10n+2O5n+1, n=degree of polymerization of glucose)

[22,39]
. Importantly, each glucopyranose unit of cellulose chains bears three hydroxyl (-OH)

groups which protrude laterally along the cellulose chain. The resulting equatorial

positions of hydroxyl moieties enables the cellulose chain to readily form intramolecular

hydrogen bonding with each other [41,43]. Driven by hydrogen bonding force, there are

about 30-100 individual cellulose molecules could be merged into elementary fibrils or

protofibrils depending on the plant species. It is worth-to mention that the common

average size of elementary fibril is 5 nm [36,44]. Moreover, the elementary fibril also can

be named as microfibrils by its length of several tens of microns. A numbers of

microfibrils could be packed into larger units called microfibrillated cellulose (MFC) or

9
microfibrils aggregate for lengths that can reach several micrometers [36]. Since each of

the MFC has diameters ranging from 20-60 nm, MFC is expectedly composing of 10-50

microfibrils if considering that the microfibrils have a 2-10-nm-thick fibrous cellulose

structure [36,45]. When the adjacent glucan chains form microfibrils and even MFC, the

cellulose portions with –OH groups tend to be crystalline packing into highly ordered

whisker stabilized by strong hydrogen bonding. Whereas the remaining chains’ portions

lack of -OH groups would be associated into disordered domains [22]. Thus, the

microfibrils are not perfectly crystalline as the amorphous (or para-crystalline) phases

existed together alternatively with crystalline domains (or whisker) along the microfibril

axis, while such crystalline structure is one of the nanocellulose, cellulose nanocrystal

(CNC) [22,46]. Another type of nanocellulose is belonged to nanofibrillated cellulose (NFC)

which is actually a web-like/network structure of isolated microfibrils as frequently

displayed by SEM images [22,45]. However, the unique fibrillar nanostructure endows

single microfibrils with more excellent reinforcing capabilities as compared to NFC with

cellulose fibril aggregates, but it is impossible to completely disintegrate MFC into single

microfibrils in reality [22].

It has been known that the cellulosic materials (CNC or NFC) are not alone existed in

plant cell wall instead of the bundles of microfibrillated cellulose further combined with

non-cellulosic matrix (like hemicellulose and lignin), assembling into individual cellulose

fiber as presented schematically in Figure 1 [39,43]. Implicitly, the removal of cementing

materials surrounding the microfibrillated cellulose is a critical step prior to further

processing of cellulose fibers into CNC and NFC as specified in Figure 2 (which has

10
outlined the main preparation steps of NCs). As listed in Table 1, many attempts of

purification have been applied on cellulose fibers to remove the non-cellulosic materials

which are non-contributable to reinforcing effects of NCs. In worse, they might act as

defects in polymer matrix. Among the purification techniques, the alkali-bleaching

treatment is the most popular method to be utilized. There are some researchers modify

the sequence of alkali-bleaching treatment into bleaching-alkali treatment [47]. Since the

acids also can dissolve and hydrolyze cementing materials, some of the researchers used

alkaline-acid treatment for solubilization of lignin, hemicelluloses and pectins [42,48].

Following after purification step, the obtained highly purified cellulosic fibers are

available to be processed into nanometer-sized cellulose by various biotechnology and

nanotechnology methods as summarized in Table 2. Generally, CNC and NFC can be

manufactured by acid hydrolysis and mechanical defibrillation, respectively [26]. When

undergoing the synthesis in acidic environment, the amorphous regions of native

cellulose are responsible for the transverse cleavage of the microfibrils into short

nanocrystals [49]. Under mechanical treatments, the nanofibrillation of cellulose fiber

suspensions could liberare NFC after several passes of highly energy intensive process
[36,50–52]
. The application of higher degree of fibrillation to produce better quality of well-

defibrillated NFC would lead to higher energy consumption, especially when involving

several mechanical passes of homogenizer/grinder/fluidizer (Figure 2) [52,53]. In order to

avoid the high expenses for energy, the reduced energy consumption lies in the lesser

mechanical passes through machine by applying the pre-treatment prior to mechanical

treatment as introduced in Table 2, mainly chemical or enzymatic pretreatments [36].

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Alternatively, NFC production could also be finished at the identical step without

repeated passes, such as compounding of the composites using kneading process of twin-

screw extruder [50,51]. Upon extraction of NCs, a number of post-treatments (Tables 2)

have to be done to produce NCs with more purified form and finer size, towards ensuring

the fundamental reinforcement can be fully exploited [36]. In most cases, the extracted

NCs are evenly dispersed throughtout the water in form of an aqueous suspension as

shown in Figure 2. The aqueous suspension normally presented as a stable colloidal

system based on the strong hydrophilic tendency of NCs containing –OH groups to react

with water molecules, the resulting cellulose-water interfaces thereby enabling the system

to remain thermally or kinetically stable throughout a range of water contents [54]. The

final step of drying aqueous NCs suspensions is selectively conducted and the dried-

form-NCs has been usually emphasized by melt-processing of composites. Interestingly,

there are many drying approaches generated nowadays which will be introduced and

further discussed in section 4.1 [25].

Eventhough there are four particle types of cellulose fibers on nano-scale have been

discovered, this review mainly concentrates on nanofibrillated cellulose (NFC) and

cellulose nanocrystal (CNC). They are collectively designated as nanocellulose (NC) in

current review based on their common cellulose constituent [32]. However, their structure

and reinforcing potentials are mostly different but the celluloses with different

functionalities clearly open novel fields of application. Thus, it is of great interest to

examine the difference of both nanosized-cellulose in several aspects as tabulated in

Table 3. One can notice that the intrinsic difference in aspect ratio and crystallinity of

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CNC and NFC mainly drives the difference in reinforcing ability of them. Several

fundamental characteristics of NCs also have been included in Table 3.

3. CHARACTERISTICS OF NANOCELLULOSES COMPOSITES

Generally, the NCs have attracted the great interest of the polymer composite community

due its extraordinary tensile strength, high axial stiffness, high thermal stability, low

defects, low coefficient of thermal expansion, low density, high surface area to volume

ratio, and engineered surface chemistry [27,46]. Based on this unique set of characteristics,

the incorporation of nanocelluloses can impose significant influence on the mechanical-

thermal properties of relative composites [55,56]. However, in the nanocomposite system,

properties also strongly dependent on “molecular” characteristic, which principally

denoting on the nature and dimensions of the polymer-filler interfaces, the mechanisms

of interaction between the polymer and filler components, the structural and dynamic

properties of either the polymer or filler phases [2,57]. By referring to numerous studies,

the intensive discussion will be developed on various mechanical and thermal properties

of NC-reinforced composites, involving the tensile properties, flexural-impact properties,

thermo-mechanical properties, thermal stability and thermal insulation.

3.1 Tensile Strength

The tensile properties are among the most widely tested properties of polymeric

composites. The tensile strength of nanocomposites is investigated by static mechanical

tests which reflects the average stresses distributed throughout the specimen cross-section

or thickness [6,58]. Tensile strength also represents the maximum applied straining stress

13
which can be sustained by the sample during the axial tension test. If maximum tensile

stress occurs at either the yield point or the breaking point, it is designated as tensile at

yield or at break, respectively [59].

It has been recognized that the nanocellulose has remarkable potential as a highly

strengthening constituent in composites by introducing the new stress transfer

mechanisms into the nanocomposite system [60]. This can be contributed by the high

density of hydroxyl groups exposed on nanocellulose (cellulose nanofibrils or

nanocrystals) as demonstrated in Figure 3a-b. Accordingly, the strong bonding ability

between NCs and matrix could establish interfacial hydrogen bonding bridges which

allowing the effective transfer of applied straining stress from matrix to filler [40,60]. In

other words, the incorporated NCs play as load bearing entities for relieving the loads

applied on the polymer matrix during tensile straining [60]. It is believed that the elevation

in tensile strength strongly depends on the efficiency of stress transfer which could

induce more axial stress applied on deformed matrix, contributing to the delay of the

stretching damage to higher stress [58,60]. The strong polar interaction developed at the

interface between NC-matrix in form of hydrogen bonding can be identified via infrared

spectroscopy analysis [61]. The intensity of the peak around 3000-3700 cm-1

corresponding to OH group of cellulose would be decreased in the spectrum of

nanocomposites, implying the hydroxyl group on the NCs has been interacted with OH

groups of hydrophilic polymer.

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It is reasonable to state that efficiency of stress transfer strongly depends on the intensity

of intermolecular hydrogen bonding which could be mainly determined by numbers of

contact sites at the filler-matrix interface. Hence, the NCs with higher aspect ratio as

shown in Figure 3a is the desirable factor that enabling a critical length for stress transfer

from the matrix to the reinforcing phase [22]. This is mainly because of the larger specific

area of higher aspect ratio of NC could be more extensively interact with matrix by

increasing contact surface area, whereby promoting higher degree of interfacial

interaction between NCs-polymer [62,63]. However, the higher crystallinity of NCs have

been reported as greater effectiveness of nano-size reinforcement on the tensile strength

rather than characteristics of higher aspect ratio as according to study of Silverio et al.

(2013) [64]. The is due to the higher number of contact sites can be provided by CNCs

with higher crystalline ratio (Figure 3a) than NCs with lower crystalline ratio (Figure 3b)

which reduced by presence of amorphous portions [43,65]. The hydrophilic surface of

crystal/whisker strings surrounded by plentiful –OH groups is only qualified to create

contact sites for hydrophilic matrix to interact with each others. This is unlike the

amorphous segments which lacked of –OH groups are unavailable to develop hydrogen

bonding between fillers-matrix [46,64]. The worse is such non-crystalline domains might

act as structural defects to deterioate the stress transfer efficiency [43,46,65]. Thus, it can be

concluded that the intensity of intermolecular bonding at the NC-matrix interphase is

significantly influenced by degree of crystallinity than aspects ratio of NCs considering

there are higher crystalline portions of bearing hydroxyl groups to interact with functional

groups of polymer. However, the higher aspect ratio of NCs could provide better

flexibility which is expected to enable mutual entanglement between long cellulose fibrils

15
and polymer chains. Nevertheless, this is considerably less participated in the improved

strength properties but contributing to better reinforcement performance [7].

Even without the mutual entanglement between short NCs and matrix chains, the better

reinforcement also can be offered by stiff cellulose network formed through the hydrogen

bonding of adjacent NCs among each others [1,25,66]. The interconnected stress bearing

network as formed by the nanofillers is another mechanical reinforcement of NCs to

enhance the interfacial energy transfer between matrix-filler to higher extent [9,58,60,67].

The establishment of nanocellulose network stabilized by hydrogen bonding has also

been governed by a percolation mechanism under good nanofiller dispersion as shown in

Figure 4a [68,69]. Notably, the cellulose linkages are certainly initiated at the limit of the

percolation threshold, i.e. the concentration point at which mere sufficient amount of NC

is added to induce connectivity [70]. For cylindrically shaped cellulose nanoparticles, the

percolation threshold (Φc) can be related to the aspect ratio (L/d) of the nanoparticles by

the general equation of Φc = 0.7/(L/d), indicating the percolation threshold is inversely

proportional to the aspect ratio [27]. Implicitly, the NCs with higher aspect ratio leading to

the formation of percolating cellulosic network is earlier achieved by lower Φc is

required [27]. In comparison, the CNCs which exhibit lower aspect ratio than NFC

requires larger Φc as well as percolating network which is only available formed by

higher quantities of filler. As the filler concentrations increased above Φc, the higher NCs

loading enable the larger mechanical percolation of the interlinked-NC possible to be

formed and hence, sharp increase in tensile strength can be expected [1]. The existence of

rigid cellulose network can be evidenced by gel fraction test, as supported by the fact that

16
continuous network structure hold by strong hydrogen bonds is not easily disintegrated

and even dissolved into solvent (e.g. toluene) [71]. During this test, the residual gel

recovered at the end of the swelling experiment would be further used to measure the gel-

fraction of samples.

Ideally, the tensile strength can be improved with increasing NCs loading considering

more touching surface area and contact sites on NCs could be provided for surface

bonding with matrix, allowing the increased hydrogen-bonding interactions to more

effectively transfer the load from matrix to NCs [40,60,61,72]. This ideal case, however,

is only realizable under the conditions of high nano-scale dispersion quality as long as the

formation of NCs aggregates as shown in Figure 4(b) has not been initiated [64]. Mostly

when the loading levels exceed optimum filler concentration or even percolation

threshold, the intermolecular aggregation of NCs might cause stress concentration at the

fillers surface or agglomerated NCs tend to act as defects to weaken the effective stress

transfer from the fillers to matrix [17,67]. The unhomogeneous dispersion of NCs also

represents the discontinuity of interfacial hydrogen interactions between filler-matrix,

thus resulting in an uneven stress distribution throughout the polymer during tensile

drawing and eventually delined tensile strength [61,73].

3.2 Young’s Modulus

The mechanical property in term of Young's modulus can be determined from the slope

of initial linear part of the stress–strain curve. The Young's modulus (E) value is a

measure of the stiffness or ability of an end material to against the irreversible

17
mechanical-deformation or even loss of reversible/elastic properties by retarding the

deformative stress applied on matrix [74]. From the perspective of strongly retaining the

elasticity behavior, the elastic modulus of composite system also considerably represents

the degree of resistance on molecular motion from initiating irreversible plastic

deformation, mainly depending on rigidity/stiffness and degree of crystallinity of

nanocomposite and the most importance is degree of intermolecular bonding.

Since crystalline structure of NCs is highly order system, one can always exploit the high

rigidity of this regular system to impose significant reinforcement effect in the elastic

region of composite material [60,75,76]. The high crystallinity of NCs mainly originates

from the cellulose chains are packed by hydrogen bonding stabilization into greatly

ordered compact system (crystallites) [27,32,76]. The increment in the crystallinity index of

NC results in the high Young’s modulus of nanocelluloses have been experimentally

determined to be around 150 GPa [64,66,77]. This higher modulus value than the polymer

matrix always making the NC posseses higher rigid nature or stiffness, leading they are

potential to exert stiffening action in composite materials followed by the formation of

stiffer composite systems [58,66,73,78]. Furthermore, the increased rigidity of

nanocomposites could also be precisely related to the lower amount of nanoholes inside

the matrix by the increment of cellulose amount. This is in agreement with previous

publications that highlighted the tensile modulus increased as the concentration of rigid

cellulosic filler increased [63,76]. There are mechanical percolation of the homogeneously-

dispersed NCs which induce reinforcement to produce high stiffness of cellulosic

network structure. This is originated from rigid NC-NC interfaces or strong hydrogen

18
bonds formed between the cellulose surface [27,67]. Also, higher crystallinity of NCs is

desired to obtain more rigid NCs which could induce higher stiffening effect on matrix.

The NCs with higher crystallinity are responsible to produce the higher-stiffness

composite by increasing percentage crystallinity of polymer.

It is obvious that the crystallinity of the matrix influenced the mechanical behavior of

nanocomposites [25]. It has been well-reported that the increased crystallinity of polymer

could improve tensile modulus of the nanocomposites by high compactness of cohesive

system [23]. The crystalline domains of polymer can be enlarged or converted from

amorphous phase by the nucleating potential of NCs which could induce geometrical

growth of crystallites by steering the realignment of amorphous chains in the vicinity of

primary nucleation sites [77,79] As a result, the Young’s modulus of nanocomposites can

be improved by the larger number of crystalline regions which consisted of polymer

chains with strong restriction in mobility upon being stabilized by secondary bonding as

cohesive systems. The effectiveness of recrystallization process are desired to be

amplified by higher crystallinity or larger amount of NCs, since more growth sites of

crystallites could be provided to weaken the crystallization activation energy required for

composites [6,79]. When the NCs content is increased above optimal level, the

crystallization process might be disturbed by aggregates or hindered by an increase in the

viscosity, resulting in less crystalline structure could be formed [4,77]. The nucleation

action of NCs also commonly suppressed in the hydrophobic polymer matrix since the

poor compatibility between filler-matrix is unfavorable to create primary contact sites for

initiation of NCs’nucleation. Based on this concern, some work suggested that the NCs

19
merely need a slight increase of surface compatibility for inducing nucleating effect by

the surface chemical modification, subsequently the increase of %crystallinity of

composites can be expected [9].

Apart from the above-mentioned contributions of high NCs’ crystallinity, the high aspect

ratio is another key factor that improved tensile modulus, which relating to increased

degree of intermolecular bonding. As the incorporated NCs have higher aspect ratio, the

larger surface area of NC able to increase the interfacial contact area between the NC-

matrix through intermolecular bonding. Thus, higher extent of matrix can be impeded in

molecular motion [29]. In addition, the formation of interfacial interaction also lies in the

high chemical similarity/functionality between matrix-NCs. This is mostly represented by

strong hydrophilic affinity between hydrophilic polymers and hydrophilic NC. Such

formation of rigid filler-matrix interface through hydrogen bonding is highly effective to

immobilize polymer chains [29,80]. Furthermore, the highly flexible behavior of high

aspect ratio NCs can promote the moving confinement effect on the polymer chains

surrounded the NCs. This might also be further amplified by mutual entanglement

between NCs and polymer chains [7,31,62]. Moreover, it can be anticipated that improved

modulus of hydrophobic polymer (without -OH groups) can be found as long as the

restriction of polymer chains’s movement merely related to mechanical interlocking

between flexible NCs and polymer chains [81]. Finally, the application of NCs with higher

superiority of aspect ratio is more prone to initiation of hydrogen bonding among NCs to

form percolated cellulose network structure. The physical linkages/interaction between

matrix and continuous NCs network could extensively restrict the segmental motion of

20
polymer chains [58,82-84]. However, the interfibrillar stress transfer mechanisms in the

elastic region hard to be initiated at NC content above percolation threshold since such

reinforcement effect is only credited to the NC percolation network formed at percolation

threshold [85].

3.3 Elongation Behavior

Elongation at break (EB) is an indication of the films’ flexibility and stretching ability,

which is determined by the point when the film breaks under tensile testing and is

expressed as the percentage of change of the original length of the specimen [59].

Investigation of the ductility/flexibility is important in order to deal with the fracture

toughness of nanocomposites of highest relevance for the packaging industry and to

gauge their applicability/potential use in the composite processing [45]. The percentage

elongation at break is generally influenced by the extensibility of polymer chains and the

distance of inter-chains slippage for sustaining the deformed matrix without reaching of

failure energy and even breakage. In nanocomposites system, the elongation at break

mainly depends on the interaction between NCs-matrix, the dispersion of the NCs in the

matrix and the volume fraction of the incorporated NCs [3].

Commonly, it is difficult to obtain improved stiffness/strength of nanocomposites without

sacrificing the flexibility of matrix [70]. This represents the increased brittleness of

polymer under embrittlement effect of NCs. Indeed, based on the rigid nature of the

nanocellulose, stiff reinforcements of NCs tend to cause substantial local stress

concentrations to decrease the elongation at break as filler concentration increased [76,80,86].

21
In primary of the stiffening action of NCs, the strong intermolecular interaction between

polymer-NCs tend to inhibit the regular tropism of molecule chains from slipping during

tensile drawing, causing lesser plastic deformation in length of samples and thereby

reduced matrix strain [40]. Implicitly, the EB is inevitably reciprocal to high bonding

interaction at the matrix-NCs interface which is also beneficial to improve strength and

stiffness [25,40]. Similarly, the nucleating effects of NCs can improve composites’

crystallinity. But, it would have lower EB by less numbers of inter-chains available to

have slippage, while rigid secondary bondings in crystalline regions also tend to behave

against the extension of matrix. Apart from these, the 3D hydrogen bonds network either

formed by interconnections between matrix-NCs or NC-NC has even exhibited the fact of

the notably decrement of elongation at break by resisting the applied stress independently

of the softening of matrix during mechanical deformation [15,26].

Dissimilar to preferential strengthening effects of NCs above, the EB of composite matrix

could be undesirably weakened by following unfavorable two causes, i.e. (1) flaws

formation by NCs, (2) severe processing conditions of nanocomposites. For the first issue,

it is well-stated that defects or flaws distributed throughout the composite structures

would form break points with a greater possibility/propensity to initiate the rupture of the

matrix at less elongation [73]. The NCs without chemical treatments form co-aggregation

of NCs which could be easily achieved by the vaporization of the water during drying,

caused the defects in matrix during elongation [87]. By the utilization of hydrophobic

matrix or excessive NCs filling, the improper dispersion of NCs would result in uneven

stress distribution throughout the composite when being subjected to mechanical tension

22
which tends to isolate aggregated NCs to produce numerous fracture initiating points [88].

Meanwhile for the matter of harsh processing conditions, the molecular length of filler or

polymer chains could be shortened by thermal degradation or shearing effect that lead to

a decrease in the distance that the molecular chains could be sliding past each other

during tensile stretching and reduced extensibility of polymer chains. During

nanocomposite processing, the thermal degradation can be caused by high temperature

melt compounding, long processing times as well as the extreme mechanical shearing

which might be occurred during solution casting like prolonged time of sonication [23].

The nanoscale cellulose could also deliver enhanced toughness to the composites through

the improved EB in nanocomposites compared to virgin [1,61]. The extremely strong

interactions at the NC-matrix interface can be the possible reason of such dramatically

increased strain-to-failure [6,66,67]. This is owing to the filler efficiency of enhancing

plastic response of the brittle polymer by introducing stress transfer mechanisms to

reduce the mechanical stress suffered by matrix alone through the non-critical but energy-

absorbing failure events [60,67]. In other words, the formation of bonding bridges between

the matrix-NCs are capable of retarding the fracture/breakage of brittle matrix with

higher sustainability of plastic deformation and even extension [75]. However, in case of

hydrophobic matrix, the fracture toughness of composite also possible to be improved

even if lack of hydrogen bonding formation. In contrast, the poor compatibility between

hydrophilic NCs and matrix could encourage the slippage of intermolecular chains during

stretching [11]. More importantly, good dispersion of NCs is a crucial condition to be

considered in retaining the high EB or toughness of polymer by preventing the formation

23
of stress concentrating points (i.e. aggregates or defections) throughtout the composites
[58,60]
. The excellent elongation at break can also be expected from the percolated network

formation of well-dispersed NCs. This could retard the propagation of cracks during

tensile failure, contributing to the delay of the stretching damage to higher strains [58,60].

In the case of EB value reduced as the dispersion level decreased, this decrement trend

might be stopped instead of being reboundingly increased as long as the continuous

increment of loading level has agglomerated the NCs into micron sized aggregates [61]. It

is quite low possibility for the aggregates to restrict the movement of polymer segments

under stress. Hence, high flexibility of molecular chains can be expected.

3.4 Flexural-Impact Properties

Prior to applications of polymeric composite, flexural and impact properties are important

mechanical parameters in terms of ability of an engineering material to resist flexural-

impact plactic deformation [89]. The flexural-impact resistance is a criterion of measuring

deformability carried out by three-point bending test and impact fracture test respectively
[6,90]
. It should be reminded that in a flexural test the combination of tensile and

compressive strength occurs, and therefore, any measurement is affected by both flexural

and shear stresses [89]. The flexural test is strongly influenced by the properties of the

specimen closest to the top and bottom surfaces since the stresses in flexure vary from

zero in the middle to maximum in the top and bottom surfaces. An Izod impact test is

basically a flexural test with a transient load being applied, involving two different

fracture mechanisms from notched and unnotched Izod impact tests [6]. Dissimilar to

24
notched impact, for the unnotched sample, impact loading applied at the opposite side of

the notched tip and the crack was initiated and then propagated from the impact point [45].

In a similar manner, flexural and impact properties could serve as good indicator for

plastic deformation resistance, fracture initiation resistance and cracking-propagation

resistance of nanocomposites [6,45]. Although the stiffness of a single NC is theoretically

higher than steel, but its density is much lower, making it a promising energy absorber

for composite materials by its loose structure [13]. Hence, the improved plastic

deformation resistance upon the inclusion of NCs mainly attributed to the ability of NCs

to effectively transfer imposed load from matrix by altering the stress state in the matrix

alone [6,45]. The NCs have been used as load-bearing constituent in developing composite

materials likely due to their high aspect ratio which posseses high efficiency of energy

transfer to induce more energy absorption for plastic flexural deformation [75]. In addition

to NCs with high aspect ratio, the fibrils entanglements which act as resistant junction

points against deflection forces also contributed to enhanced plastic deformability [89].

Generally, flexural strength and unnotched impact strength able to show good

enhancement by increasing cellulose filler loading because of the increased ability of

composite to absorb energy for plastic flexural deformation. This is because the increased

nanocelluloses tend to elevate the energy consumption for matrix deformation and

increased numbers of stiff interface [6,11]. On the other hand, for the brittle material has

inherently poor plastic deformability, the plasticization efficiency of the NCs on the

matrix could increase the impact/flexural strength. The possible plasticization effect of

the NCs addition also tend to additionally increase efficiency energy absorption in the

25
process of plastic flexural deformation, contributing to higher flexural/impact strength

finally. However, these positive outcomes of improvent of flexural/impact properties

could only be realizable under the absence of NCs agglomerations. The flexural strength

and unnotched impact strength were affected by the energy consumed for plastic flexural

deformation prior to crack initiation [45]. The energy consumed for plastic deformation

would be excluded in final impact strength of notched sample since the notched tip

already act as stress concentrating point for fracture initiaton when impact occurs [45].

Without experiencing energy absorption for plastic flexural deformation, the notched

Izod impact energies are thus inevitably smaller than the unnotched Izod impact energies
[45]
.

In turn of fracture initiation stage, the notched tip of notched samples and fracture point

at filler-matrix interface play an important role to induce the initiation of fracture since

they are stress concentrating point, especially the addition of filler enabling the

occurrence of fracture to become easier [45]. For the higher fracture initiation

energy/resistance in ideal case, the flexural/impact strength could be improved by higher

debonding energy of filler-matrix than dissociation energy of backbone chains of neat

matrix. In this case, the improved flexural/impact strength mainly related to the ability of

filler-matrix interface under good level of interfacial adhesion to effectively absorb

energy from deflection/compressive force and high speed impact for debonding while

increasing resistance of fracture initiation [89]. Apart from that, the presence of stiff

nanoreinforcement is also reponsible to render high flexural/impact strength to the

polymers by resisting the fracture initiation of the adjacent matrix via rigid filler-matrix

26
interface [91]. Such factors resulting in higher energy consumption required to initiate

mechanical fracture/cracking at such interface adding to the absorbed energy increased

by deformability [45]. Normally, the higher stiffness and density (~1.6 g/cm-3) of NC as

compared to matrix enabling the density of overall composite materials could be

increased by strengthening/stiffening effect of NCs exerted on matrix [13]. The higher

density/molecular weight of composite has been know to possess higher flexural strength,

which is likely due to the strong intermolecular forces generated from dense

intermolecular structure able to withstand against the debonding mechanism occurred at

interface [46,91]. In fracture initiation stage, the higher NCs’ length has higher priority to

improve the flexural strength and modulus values of composites because of increased

contact area to maximize the intermolecular bonding strength [6]. Indeed in real

application, there is possible generation of flaws or self-assembly of NCs which tend to

create interspace facilitating the initiation of fracture with lower resistance or bond

dissociation energy [45]. Otherwise, the strength improvement might be unsatisfied

because of the poor compatibility between the cellulose and the matrix [11].

Furthermore, the cracks propagation stage occurred during mechanical testing mainly

determined by cracking propagation resistance w [45]. Cracking propagation mainly

resulting from the cavitation mechanism/voiding effect generated from rigid particles

following at the particle-polymer interface after fracture initiation and debonding [45]. If

the filler particles are homogeneous distributed throughout the polymer matrix, cracks

will only be initiated/propagated at the NC-matrix interface by high enough crack

initiation energy [45]. The notched impact strength is more influenced by matrix polymer’s

27
resistance to crack propagation than flexural strength and unnotched impact strength

since the total impact energy of notched sample is mostly consumed for cracking

propagation [45]. By dispersing NCs of higher aspect ratio, the larger effective surface

area of NCs available for contact with the matrix or bridging formed in between them

under high fillers content could create stronger filler-matrix interfacial adhesion to

compete with tendency of propagation [89]. Nevertheless, it is generally observed that the

improvement of cracking propagation resistance difficult to realize even under the good

NCs dispersion by the increased incorporation of stiffness nanocellulose likely due to

increased crack initiating points [89]. The increased NCs loadings could also decrease the

plasticity of matrix polymer and increase brittleness. Brittle material generally posseses

high cracking sensitivity which leading to the facile propagation of the crack occured in

sample with increased filler-matrix debonding points, and hence lower strength [45]. The

worse is there is no impact resistance in the brittle fracture zone beyond the slip-stick

point in real applications [45]. The cracking sensitivity could be aggravated by

agglomeration of filler particles with poor NCs dispersion quality or the filler-filler

contacts in the composites leading any cracks to propagate easily in the composite than

the filler-matrix interface in the matrix polymer [35,45].

3.4 Thermo-Mechanical Properties

For the industrial potential of NCs application, one should consider that the mechanical

properties of polymers are inevitably varied with the temperature and the issues of loss of

mechanical properties at high temperatures probably occurred to limit the implementation

[25]
. In this concern, many efforts have been dedicated to investigate thermo-mechanical

28
behavior of the nanocomposites using dynamic mechanical-thermal analyzer (DMTA)

while the sustainability of mechanical properties at elevated temperature by the addition

of NC can be anticipated [9,59]. DMTA is an official standard method to investigate the

reinforcement efficiency of the NC on the viscoelastic properties of materials in a wide

range of temperatures [92]. As generated from DMTA, the representative data of dynamic

mechanical properties involve storage modulus (E’) and loss tangent (ratio of loss

modulus/storage modulus) which measured as a function of temperature [13]. Temperature

scans run can be ranging from -50 °C to 200 °C at a specified heating rate with a

frequency of 1 Hz and strain amplitude of 10 μm [93]. It is worthy to mention that the

typical dynamic moduli are maximally tested at temperatures around 200 ºC to avoid

possible NC degradation [60].

3.4.1 Storage Modulus

Storage modulus (E’) is a measure of the maximum energy, stored in the material during

one cycle of oscillation [68]. The E’ provides information on interactions for incorporation

of NCs within the polymer matrix, i.e. NC-matrix entanglement, NC-NC interactions and

NC-NC entanglements [71]. According to typical graph of E’ against temperature as

shown in Figure 5(a), the samples display a typical behaviour of thermoplastic based on

three different zones: glassy plateau, glass transition, and the rubbery plateau before

melting starting [9]. The glass transition temperature (Tg) corresponding to -relaxation

transition temperature (T ) which is used to distinguish the significant changing of E’,

indicative of polymer reinforced by NCs is temperature dependent [10].

29
By referring to Figure 5(a), the nanocomposites show storage modulus outperforming

over neat polymer while the storage modulus of the composites increased as the NCs

content raises [58]. Basically, this is an indication of strong reinforcement effect obtained

with the addition of NCs which allowing the restriction of the mobility of the polymeric

chains under the good interactions at the interface level of filler-matrix [9,68]. Initially, the

storage modulus does not show much variation or almost remained constant with

different NCs loadings in the glassy plateau, simply due to the NCs unable to further

immobilize the molecular chains at low temperature to a greater extent [60]. This is

expected for the relatively low volume fraction of the reinforcing phase at low

temperature and the slight E’ enhancement in the glassy plateau is considerably belonged

to the enhanced immobility of polymer chain by strong interfacial interaction [48]. Since

the crystalline polymer chains also posseses strong interactions via intermolecular

secondary bonding, it is believed that the enhanced degree of crystallinity by nucleating

effect of highly crystalline NC also contributes to improve glassy modulus [94]. Unlike

polymer chains of glassy state, the moving polymer chains in rubbery region enabling the

NCs exhibit its reinforcing effect to a higher extent, thus making the improvement in

storage modulus of rubbery region is prominent.

For the rubbery state above Tg, it is realized that the stabilization effect on E’ of NC-

reinforced polymer is enhanced with NCs concentration. The E’ of composites filled with

highest NC loading appears almost constant and long plateau in the rubbery state [88]. The

strong increase in composite thermo-mechanical stability cannot be merely understood by

the strong interfacial interaction between NC-matrix. There is also another possible

30
reason of reinforcing action of NC improves the modulus in the rubbery region. The most

probable factor belongs to the formation of stiff celluloses network governed by

percolation threshold associated with tangling effects within the material [68]. As

compared to the stiff percolation network without entanglement effect which could

highly reduce the polymer chain mobility, the additional mutual entanglement between

filler-filler or filler-chains could further contribute to the high elastic modulus measured

in the large temperature range [1,25]. By referring to Figure 6, there are differences

between a simple contact and an entangled contact between two fillers. Irrespective of

entanglement between filler-matrix, the entangled percolating cellulose network could act

as a load bearing framework which has high ability to prevent the polymer from flowing

like the pure matrix as a viscous fluid at high temperature [1]. For the percolating cellulose

network accompanied by entanglement properties, physical linkage within a fibrous

structure is also responsible for the elastic response of this web-like structure [88]. The

mutual entanglement between NC-matrix enables more highly impede flowing tendency

of polymer chains, whereby to sustain the improved stiffness of composites despite of

high temperatures [7,25,70]. This desired outcome might be realized by using NC with high

enough aspect ratio considering the good flexibility properties of long fibrils favorable to

exhibit a tangling effect with the polymer matrix.

In addition, when above the polymer softening temperature, the slope of the rubbery

plateau could also exhibit an indication about reinforcing efficacy of the NCs as well as

the steep slope corresponding to pure polymer as observed in the Figure 5(a) represents

the facile drop of modulus with elevated temperature. In the absence of nanofiller, the

31
rubber-like behaviour is also increasing prominently with temperature [95]. In the aspect

of nanocomposites, the slope of the rubber plateau is generally lesser steep than for the

unreinforced matrix, suggesting an increasing stabilization effect and contrast of the NCs

with matrix modulus [70]. The contrast is known to be the great influence of reinforcement

effect of the NCs, mainly the entanglement effect among NCs and/or between filler-

matrix. In case of the difference between the slopes of composites is small or similar for

different NCs content, it is poised to exclude the presence of entanglement effect within

NC network and/or matrix-NC. Whereas, reinforcement mainly induced by sole stress

transfer between matrix-filler [88]. If the slope of the E’ curves of composite being steeper

close to pure polymer, a very low mechanical reinforcement can be a possible cause [83].

Hence, it is believed that the NC content is below the critical percolation threshold,

leading to the dispersed NCs difficult to interact with each other and limits the hydrogen

bonds formation among cellulose nanofillers. In addition, the lack of reinforcing action of

percolated cellulose network expectedly causes the disability of material to sustain the

storage modulus to higher extent with increasing temperature [63,95]. Within rubbery

temperatures, it is reasonable to state that the increment of composites’crystallinity by

nucleating process of highly crystalline NC also contributes to highly stabilized rubbery

modulus as long as without exceeding the melting temperature (Tm) to avoid the enlarged

crystalline regions from being affected/melted that desired to sustain the modulus

originated from crystalline structure [94].

Between the glassy and rubbery region, the flow temperature or polymer softening

temperature acts as the transition temperature from glassy state to rubbery state, so called

32
Tg. In brief, with respect to neat polymer, the flow temperature could be shifted to higher

value by the addition of NCs in which the delay of the polymer molecular motion to

higher temperature. Upon the energy-absorbing failure events found results from the NCs

addition, the energy transfer from matrix to NCs in composites can retard the thermal

energy-induced free motion of polymer chains [58]. In many studies, one can note that the

incorporation of NCs has resulted in improved modulus along with the reinforcing

efficacy is higher at temperatures which is greater than Tg [13].

3.4.2 Loss Tangent

Another dynamic-mechanical property, tangent of the loss angle (Tan ) is a meaningful

value obtained from DMTA to evaluate the interfacial bonding in composites since

tan value is dependent on the filler-matrix adhesion level in composites systems [68]. In

the obtained damping curve, the tan as a function of temperature for the composites

samples is analyzed [61].

With the increasing of temperature, the value of tan mechanical damping factor ascend

and decend matching with the material changes from a rigid to a more elastic state,

resulting in the formation of tan peaks [2]. Habitually, two main tan peaks appeared,

the first (above room temperature) is normally assigned to the -relaxation while another

tan peak (maximum) occurring at higher temperature side is designated as the -

relaxation [66]. A noteworthy fact is that the maximum tan trace (damping peak) exhibits

a well-defined relaxation, more suitably representing the glass transition of composite

material. In other words, the corresponding peak temperature (T ) at maximum tan

33
could accurately determine the glassy transition midpoint and is most frequently used to

estimate Tg of composite material [67]. The magnitude of mechanical damping factor is

regarded as the ratio between the loss energy and the storage modulus [61]. Implicitly, the

increase in tan value with temperature along the curve is a result from the increment of

loss energy in line with decrement of mechanical damping until the cooperative

movements of long chain sequences of molecules at Tg, following by decrease in tan

value with temperature.

The positive reinforcing effect of NCs could be evidenced on mechanical damping curves

in Figure 5(b) through the clear dependence of tan value with cellulose concentration

involving the shifting of maximum peaks of the tan curves towards higher temperatures,

broadening of half-peak width of tan peak and reduced intensity of tan peak. Indeed,

the good interfacial bonding between NCs-matrix could explain these phenomena. This

can be explained that the ability of NCs to limit segmental movement of the polymer

chains. Thus, lesser energy could be dissipated encouraging more energy supplied to

regain the relaxing of polymer chains. Subsequently, higher T relaxation as well as the

shift of peak temperature to higher range [63]. When the interaction at the NCs-polymer

interface is increased as functions of NC content, the increase in the peak temperature

could be resulted. For the second phenomenon, the substantial broadening in the tan

peak with the increment of NCs content could be attested by the broadening of line-width

at half-maximum height or half-peak width of tan peak as well [13]. This broadening

effect indicates that the molecules mobility of the polymer matrix is hindered to a certain

degree by NCs towards diminishing the magnitude of the relaxation process, while such

34
effect could be magnified at higher loadings [9,95,96]. For the third phenomenon, the

decreasing trend of peak intensity of maximum tan represents the fewer amount

polymer chains are relaxing at the glass transition by higher NC content that consisted of

restricted molecular motion at rigid filler-matrix interface. The reduction of the number

of relaxing chains might not purely ascribed to the large interfacial interaction between

filler-matrix, but also possibly relating to stiff fibrils network structure with/without

physical entanglements that tend to limit the number of mobile units participated in the

relaxation phenomenon [23,58,63].

When the height of tan peak does not show decreasing trend with NCs loading, this

evidences the incorporation of cellulose solid fillers into matrix unable to control the

movement of polymer chains facilitating high fraction of polymer chains taking part in

the relaxation [63]. This phenomenon mostly occurred on composite material with very

poor fillers-matrix interfacial bonding which tend to dissipate more energy when exposed

to an oscillating stress [67]. Since the related relaxation process is strongly influenced by

the magnitude of the storage modulus drop as compared to energy losses, the

unsuccessful reinforcing action of NCs tend to more favorably induce the weakening of

storage modulus, exhibiting rise to elastic behaviour rather than viscous nature [61]. One

might observe that the tan peak lack of significant shift to higher temperature or there is

only small changes in the Tg [31]. This indicates that the reinforcing effect and thermal

stability of composites is merely associated with the cellulosic network structure and/or

strong interaction among the NCs particles.

35
3.5 Thermal Behavior Studied By DSC

Differential Scanning Calorimetry (DSC) analysis is popularly performed to investigate

the thermal properties of nanocomposites, mainly non-isothermal crystallization and

melting behaviour. Although the isothermal crystallization behavior has been included in

DSC measurement but it is out of scope in current review due to rare researches were

taken [86]. During DSC experiment, the non-isothermal procedure consisted of heating the

sample using a constant heating rate followed by annealing the sample at end temperature

(isotherms) to erase any thermal history the samples before being cooling at a same rate
[18]
. Heating-cooling scan is preferentially repeated another time at the same rate in order

to investigate the intrinsic properties after erasing thermal history of non-isotherrmal

heating, while the multiple session analysis (heat-cool-heat-cool) is also useful to make

comparisons [23]. Basically, the tested samples are heated and cooled back under a

nitrogen environment to avoid thermal-oxidation of samples while the end temperature at

the heating scans is not beyond 210 ºC to avoid thermal-degradation of the material [23,97].

The information provided from typical DSC thermograms as shown in Figure 7 is

beneficial to collectively study the material’s glass transition, cold crystallization and

melting of nanocellulose-composites in relation to their composition [75,97,98]. These three

thermal events are typical for semi-crystalline polymer while the area under the curve are

useful to estimate the degree of crystallinity (Xc) by using enthalpy or heat of fusion

from the endothermic peak (ΔHm) and exothermic peak of cold crystallization (∆Hcc)

during first/second heating scan [97,99]. The calculation of degree of crystallinity (Xc) of

the composites are therefore expressed in the Equation (1):

36
 Hm H cc
Xc = 100%
100% (1)
Hm

In case of DSC analysis lacks of ∆Hcc data, the Xc can be calculated by Equation (2):

Hm
Xc = 100% (2)
w Hm100%

Here, w is the mass fraction of based polymer in the composite [30,97]. The ∆Hm100% (also

called ∆Hm∞) is the theoretical enthalpy of melting per gram of 100% crystalline (perfect

crystal) or enthalpy of fusion (ΔHf) of repeating unit of the perfect crystal of infinite size

of polymer [9,86]. As compared to Xc calculated from the first heating run, the data

obtained from the second heating cycle are expectedly much more reproducible and

reliable since crystallization has already taken place during the cooling of as produced

samples upon processing, making the kinetics of which is difficult to control and data of

first heating run are difficult to interpret [9]. Additionally, the changing of the Xc of as

produced samples calculated from the first heating scan typically is not proportional to

the ΔHm.

3.5.1 Crystallization Behaviour

Crystallization is commonly referred to the ability of polymer chains under moving state

to perform crystalline packing into ordered and compact system. Crytallization is

normally stabilized by hydrogen bonding or secondary bonding. The introduction of NC

into the thermoplastic inclines to change the intrinsic trend of DSC curve of neat polymer

involving cold crystallization in heating run and crystallization from melt during cooling

run.

37
In the heating scans, the samples showed a distinct exothermic peak, attributing to the

cold crystallization during heating process [86]. The observed exothermic peaks could be

used to estimate the corresponding cold crystallization temperature (Tcc) [99]. By the

positive modification of NCs, the shift of Tcc to lower value in the non-isothermal

crystallization is highly taken place in the heating run [97]. This behavior reveals the faster

rate and earlier initiation of cold crystallization process upon experiencing the

enhancement of the nucleation rate since the nucleating potential of NCs could weaken

free energy barrier of initiating crystallization process [9,99]. When increasing NCs content,

the crystallization process is accelerated within polymer matrix by the increased number

of primary nucleation sites within amorphous matrix in line with reduction of the

nucleation induction period [97]. The increased nucleation rate by addition of NCs is also

beneficial to increase/broaden area of crystallization peak as well as Hcc which is the

enthalpy of exothermic peak that is absorbed by the crystals formed during the DSC

heating scan [86,97]. Moreover, the Hcc is inversely proportional to inherent crystallinity

(Xc) of sample as hinted by Equation (1) based on larger amorphous region could be

provided for recrystallization. In contrast, the high inherent crystallinity of composite is

undesired to encourage the further growth of crystallites and hence the reduced Hcc is

expectable. For the shift of Tcc to higher value by the introduction of NCs, the poor

ability of recrystallization can mainly explained by the strong interfacial interactions

between NC-matrix which tend to amplify the free energy barrier for initiation of

crystallization process [87]. This situation is especially occurred when high amount NC is

added towards increasingly suppress the molecular motion of the polymer matrix in the

vicinity and even delaying the crystallization process to higher temperature for gaining

38
sufficient energy to induce nucleation in polymer matrix. In addition to high loading level,

one can note that the stronger adhesion between the matrix and NC created by surface

chemical treatment on NC could also hinder the motion of the hydrophobic polymer

chains to higher extent, retarding the recrystallization eventuallly [97]. However, the NC

which is completely incompatible to matrix (such as hydrophobic polymer) also

undesired to exert its nucleation action on adjacent polymer chains due to lack of primary

contact sites. Therefore, some works suggest that the NC just needed the slight increase

of compatibility for inducing the nucleating effect that could be realized by surface

chemical modification [9]. Remarkably, the improvement of surface compatibility to very

high extent is not recommended to avoid poor recrystallization by high restriction of

molecular motions, wheares a certainly low compatibility can beneficially favour

nucleation.

In turn of cooling run after heating run, the heat flow from the sample ( Hc) and the

crystallization temperature (Tc) could be interpreted from the observed exothermic peak
[23]
. The increasing of Tc by the addition of NCs denotes the crystallization of NC-

reinforced polymer from melt would be initiated earlier during the non-isothermal

cooling process [87]. This can be explained by the role of cellulosic filler to serve as sites

for heterogeneous crystal nucleation in the composites [18]. The nucleation of

crystallization could also be enhanced in the case of earlier melting of samples when

being heated up followed by the earlier formation of crystalline structure when being

cooled down, while the issues of lower melting point will be discussed in next sub-

section [18]. If there are less crystalline region could be melted indicating less formation of

39
crystalline structure during cooling step, the releasing of exothermic heat or

crystallization enthalpy ( Hc) is therefore become lesser [87]. When Tc decreased in the

non-isothermal crystallization study, the poor crystallization resulted from low dispersion

quality by increasing NC content could be the reason. This is due to the good growth

geometry of the crystals requires the high dispersion quality of NCs which could ensure

the proper contact between each filler and matrix for initiating heterogeneous nucleation

mechanism [9,23]. The decrement of crystallization temperature and enthalpy with

increasing NCs content could also be resulted from material degradation of hydrolyzable

polymer through the hydrolysis action of residual moisture on NCs [23]. This can happen

during second cooling scanning cycles, suggesting the nucleating effect of NCs inhibited

within degraded matrix under the lack of primary nucleation sites to initiate

crystallization along with the loss of crystalline packing ability of degraded chains.

Accompanied with decreased Tc in the cooling scans, the exothermic peaks with very low

intensity or narrower area are also possibly observed for the NFC-reinforced composites,

indicating a rather low crystallization capability since the entanglement effect of long

fibrils highly restricts the molecular motion of the polymer matrix [18,86,87].

3.5.2 Melting Behaviour

At temperature greater than Tc during heating scan, the samples exhibit an endothermic

curve. Under this curve, the covered region is a signature of the fusion of crystallites in

composite, while the magnitude of corresponding area is essentially expressed as

endothermic/melting enthalpy [75,97]. Overall, the melting behavior is mainly affected by

crystallization behavior, degree of crystallinity and size/perfection of the crystalline

40
lamellae, which supporting that the crystalline structure of different materials obtained

after the melting/recrystallization process are almost the same [97]. According to equation

(1), the Hm is proportional to the degree of crystallinity (Xc), representing the increase

the melting enthalpy ( Hm) during heating run of DSC mainly related to larger crystallite

size or thickness by the addition of NCs [75,97]. The Xc of nanocomposites could be

increased by increased NC content since the NCs serve as bio-based nucleating agents

which is responsible to reduce the nucleation induction period in line with improving

crystallization kinetics in amorphous matrix [77]. The corresponding temperature at

melting peak in endotherm is designated as melting temperature (Tm). In many cases, Tm

is mostly localized in same position without any significant shift after addition of NC,

this can be deduced that the incorporated NC has low ability to modify the original

crystalline structure [97]. Especially in case of unmodified NC used in the hydrophobic

matrix, the resulting incompatibility of NC and polymer leading to the high stabilization

of equilibrium melting point [9]. Studies reported that melting point increased as a

function of the NC content, confirming the nucleation effect of the NCs has increased

degree of crystallite perfection as well as crystallinity of polymer [97]. Indeed, the

increased formation or perfection of crystallite lamellae represents higher intensity of

secondary bondings which require higher thermal energy (higher Tm) for bonds

dissocation of interchains within crystalline structure. Similarly, the increased intensity of

molecular bonding between the increased amount NCs and polymer chains also requires

higher melting heat with higher temperature to dissociate strong hydrogen bonding [75].

Unlike hydrophilic polymer, the creation of well-adhesion between the matrix-filler in

hydrophobic polymer requires the surface modification of NCs [75]. However, some

41
works also support the concept that there will be an increase of the polymer chains

mobility when the hydrophobic polymer is confined near a non-interacting interface on

unmodified NCs, contributing to higher flexibility of polymer chains to initiate crystalline

reorientation and even higher crystallinity [97]. The excellent improvement of degree of

crystallinity mostly depends on crystallinity of NCs since the highly-crystalline NCs

(especially CNCs rather than NFC) could induce significant nucleating process in

amorphous domain of any semi-crystalline polymers (e.g. polyamides) [67,100].

Additionally, by using CNC instead of NFC, it was postulated that the chain mobility

near a non-interacting surface could be increased by a reduction of the entanglement

effect of NFC [97]. When using NCs having lower degree of crystallinity than based

polymer, these low crystalline NCs are unexpected to offer significant nucleating

potential for matrix [37].

The undesirable depression of melting point and melting enthalpy by the introduction of

NCs shows that the crystalline structure could be melted more easily with requiring less

melting temperature (or heat) for dissociation of secondary bonds [18]. This is mainly

related to the less formation of crystalline region which could be melted and eventually

making the earlier initiation of melting at lower temperature when being heated up [18].

The magnitude of this shift possibly increased with NCs concentration due to the stronger

restriction of polymer molecular mobility which are close to the NCs under the

reinforcing action of NCs. This causes less efficiency of recrystallization as well as less

perfection/thinkness of crystallite and crystalline ratio of composites [97]. The reduced

degree of crystallinity could also be the explanation of the lower Hm based on Equation

42
(1) resulting in a decrease in the heat of fusion [87] Despite of high loading level, it was

postulated that the entanglement effect among nanofibrils in NFC could more effectively

cause a decrease of the chain mobility rather than CNC while surface modification of

NCs could also induce stronger adhesion between the matrix and the NC [97]. Although

the higher loading level of NCs could more extensively hinder the nucleation action of

NCs, the too small contents of NCs also might be insufficient to initiate significant

crystallization due to lack of primary nucleation sites for crystal packing of polymer

matrix [67,81,99]. The high provision of primary nucleation sites by NCs might be difficult

to be realized under the high affinity of NCs to agglomerate with each other. This is

possible to form defects towards affecting the crystallization process as well as forming

imperfect crystallites. Moreover, without the physical covalent linkages between matrix-

NCs, the clusters of NCs tend to be isolated beyond matrix with increasing processing

viscosity which could exert hindrance on polymer segment motions and subsequently

retard the recrystallization mechanism [77,101]. The polymer degradation caused by the

addition of NCs also tends to impose adverse effects on melting temperatures as well as

melting enthalpy which would be aggravated by NCs concentration. This has been

occurred under the utilization of hydrolyzable polymer, where the residual moisture on

NC surface caused backbone degradation of based polymer through hydrolysis under

high processing temperatures, making such degraded composites are therefore melted

easily during secondary thermal scanning cycle. This undesired outcome was related to

the abundant OH groups on excessive NCs have been strongly reacted with water

molecules. Indeed, an additional step of drying the NC masterbatch in an oven was also

found to be ineffective in removing the residual moisture [23]. Thus, further study is

43
needed towards removing moisture from the NC along with tackling strong hydrogen

bonding between cellulose and water molecules, which will be discussed in section 4.1

later [23].

A rare phenomenon has been observed about the appearance of minor exothermic or

endothermic peak just before the main melting peaks. This happen because of incomplete

recrystallization process during first heating run which mostly due to the too low cold

crystallization temperature. The remaining recrystallization is therefore finished at higher

temperature but slightly lower than melting point. Subsequently, the formation of small

exothermic peak by melting/recrystallization mechanism also possible to be explained by

an increase of the thickness of the crystalline lamellae formed during cold crystallization
[97]
. The formation of minor endothermic peak is mainly related to some of the polymer

crystals have a large tendency to reorganize into more stable structures through

continuous partial melting-recrystallization-perfection mechanism during first heating run.

Afterwards, the reorganization or recrystallization of these crystals during the following

cooling run might result into the formation of small/imperfect crystals associated with

more perfect crystalline structure in the second heating run consequently. While the less

perfect crystalline structure or defective crystal is corresponding to the formation of the

shoulder peak at lower temperature than main melting point. Although the total melting

enthalpy ( Hm) of both endothermic peaks remained almost unchanged compared to the

first temperature cycle, a bit higher value can be observed [97].

3.5.3 Glass-Rubber Transition

44
On the typical DSC curves, a slight endotherm would be overshoot at lower temperature

than Tcc while the corresponding temperature is taken as the inflection point of the

specific heat increment at the glass-rubber transition and this is defined as glass transition

temperature (Tg) [75,97]. Usually, the glass transition temperatures (Tg) could be more

precisely investigated by second heating period since the first heating step has been run to

remove water absorbed by hydrophilic polymer or NCs [26].

It is known that the glass transition (Tg) is a complex phenomenon which depends on

several factors including intermolecular interactions, steric effects, the chain flexibility,

the molecular weight, the branching and the cross-linking density [97]. Therefore, Tg is an

effective value measured to ascertain the mobility of the macromolecules and also could

be a measure of ability of crystallization in the previous cooling step. The material which

contains highly crystalline region like the increased crystallinity of polymer by the

nucleation action of NCs reflects increased amount of polymer chains with restricted

mobility [77]. Hence, it is necessary to be melted at high temperature while unable to

perform transition from solid to rubbery state previously. For the higher Tg of composite

as compared to pure polymers, the addition of NC has significant effect on the mobility

of polymer matrix. When increasing the NC content or volume fraction, a stronger

inhibition of the polymer chains segmental motion could be exerted by NC particles in

the matrix through either the restricting effect of the NFC network or hydrogen bonding

between matrix-CNC [26]. It is usually no major shift of the Tg could not be significantly

observed, evidencing the inadequate sensitivity of DSC to detect the small modification

by low weight fraction of cellulosic fillers on chains mobility, or only small fraction of

45
amorphous chains could be modified by low amount fillers. When the endothermic peak

at Tg is hardly observed by too small area along with the absence of cold crystallization

peak, indicating the materials has been highly crystalline in the end of the previous

cooling step [97].

On the other hand, the Tg could be decreased by weakened interactions between polymer

chains or increased chains flexibility through the generated plasticizing effect as well as

reduced formation of intermolecular bonding. Such as the addition of NCs with high

concentration, the excessive NC particles might act as plasticizer to induce disturbance

on the dominantly original interactions among the matrix polymer chains and hence,

easier to initiate the chains mobility at lower Tg [26]. If the NCs have been agglomerated

as defects, the formation of intermolecular bonding between matrix-filler might be

interfered by cellulose aggregates during composite processing. The reduced restrictions

on molecular motion could therefore decreasing Tg. The interchains mobility could be

increased by plasticizing effects through the degradation products since the isocyanate

(ICN) modified NC might thermally degrade during the non-isothermal crystallization [9].

Moreover, the usage of water during composite processing involving hydrophilic

polymers might leave the physically bound water or free water molecules which have

strong plasticizing tendency [30]. In case of hydrophobic matrix, although the usage of a

surfactant promotes filler dispersion, the residual amount of desorbed surfactant

molecules is possible left over in the film, imposing plasticizing effect on polymer chains
[15,26]
. Without the application of coupling/grafting agent for better interfacial adhesion of

hydrophobic matrix to NCs, the non-interacting NC also possible causes disturbance to

46
the matrix polymer, and therefore inducing the plasticizing effect [26]. Another reported

case, the Tg could be decreased upon blending PLA with cellulose nanowhiskers

modified by lactide oligomers while the oligomers protruding in the matrix phase also

posseses plasticizing behavior [9].

3.6 Thermal Stability and Degradation

In order to further infer the information about the thermal properties at larger temperature

range than DSC, the thermal degradation profiles and thermal stability of nanocomposites

are assessed using a Thermogravimetric analyzer [98]. Generally, thermal degradation or

reduction of thermal stability of polymeric materials at high temperatures is among the

major issues that limit application [25]. Thermogravimetry analysis (TGA) measurement is

conducted with the samples fitted in a nitrogen-based atmosphere to avoid thermal

oxidation [7]. The TGA graph and differential thermogravimetric (DTG) curves of

samples can be obtained from analyzer as shown in Figure 8 (a) and (b) respectively [58].

The given mass loss information from TGA curve is useful to evaluate the effects of NC

on thermal stability of polymer. DTG curve can have a detailed view over mass loss

pattern or weight loss rate occurred during tests, based on a plot of dM/dT versus

temperature by first derivation of mass loss data [7]. Three peak points in DTG curve

(Figure 8b) represent the degradation temperature (Td) at which maximum rate of mass

loss takes place at different decomposition stage [14]. Thermal degradation of polymeric

composites consisted of three main step as respectively represented by the three peak

points in DTG curve, involving the elimination of volatile matter, main molecular weight

depolymerisation and degradation of carbonic residue [25].

47
3.6.1 First Degradation Step

The first weight loss occurred in the range of 25-150 ºC, mainly related to elimination of

low molecular weight compounds involving volatile matter or evaporation of water

remaining from the composite processing and possibly originated from unsatisfied

conditioning [47,81]. By referring to Figure 8a, the decomposition temperature

corresponding to initial 5% weight loss is referred to as T5 which could be the most

representative indicator of elimination of loosely bound volatile matter like moisture [14].

One should take the first note that the weaker thermal stability of composite can be

evidenced by the earlier onset of the thermal decomposition, and thus primarily

deteriorated thermal stability of nanocomposites. This could be represented by the

decrement of T5 with increasing NC concentration as manifested in Figure 8(a) [81]. This

indicates the high tendency of dehydration due to the higher water content has been

absorbed by hydrophilic NCs during the nanocomposite processing. Indeed, the absorbed

water is also possible to induce polymer degradation through hydrolysis which could

result in the possibly secondary deterioration of thermal stability [23]. Meanwhile, the

increment of T5 possibly related to the high ability of –OH groups of NCs to react with

water molecules by formation tightly bound water which is difficult to eliminate unless

higher temperature [102]. Another possible explanation is the high heat resistance of

cellulose nanofiller and/or intermolecular bonding between filler-matrix nanofiller

retarding the heat gaining for evaporation of volatile matter. Cellulosic nanoparticles also

possibly interacted with volatile decomposition products with retarding their diffusion out

of the sample [57].

48
3.6.2 Second Degradation Step

For the secondayy main degradation step of exhibiting hte largest weight loss rate along

the DTG curve, the corresponding decomposition temperature is typically named Td.max

(temperature of maximum degradation step), provide the most important indication of

thermal stability. Alternatively, the main degradation mass loss could be represented by

50% weight loss while the corresponding T50 (the decomposition temperature at 50%

weight loss) is critical point for the largest mass loss rate of composite approximate to the

Td.max. In general, NC-filled-composite is thermally more stable than pure polymer as

ascertained by shift of Td.max (also called DTGmax) to higher temperature [7]. For instance,

the enhancement of thermal stability also could be evidenced by increased values of T50

in TGA curve of nanocomposites [81]. This is mainly contributed by the NCs playing

important role in changing the response of polymer towards greater thermal stability by

its inherently high thermal stability and reinforcing effect in matrix. Firstly, the high

thermally stable NCs which exhibit higher Td.max could impart improved thermal

stability on corresponding composites with efficiently hindering the thermal

decomposition of composites and improving thermal resistance [103]. Moreover, the

nucleation action of NCs of highly crystalline NCs contributes to the increment of stiff

and rigid crystalline structure in the composites, which is likely thought to be less

sensitive to thermal attack [61]. The second factor is originated from the thermal stability

of a composite material which also strongly depends on the molecular interactions

between the different macromolecules. The strong intermolecular bonding between NCs-

matrix could be formed through either physical interaction (cellulose network structure)

49
or chemical interactions (bonding between functional groups of polymer/NCs). These

stiff and rigid intermolecular bonding could boost the bond dissociation energy (thermal

energy) required in chain cleavage at crucial decomposition stage [104]. By strong

intermolecular interactions, the decreased chains mobility of matrix phase in the vicinity

of the NCs also possible to promote the diffusion of degradation products from the

system. Hence, the highest mass loss rate would be reached tardily at higher Td.max [94].

When there is lack of evident shifts of Td. max to higher temperature even though the

presence of high NCs loadings, this implying the thermal stability of nanocomposite is

merely related to the good interfacial adhesion between the matrix and good dispersed

phase [75]. The thermal stability of the polymer matrix at T50 can improve to higher with

the formation of char originated from the cellulosic filler decomposition. This could

hinder the out-diffusion of decomposition products of polymer under the condition of

higher thermal stability of polymer than NCs facilitating the prior char formation from

degraded NCs [25].

In contrast, the deterioration of crucial thermal stability of polymer at Td.max after

inclusion of NCs could be also signified from the T50 on DTG curves shifted to a lower

temperature [10]. One can deduce that the poor thermal stability of NCs as well as lack of

adhesion of NCs to matrix are liable to earlier degradation of composites. One of the

factors weakening the inherent thermal resistance of CNCs mostly belonged to the

presence of high-heat-sensitive acid sulphate groups (upon acid hydrolysis) which could

catalyze the thermal degradation of cellulose even at low temperature through

dehydration reaction [77,105]. Another factor involves the imperfect purification step of

50
cellulose fibers during preparation of nano-size cellulose, subsequently leading to as-

produced nanocelluloses still containing certain amount of thermally-unstable non-

cellulosic material [84]. Since crystalline structure is less sensitive to thermal attack, the

inherent crystallinity of NCs cut down by intensive high-pressure homogenization or acid

hydrolysis during preparation of NCs has consequently caused the poor thermal stability

of NCs. Overall, the poorer cellulose thermal behavior than based polymer can lead NCs

start to decompose at lower degradation temperature than based-polymer. The degraded

cellulose residues would weaken the thermal stability or reduce Td.max of composites [75].

At such higher Td.max of based-polymer than NCs, it is interesting to note that the

influence of the prior second degradation step of NCs on the main thermal stability of

nanocomposites could also be evidenced by the lower T5 of nanocomposites with high

amount of NCs [25]. In addition, the thermal degradation of substantial low-thermally-

stable-NCs could result in the increased degree of weight loss which contributing to

another detrimental effect of high NCs content besides the decrement of Td.max [58].

Moreover, the reduced formation of thermally stable interface between NC-matrix under

the agglomeration of high amount NCs might considerably decrease the efficiency of

resisting heat flow to the composite in line with lowering heat energy (lower Td.max)

required to decompose materials [29].

3.6.3 Third Degradation Step

The third step mass loss is regarded to degradation of charred residue into gaseous

products [25]. The charred residue or ash could be referred to the remaining weight% on

the TGA curve and in fact, it is designated to degradation product of second degradation

51
step containing carbon like polymer and cellulose, thus so-called carbonic residue [25].

One might observe is the lesser amount of ash content could be obtained upon addition of

NCs, this is mainly related to the stronger thermal stability of composites to against heat

and even inhibiting the ash formation [7]. As the char residue could be increased with NCs

contents without significant mass loss in third degradation step, one can thus estimate that

the composite material possesses good flame resistant property which is dissimilar to

aforementioned strong thermal stability. As contributed by high flame retardant tendency,

the char formation is beneficial to protect composite materials when encountering

intensive heat sources, therefore lower mass loss and high thermal stability. Such flame

retardation potential could be mostly found in the nanocomposites reinforced by acid-

hydrolysis-produced CNC which containing sulphated groups with intrinsically flame

resistant [3,29]. It is worth to remind that the produced sulphate group during sulfuric acid

hydrolysis could be continuously increased with increase in the hydrolysis time [106].

3.7 Vicat Softening Temperature

For the polymers and composites material used in an elevated temperature application,

the heat resistance is the most important consideration point which could be evaluated by

vicat softening temperature (VST). Generally, the measurement of VST can be conducted

using the VST tester in accordance with standard of ASTM D 1525. The VST test

enables the users to find out the ability of their product towards retaining the surface

properties at high temperatures. The incorporation of NCs could offer better thermal

resistance to pure polymer can be evidenced by the increasing values of VST [61]. Within

composites systems, VST value mainly depends on the uniform dispersion of NCs and

52
corresponding network structures throughout the nanocomposites, which generating high

resistance to the heat flow. This positive outcome also can be contributed by the high

ability of strong interfacial interaction between matrix-nanocellulose to impede the

movement of adjacent polymer chains and even to prevent the polymer matrix from

undergoing plastic deformation and loss of elastic properties induced by heat. The heat

resistance increases continuously with NCs loading, this behavior is mostly related to the

free movement of polymer chains could be more extensively confined by larger amount

NCs through strong filler-matrix interaction [61]. It is desired to obtain VST value of much

higher than room temperature, taking into account the importance of available usability

and sustainability of tested nanocomposites over a wider temperature range or higher

temperature [58].

4. FACTORS INHIBITING IMPROVEMENT OF MECHANICAL-THERMAL

PROPERTIES

Based on aforementioned discussion, one can conclude that the nanocelluloses possess

ability to improve mechanical and thermal properties of nanocomposite by their intrinsic

reinforcing potential, enabling to broaden the application potentials of based-polymer.

With an attempt to have a detailed overview, the final expressions about the relevant

reinforcing system of NCs on polymer have been proposed in Figure 9. As recorded in

Figure 9, the reinforcing system of NCs would be collapsed by lack of either high aspect

ratio or high crystallinity of NCs, which could explain the movement of widespread

usage of cellulose-nanocomposites. In other words, the incorporated nanocelluloses are

useful only when they demonstrating high aspect ratio and high crystallinity within

53
cellulose nanocomposite, except some factors have disabled the high reinforcement of

NCs as listed belows:

a) Inappropriate manufacturing conditions of NCs

b) Utilization of hydrophobic polymer

c) High loading level incorporation of NCs

d) Improper nanocomposite processing conditions

It should be noted here, these four issues have been usually known as common reasons

towards reducing the aspect ratio and/or crystallinity of NCs.

On the other hand, others challenges of restricting reinforcing potential of NCs to lower

extent are still being investigated, this could include the existenence of impurities (water,

bubbles or degraded material) throughout the nanocomposites. Firstly, the water has been

recognized to exert plasticizing effect and cause hydrolysis of hydrolysable polymer.

Secondly, the bubbles might be unintentionally formed during improper processing in

line with resulting in voids/cavities formation throughout matrix. Thirdly, the degraded

material could act as defects to exert plasticizing effect on matrix and reduce thermal

stability of nanocomposites. Improper nanocomposite preservation conditions also a

possible factor to deactivate the reinforcing action of NCs. It is well realized that the

absorbed water by nanocomposites could drastically affect mechanical properties (such as,

compression, flexural and tensile) of the film, while inducing a strong plasticizing effect

on the matrix [27]. These undesirably negative effects mostly happened under inadequate

54
conditioning of samples upon processing. Therefore, storage of synthesized films under

specific environments (oven, dessicator over silics gel or vacuum) are necessary work

especially for hydrophilic based-polymer like PVA, TPS, PVOH and etc.

4.1 Inappropriate Manufacturing Conditions of NCs

According to the aspect ratio formula (length divided by diameter/width), aspect ratio of

NC could be reduced by either decrement of NCs length or increment of NCs size. Under

intensive processing of NCs, the aspect ratio and crystallinity of NCs could be reduced by

breakage of cellulose chains and destruction of inherent crystalline structure. The size of

NCs could be increased by self-assembly (aggregation) during conventional drying of

prepared aqueous NC suspensions.

When acid hydrolysis is used to extract cellulose nanocrystals from cellulose fiber, it is

actually difficult to regulate the processing conditions until optimum parameters (such as

reaction time, temperature, acid concentration) depending on different plant sources

[38,106]
. In order to obtain the desired degree of crystallinity and length of acid-hydrolyzed-

products, the reaction time is a critical condition which should be considered to avoid

extensively decreasing the length of NCs (aspect ratio) ensuring minimize amorphous

phase along the microbrils axis under optimum hydrolysis time. These reductions in

length usually relates to the removal, not only of the amorphous phase, but also to the

partial destruction of the cellulose crystalline regions under prolonged hydrolysis time.

Indeed, surface erosion by acids on the crystalline domains immediately after hydrolysis

of the amorphous cellulosic regions will turn to reduce crystallinity of CNC concurrently

55
[64]
. Similar behavior has been observed when preparing NFC by using mechanical

grinding process which could apparently degrade the pulp fibers’ length. Especially the

application of microfluidizer could cause intensively shortens of chain length compared

to grinder [36]. In opposite, the mechanical fibrillation by using homogenizer process can

cause less damage on the crystalline structure of cellulose [36]. After preparation of

aqueous NC suspension, there is high potential of NC to be attacked by microbial since

cellulose is organic compound. Thus, it is suggesting addition of few drops of

chroloform into suspension for conditioning purpose as specified in Figure 2 [9]. One

should remind that the increased hydrolysis time could also increasingly leave the

residual sulfate groups (SO42-) on CNC which subsequently weakening thermal stability

through the dehydration reaction of cellulose. However, this problem could be solved by

alkali-neutrallization or dialysis [10,41,64].

The important step during preparation of cellulosic nanofiller is the drying of NC

aqueous suspensions as specified in the final step of Figure 2. This is due to the NCs

prepared in form of dried-solid-state are desired to meet the demand of industrial large

scale fabrication of nanocomposites at low cost by its facile processibility using melt

compounding. Indeed, this is one of the most efficient and easy to scale-up method [25].

The drying step is also essential to eliminate the remaining water on NCs to avoid the

undesired plasticizing effect and backbone degradation of hydrolysable polymer through

hydrolysis as mentioned in section 3.5.2. Up to date, there are four drying techniques

have been recently proposed to dry aqueous NC solution as summarized in Table 4, while

each drying approach has significant influenced on final performances of dried cellulose.

56
However, as soon as these polysaccharides nanoparticles are dried by these conventional

drying techniques, strong hydrogen bonds establish and most of the time aggregates are

obtained limiting the nanosized reinforcement [27]. The most significant agglomeration of

NCs upon drying definitely is the conventional oven drying which can change the

nanoscale dimensions of NCs to hundreds of microns or even to millimetres driven by

their high hydrophilic affinity [8,25]. Moreover, oven-drying also produces a mat of

microfibrils where mostly none of them remained individualized [36]. Although the drying

of NCs suspensions using freeze-drying and spray-drying can more preferably produce

water-redispersible nanocellulose in powder form having nanoscale dimensions, the

different NCs agglomeration mechanisms also might be developed in each drying method
[54]
. For freeze-drying, the dried samples globally formed a mat corresponding to the

microfibril aggregates, in which some of the microfibrils remained distinct. In particular,

the freezing step at −20 °C seemed to play an important role in the formation of

agglomerates [36]. In this concern, the aggregation problem could be recovered by a small

amount of water (~0.1%) which is necessary to stabilize the suspension of re-dispersed

freeze-dried cellulose nanocrystals [27]. In turn of spray-drying, although there are no

microfibrils or bundles could be observed in the case of atomization, the thermal

degradation of dried samples is the main problem predominant the agglomeration. During

this drying process, water was removed in the two first drying processes resulting in the

increasing number of contacts among fibrils followed by degradation of one microfibril

and even implicating the degradation of the surrounding fibrils [36]. The degraded fibers

certainly presented a lower degree of thermal stability than that of the original fibers,

since the degradation began at lower temperatures. Some very recent works have showed

57
that post-treatments such as hydrophobization can strongly improve this thermal stability
[36]
.

It is safe to conclude that these four drying approaches are not perfectly suitable for

obtaining solid cellulosic filler in nanosize based on discouraging results were obtained in

the past, also attributed to the probability of thermal degradation [54]. In this concern,it is

crucial to develop others robust processes to dry NCs suspension, while maintaining of

nano-scale dimensions of the NCs [54]. In general, chemical pre-treatments (before drying

step) can be used to produce dried, non-aggregated cellulose nanoparticles like the

acetylated NCs have ability to be stored in a dry form which possible to be adaptef for

industrial-scale production [36]. On the other hand, a novel drying-redispersion method by

cation exchange of the H+ counterions on CNW into Na+ counterions has been very

recently attempted [9]. It could also obtain the nanocomposite with nano-scale dispersion

of cellulosic filler without undergoing drying under solution casting and melt-extrusion

of starch-based composites requiring water as plasticizer, which allowing cellulose

nanofibers with high water content as the reinforcement [24].

4.2 Utilization of Hydrophobic Polymer

In case of selection of hydrophobic polymer (such as PLA, PE and PP) as based-matrix in

cellulose-composites, the occurrence of reduced aspect ratio of NCs would mostly be

happened. As originated from hydrophilic characteristic of NCs, the NCs are

incompatible with hydrophobic matrix based on their lack of similar functional groups for

reaction. Based on the high interfacial tension at the interface between NCs and

58
hydrophobic polymer, they have high tendency to repel with each others followed by

facilitating the formation of cellulose aggregates or clusters driven by intra-/inter-

molecular hydrogen bonding among adjacent NCs [43,53,60,99]. The increment of filler size

by aggregation has therefore explained the decrement of aspect ratio which could bring in

the several detrimental effects.

Importantly, the low aspect ratio NCs would be less efficient to exert reinforcing action

on hydrophobic matrix, explaining the inferior mechanical-thermal properties of

composites. Indeed, the possible occurrence of phase separation forms cavities/holes

formation at the filler-matrix interfaces while causing the discontinuity of stress transfer

and also insufficient heat resistance/stability [107]. Due to the full reinforcing capabilities

of the NCs cannot be exploited within hydrophobic matrix, the resulting low usefulness

might leave composite vulnerable to environmental attacks subsequently decrease its life

span [43,53,60]. The poor adhesive behavior of NCs towards hydrophobic matrix would

induce the non-uniform dispersion of NCs by hydrophilic affinity among NCs, explaining

the poor mechanical-thermal properties of nanocomposites mainly due to the nucleation

effect of NCs could not be induced at the poor interface/contact between the filler-matrix
[9,86,99]
. Moreover, another adverse effect is because of the options of based-matrix in

nanocomposites has been restricted to compatible/hydrophilic polymer for ensuring the

nanoscale-dispersion level as well as the improved properties [32]. As a result, there have

been very few reports on using hydrophobic thermoplastics such as polyolefins [87] The

worse is the processing of nanocomposites is difficult to be scaled up to an industrial

level since the melt extrusion process for the compounding of polyolefins are not

59
promosing unlike the solvent casting is almost available for miscible system [87] This is

the main reason water-soluble polymers or latexes have been used as matrix resins to

improve the dispersion property [87] However, these fully hydrophilic nanocomposites are

inherently highly sensitive to humidity. Therefore, it is difficult to confirm absence of

water in the film after synthesizing which requires further attention. The storage of films

under specific environments (silica gel and vacuum) is an important conditioning step to

prevent water from inducing a strong plasticizing effect and greatly affecting the

properties of the film [27]. Eventhough the unmodified NCs are poorly compatible to

hydrophobic matrix, however, the lack of strong interaction also could be beneficial to

facilitate the NCs’ nucleating action by less restriction of molecular motion, and effective

recrystallization process can be expected.

With an attempt to solve the problem of lowered aspect ratio, the factors of causing

hydrophilic affinity of NCs should be comprehended and overcome primarily towards

enhancing the compatibility between apolar matrix and NCs. It is well-established that

the nano-scale cellulose structures with highly developed specific surface (S) have an

increased thermodynamic potential (G) (ΔG = σΔS<0) which is the main cause of

instability of NCs to draw the aggregates close to each other [53]. Since the high surface

energy has been investigated as the main cause of incompatibility, a nano object or phase

must decrease its surface energy, in order to achieve a more stable state [53]. Inasmuch,

many efforts have been focused on tuning the specific surface energy (σ) of NCs,

intending to modify the surface of NCs into surface with lower propensity to form

hydrogen bonding and higher repulsive effect among each others [53]. As a result, the high

60
aspect ratio of NCs could be retained by preventing cellulose size from becoming larger

and even to recover the nano-reinforcing effect of cellulose [108]. As benefited from the

high density of -OH groups exposed on NC surfaces which are high chemical reactivity,

NC surface can be readily modified by various techniques as summarized in Table 5.

These surface modifications of nanocelluloses can be broadly categorized into five

distinct strategies: (i) via introduction of electrostatic charges, (ii) adsorption of

molecules to the surface of the particles, (iii) chemical modifications, (iv) physical

modifications, (v) bacterial modification. Most of the surface modifications of NC are

based on the aim of reducing specific surface energy, which are the critical steps to

reduce the intermolecular affinity between NC facilitating the NCs turn to be more

compatible to hydrophobic matrix. Among surface modifications, the introduction of

hydrophobic layer on NCs is a most common strategy used to modify surface energy by

decreasing hydrophilicity of NCs. While the NCs with gained hydrophobicity tend to be

more compatible with hydrophobic matrix through specific chemical bonding and also

possibly bonded by a weak Van der Waals force [99]. Since the aforementioned surface

modifications enables NCs to become more covalently attached to the polymer without

high propensity to induce NC-NC self-assembly, the consequently uniform dispersion of

hydrophilic NCs in the matrix could be anticipated [1,63,87]. Essentially, the homogeneous

dispersion of NCs is a critical condition for ensuring the ability of NCs to exert

reinforcing action by the higher extent of NCs having contact with surrounding matrix.

This condition therefore allows stronger interfacial interaction to initiate stress transfer

and higher chains movement restriction to prevent chains flowing. Since the increasing in

the number of primary nucleation sites is an important condition to improve nucleating

61
effect, the higher distribution level of modified NCs in the hydrophobic matrix could

realize the increased quantities of primary nucleation sites for inducing crystal packing as

well as enlarging the crystalline regions of polymer [9,86].

Without applying the surface chemistry alternations on NCs, another process has also

recently been proposed to endow nanocellulose with a good aspect ratio and

homogeneous dispersion in hydrophobic polymer. This process belongs to the

modification of melt-compounding technology (i.e. extrusion) in which the polymer-NC

masterbatch additionally prepared prior to carry out melt processing of nanocomposite,

while this movement is much closer to an industrial process with immediate potential to

be realized. With an attempt to prepare masterbatch, the NC solution is first mixed with

the hydrophobic polymer powder to reach the desired dry weight ratio in suitable solution

(mainly organic solvent), followed by a series of stirring, sonication and centrifugation

[23,33,82,109]. Subsequently, the polymer-NC masterbatch could be obtained by

subjecting the centrifuged compounded mixture to freeze drying after being frozen by

liquid nitrogen to prevent settling of polymer powder and aggregation of NCs [23]. Finally,

the obtained freeze-dried polymer-NC masterbatch is then available to be melt-blending

with the same polymer medium through extrusion-compunding after being crushed into

powder form [23,33]. By this quite unconventional approach, the undesired flocculation of

hydrophilic NCs could be avoided during melt processing of composites, facilitating the

homogeneous dispersion of hydrophilic NCs in matrix [82]. Unfavorably, the dried sheets

of masterbastch possible contain part of the hydrogen bonds between NC-NC which are

still inevitably preserved in case of high NCs contents [1]. One can note that the polymer

62
built-in in masterbatches should be the same type with bulk polymer used in end-

nanocomposites considering the desired strong bonding ability by their chemical

similarity. For instance, polycaprolactone-grafted cellulose nanocrystals have been used

as “masterbatches” for melt blending with a PCL matrix [43]. In a similar manner with

applying modified processing technique, it has been investigated to possibly mix NFC

suspension with dissolved hydrophobic polymer by organic solvent via solvent solution

casting as will be further descripted in section 4.3.1.

4.3 High Loading Level of Incorporated NCs

In the case of the polymer which possibly improved by the introduction of nanocelluloses,

the properties of the nanocomposite further enhanced by increasing NC content might be

realizable [110]. Theoretically, the higher loading of cellulose nanoparticles results in more

rigid and compact compounds. Practically, however, the reinforcing effect at higher

cellulose loading levels might be suppressed and even deteriorated when NCs loss its

high aspect ratio due to their high tendency to agglomerate with each others. In most

factors, such optimum loading level could be either positioned as the: (1) percolation

threshold, (2) saturation level of homogeneous dispersion, or (3) NC inclusion of

reaching optimum properties. For the first factor, the cellulose fibrils no longer form the

fibrils network instead of having tendency to form entanglement and even agglomeration

once the saturation of percolating cellulose network is reached. In worse, when optimum

level might be undesirably lower than percolation threshold which makes the amount of

added NCs is considered excess eventhough concentration below percolation threshold.

This is probably due to cellulose network becomes early oversaturated [26]. For the second

63
factor, when the loading is reached beyond the saturation level of dispersion, the

excessive cellulose particles tend to be self-separated from the bulk composite as

aggregates. This is attributed to hydrogen bonding forces or Van der Wall’s force

developed between matrix and NCs habe been weakened by sharing of energy for

initiating the intra-/inter- molecular hydrogen bonding between hydroxyl groups on

cellulose molecules [26,63,99,102]. While the third factor, when loading level increased

up to a maximum value of reaching greatest properties, the higher quantities of filler

might not further increase the reinforcing effects of NCs to higher extent instead of the

the properties are drop or reciprocal to the loading levels above the optimum loading

level.

Besides inhibiting the reinforcing capability of NCs, the high loading level is also

expected to induce several undesired effects. Since the good filler dispersion is the key

factor of enabling NCs to reinforce polymer properly, the excessive NCs tend to restrict

the homogeneous dispersion in matrix by initiating entanglement or even agglomeration

as mentioned previously [99]. Such agglomeration caused by high loading level could

deteriorate the properties of composites through high heterogeneity of two phase matters

occurred between the cellulose aggregates and matrix, which limiting the extent of

reinforcing improvement contributed by cellulosic fillers [15]. This condition is more

significant for the hydrophobic polymer which considerably posseses lower optimum

loading level of NCs as well as early oversaturation of NCs within matrix by their high

phase’s interfacial polarization. More specifically, the intermolecular aggregation of NCs

as shown in Figure 4(b) throughout the polymers could result in inferior tensile properties

64
by uneven stress distribution as mentioned previously [61,73]. Also with losing nanosize

dimensions at high loads, the presence of micron sized aggregates is expected not

restricting the movement of polymer segments under stress, consequently leading to

[61,99]
higher elongation at break (ductility) associated with reduced modulus . Moreover,

at a comparatively higher loading, the micro level agglomeration could facilitate the

formation of flaws in composite structures by high phase’s heterogeneity which

subsequently weakening the mechanical properties of the composites [61].

From the above-mentioned detrimental effects, it is ideal to adjust the high loading levels

to reach the concentration lower than the optimum loading level to achieve outstanding

properties of the composites. However, the low loading levels are considered as non-

economic production of NC-based nanocomposites for an industrial large scale

application [106]. In order to realize the incorporation of high amount NCs without losing

reinforcing effects, achievement of homogeneous distribution of NCs in polymer is the

main factor considered in generating barrier on inherent NC agglomeration [111]. As

known that the homogeneous dispersion of high amount NCs is the key challenge to

prepare such composites, the dispersability of nanofillers in the polymeric matrix would

require innovative processing steps irrespective of surface modification of NCs [12].

Recently, several novel processing techniques have been proposed by researchers as

shown in the following subsections, with attempts to minimize the agglomeration

problem and even maximize the interfacial interaction between matrix and high loading

NCs [111]. These techniques have the common purpose that expectedly retaining the high

65
aspect ratio of NCs towards recovering the inherently strong reinforcement provided by

high amount NCs.

4.3.1 Casting-Evaporation Process

Out of the several template approaches proposed, the solution casting is the most

commonly used processing strategies of high loading level NCs in polymer. As compared

with the injection molded samples, the nanocomposite prepared by solution casting tends

to have more uniform filler distribution. This is mainly contributed by the high mixing

effect during the preparation of nanocomposites solution under constantly high spinning

speed enabling the fillers to be distributed equivalently throughout the polymer solution

eventhough at the high quantities of NCs [25,43]. One can note that the preparation of

nanocomposites solution using either mechanical or magnetic stirring under heating is an

important step of obtaining solid nanocomposite film by casting-evaporation. The crucial

condition of solution blending step is the ability of polymer to be fully dissolved in the

medium for completely mixing with NCs solution. Unlike the hydrophilic polymer that

can be hydro-soluble in water medium with hydrophilic NCs, the hydrophobic polymer

matrix cannot be simply processed by aqueous solution casting instead of requiring

specific organic solvent or non-polar solvent, e.g. DMF, chloroform, NMP. Meanwhile, a

risen problem is the high hydrophilic affinity of NCs to agglomerate in the apolar

medium by high surface energy, thus the aqueous NCs suspension is solvent exchanged

to specific solution by centrifugation prior to mix with hydrophobic polymer solution,

allowing the solvent treated NC could be kept away from agglomeration by reduced

surface energy [9,108,111–113]. This process is typically named as solvent-solution casting. In

66
addition to solvent solution casting method, the high surface energy of NCs that is

favourable to induce aggregation could also be reduced by surface modification as

described in section 4.2, resulting in higher mixing ability between hydrophobic matrix

and NCs and weaker attraction among the NCs [66,108]. It is notable that the dispersion of

nanoparticles in the nanocomposite film also strongly depends on another processing

condition, i.e. mixing time. This is a parameter which should be carefully selected in

order to guarantee the adequate time of allowing NCs to well interact with polymer

molecules, especially long mixing times is also desirable to ensure the homogeneous

distribution of NC [26,60,91].

It is interesting to analyze the formation of solid nanocomposite film by solution casting

as outlined in Figure 10(a). In general, the casting-evaporation is two consecutive steps

consisted of solution blending under stirring and heating followed by evaporating the

solvent conducted above the glass transition temperature of the polymer [26,111]. During

the slow evaporation by drying of the composite from water/organic solvent, the

progressively reduced solvent content could induce the Brownian motions of cellulose

particles or polymer molecules in the suspension. As the Brownian motions become

intensive, the molecular rearrangement tends to increasingly facilitate the cellulose

particles or polymeric molecules getting closer and deform. This trend is expected to

generate the following effects (1) completely relaxing of resulting structure upon the

coalescence of polymer particles, (2) completely disappearance of boundary between the

former particles by chain diffusion. Both effects are the main conditions to initiate the

formation of continuous nanocomposite films

67
As driven by these effects, the direct interaction and entanglements between NCs and

polymer chains consequently synthesizing the solid nanocomposite film containing the

uniformly dispersed polysaccharide nanoparticles [71]. Apart from casting-evaporation,

composite films can also be produced via alternative techniques such as freeze-drying of

nanocomposite suspension and compression molding of melt extrudates [32]. However,

stronger reinforcing effect has been reported for nanocomposites prepared by casting-

evaporation. This is due to the more predominant formation of cellulose network in the

evaporated films since the Brownian motion has promoted the linkage between NC-NC

through hydrogen bonding upon obtaining favourable dispersion property of NCs [27]. An

important issue should be considered for the casting-evaporation method is the

impractical solution for industrial scaling-up application since it is a time-consuming

process by slow evaporation with multi-steps unlike single step finishing in extrusion-

injection molding process.

4.3.2 Impregnation

Impregnation is another possible processing technique of nanocomposites involving high

volume fraction cellulosic nanoparticles. This technique is more suitable for stiffness and

strength of the composite contributed by cellulose nanofibers while the filling of high

filler volume fraction has been a challenge. As outlined in Figure 10(b), the impregnation

consists of two consecutive steps involving the first formation of highly porous nanofiber

network followed by subjecting dried fiber network to impregnation in polymer solution

[111]
. For the first step, the wet cellulose nanofiber network is prepared via membrane

68
filtration of an aqueous cellulose nanofibers solution driven by vacuum effect [32,62]. After

that, upon the complete filtration of water, the highly porous nanofiber network is

available to be torn off from membrane substrate [62].

For the second step, the prepared nanofiber sheet can be availably impregnated into a

very dilute as well as low viscosity polymer-solution under reduced pressure condition

which approximate to vacuum [62]. During impregnation, the mixture would be processed

into the formation of composite by filling the cavities/porous of nanofiber network with

polymer [32,111]. In the case of hydrophobic polymer solution, an additional step prior to

impregnation should be carried out by immersing the synthesized cellulose network film

in organic solvent to enable solvent exchange [110]. For the final finishing step, as long as

the solvent has been fully volatilized, the compression molding is then carried out to

induce consolidation of mixture into nanocomposite with desired characteristic laminated

structure. It is almost no significant delamination problem could be detected between

polymer layer and nanofiber layers by magnification of the interface further, proving the

successful bonding between NCs-matrix as well as good properties of nanocomposites [62].

4.3.3 Layer by Layer Assembly

Another rather facile method has been useful to produce composite films with

maintaining nanometer precision of high amount cellulose fillers, so-called layer-by-layer

assembly (LBL) [32]. The generation of this idea is originated from from a traditional LBL

method by which thin films particularly of oppositely charged layers are deposited. Up to

date, thin film LBL assembly technique has been innovatively applied on cellulose

69
nanoparticles by synthesizing multilayered films [111]. On the basis of traditional LBL, the

cellulose nanoparticles act as main components to be anionic charged in contrast to

cationic charged polymer films, e.g. polyelectrolytes, ammonium groups of chitosan or

highly deacetylated chitosan [12,111,114]. By the existence of two opposed charges, the

hydrogen bonding or electrostatic interactions could be developed between the NCs and

matrix, with desired to effectively stabilize the huge amount NCs [32,111]. The principle of

nanocomposite formation is based on sequential adsorption of positive or negative

charged species layer by layer alternatively which are deposited through spin-coating or

solution-dipping [32,111]. For each adsorption step, the excess or remaining solution is

rinsed with solvent and thus a thin layer of charged species on the surface ready for next

adsorption step is obtained [32,111]. The number of adsorption steps could be controlled

depending on interest in order to achieve the layer-by-layer polyelectrolyte film with

thickness control in nanoscale, implying the incorporation of more and more amount NCs

is possible [111,114]. Consequently, the adsorption of the NCs on matrix drives the growth

of the bilayers and even the multilayered films could be obtained [111]. Throughout the

synthesized nanocomposite film, the same charged species tend to generate electrostatic

repulsion effect among anionic charged NCs, enabling to resist them to react with each

other, matching with the effect of [32,111].

A novel LBL assembly technique has been related to conventional solution dipping

associated with application strong magnetic field as shown in Figure 10(c) by taking the

superiority of nanocrystals to orient along their long axes perpendicular to the field

direction [111,114]. Dissimilar to conventional method which does not require highly pure

70
components and sophisticated hardware, the orientated self-assembled films would be

manufactured under long exposure to the magnetic field. As stimulated by magnetic field,

a torque would be exerted on the nanocrystals to initiate the reorientation mechanism,

which contributing to uniform-dispersion of high amount NCs could be achieved on each

polymer layer in multilayered films [114]. This could be explained by such reorientation of

nanocrystals has optimized the order of layered structures and minimized the filler-filler

contact, enabling to assemble adsorbed layers in high density packing consequently [41,111].

However, this method only could allow the cellulose concentration up to about 16 wt%

considering the twist elastic barrier would be generated to inhibit the reorientation, which

leading to the concentrated suspensions become more tightly twisted [114].

4.4 Improper Nanocomposite Processing Conditions

During processing of nanocomposites, the processing conditions have an important

impact on the resulting composite performances [25]. Without the proper composite

processing, the reinforcing mechanism of NCs which determine the high performance of

nanocomposites might encounter mulfunctioning. Hence, an understanding of the

production process of NC-filled nanocomposites is extremely important especially the

conditions of process operating as discussed in the following sub-sections [91]. Basically,

the classical techniques that have been employed to process cellulose nanofibers-

reinforced nanocomposites involving the solution casting, two-roll mill mixing, extrusion,

injection moulding or thermoforming, hot-pressing, and etc. [27,94]. The processing

conditions mostly depend on different form of nanocellulose which should be subjected

to suitable type of composite processing method to ensure the nanoscale distribution of

71
NC in matrix. For instance NFC which is more unsuitable than CNC for extrusion

compounding as realized from the ease of coaggregation and strong entanglement among

the long nanofibrils via strong hydrogen bonding [87,102]. This is the main problem of

NFC’s network structure and high aspect ratio which are limiting the processing method

by restraining the well-dispersion of fillers.

4.4.1 Inappropriate Processing Temperature

For the processing temperature above acceptable level, the intensive heating may lead to

thermal degradation and even breakage of both matrix chains and cellulose chains by

high chains’ dissociation energy [115]. Therefore, the lowered aspect ratio by decrement of

NCs’ length can be expected from the degraded NCs associated with the crystalline

structure may be destroyed at high temperature, even to tampering the reinforcing ability
[23,90]
. The worse outcome is the chain-scissioned NCs possible to concentrate as small

particles or defects which are prone to aggravate the poor properties of matrix, such as

initiating propagation of cracking when being subjected to tensile straining [115]. In this

concern, it is delicate to control the processing temperature above the polymer melting

temperature but standardized to below 180~200°C which is the temperature range of

cellulosic material starts to degrade [8,32,116]. Especially in case of the CNC extracted from

sulfuric acid, the resulting appropriate processing temperature is considersably lower than

such temperature range since attached acid sulphate groups could catalyze the thermal

degradation of cellulose through dehydration reaction [77,105]. This implies the blending of

NCs in thermoplastics is limited since most of the thermoplastics are processed at

temperatures ranging between 150-250 °C, causing infeasible to undergo melt

72
compounding step [8,32,116]. Moreover, the extensive heating is also potentially occurred

during compression moulding when the temperature and time of thermos-pressing above

standard level, the ensuing polymer degradation is well-known to generate carbon

dioxide into the form of bubbles throughout the samples. Meanwhile, when insufficient

processing heat (temperature) is set during melting processing or compression moulding,

the resulting high viscosity of the melt might hinder the NCs rearrangements for good

filler dispersion in matrix. By the hindrance of NCs rearrangements, the interconnection

among NCs for dense cellulose network building also difficult to be initiated in melts

even if high enough aspect ratio [1]. Under this condition, the properties of the composites

might be moderate due to the insufficient interfacial adhesion developed between the

matrix and the NCs [88].

4.4.2 Inappropriate Compounding/Mixing Speed

Regardless of which types of processing techniques, the appropriate rotating speed of the

mixer are necessary to compound the composites, while the mixer can be either stirrer or

extruder screw. Undoubtedly, the high compounding speed desired to increase the degree

of mixing between the two phases of matrix and fillers associated to facilitate the

homogeneous distribution of NCs. However, if the rotating speeds above the acceptable

level, the extreme shear force might exert damage on the cellulosic of fillers by causing

friction and breakage, and also might cause the breakage of the polymer chains to reduce

molecular weight [25]. Both of the low molecular weight of polymer chains and breakage

of the NCs can induce detrimental effect on the final properties of composite. The

discouraging results could also be obtained from too low rotating speed which might be

73
inadequate to mix the compounds well leading to a coarsely blended composite by

insufficient miscibility of constituents [83,115]. In the case of the solution blending for

casting-evaporation, eventhough the high stirring speed desired to accelerate the

compounding reaction, the opposed effect might be the formation of bubbles induced by

entrapped air [65,91]. This can be deduced from the surrounding air tends to react with

high-speed rotating solution during blending process. The discontinuity of matrix by the

existence of voids/cavities is well-known to result in lower efficiency of stress transfer

from matrix to the load bearing entity (filler) [61,73]. Hence, it is has been well-perceived

to adjust the stirrer-treatment to a lower speed while compensated by a longer mixing

time to eventually facilitate the uniform dispersion of NCs. Eventually, the reduction of

void contents in the composites can be expected [91]. When voids already existed in the

obtained mixed translucent suspensions afterthe NCs have been well-dispersed, the

solutions are better to be degassed (to eliminate entrapped air) in the vacuum oven prior

to casting-evaporation [65]. In turn of the extrusion process, operating parameters of screw

rotation speed must be carefully controlled to minimize NC and matrix degradation

resulting from shear stresses [32]. It has been reported besides the tensile stress, the yield

stress in flexural tests for the composites could also be decreased with the increase in

screw rotation speed [6].

4.4.3 Improper Dealing of the Presence of Water

Since the drying of the NCs is not recommended in section 4.1, the preparation of

cellulose nanocomposites by melt-extrusion using aqueous NCs suspension is a possible

approach to avoid the complicated self-assembled tendency of NCs especially oven-

74
drying would induce irreversible aggregation [24]. By usage of water as a carrier, the

hydrophilic cellulose particles tend to interact with water molecules, which enabling

better separation distances among NCs subsequently promote good dispersion of

nanofillers [53,54]. It is very common to premix the undried NCs suspension with polymer

first prior to feed into extruder. However, the nanoscale-dimension of fillers could not be

guaranteed in the end-product. Instead, the NCs in premix mostly form aggregates during

melt-extrusion since the processing heat likely to induce drying of wet NCs as similar to

oven-drying [26,35]. Moreover during improper dispersion of NCs by aggregation, there is

also possible formation of voids and/or cavities in polymer. In order to assure the NCs

properly redispersed during melt processing, another effective extrusion method is

carried out by separately feeding the polymer and aqueous NCs suspension. Once the

polymer has been firstly processed into hot melt, it is immediately followed by pumping

the suspension of NC into hot polymer melt of another section during extrusion process
[25]
. This is known as liquid-feeding method in contrast to previous solid feeding direct

mixing method. Such liquid-feeding method could keep away from the problem of

irreversible NCs agglomeration NCs and thus better NCs dispersion [35]. However, the

pumping of aqueous NCs suspensions into the hot polymer melt has also been found to

be problematic in the end-products since there is a risk of foaming due to large amount

steam would be generated from the evaporation of solvent (i.e. water) [26,56]. As the steam

failed to be escaped from matrix, certain amount bubbles are expectedly remained

throughout the matrix to induce the voids/cavities formations [61,73]. However, the steam

problem still can solved by increasing amount of venting for degassing by equipping

venting system on extruder or by lowering the screw speed as well as the throughput [56].

75
Nowadays, the better degassing technique has been proposed through redesigning the

extruder screw in accordance with high L/D ratio. Other than that, the machine’s barrel

also can be redesigned [6]. In the case of the internal voids already existed in extrudates,

the properties of composites deteriorated by low density empty spaces still can be

remedied by increasing molding pressure during the following hot pressing step [90,91].

This is an efficient method to increase density of composites along with possible

reduction of the void content and it is worth to remind that the density of composites

usually serves as a good indicator for the composites’ properties [90].

Irrespective of the above negative effects induced by evaporation of water, the presence

of water at high temperatures also can be detrimental to polymers containing e.g. amide

or ester bonds [26]. In this concern, the other possibility is mixing NC suspension with

dissolved hydrophobic polymer by organic solvent, while the absence of water therefore

allows efficient compounding and drying of NC with less aggregation [26]. However, this

is not suitable for industrial large scale production. Other than that, the extrusion of NC

grafted with long chain molecules seems to be much easier and also can be processed in

solvent (i.e. water) free conditions, especially when the grafted chains can melt at the

processing temperature [32].

5. CONCLUSIONS

The introduction of nanotechnology on cellulosic plant sources has opened new

opportunities for the development of new competitive reinforcing agent in polymer,

nanocellulose which also typically named as cellulose nanocrystals or nanofibrillated

76
cellulose depending on extraction approaches. The nanocomposite reinforced with NCs

could be more environmentally benign and possesses greater renewability as compared to

the neat plastic and conventional composites. This helps in overcoming problems

encountered by plastic or reinforcing filler currently in use. For taking full advantages of

nano-size material, the nano-reinforcement achieved by nanocellulose has high potential

to improve mechanical and thermal properties of nanocomposite by two essential

priorities, i.e. aspect ratio and degree of crystallinity which the final geometrical

characteristics depending on the cellulose origin and preparation conditions of NCs. The

main contribution of high aspect ratio is the high specific surface area that could promote

good surface contact between matrix-NCs. The enhanced nanofiller-matrix interfacial

phenomena enables higher efficiency of stress transfer and more polymer chains can be

restricted in movement and flowing. By high enough aspect ratio also, the formation of

strong percolating cellulose network stabilized by hydrogen bonding can be more easily

achieved even by small amount NCs. The center idea surrounding the importance of high

crystallinity index is high nucleation ability of NCs to increase the number of crystallinity

regions in composites by increased primary nucleation sites, therefore higher modulus of

elasticity and heat-flow resistance of samples. The high crystallinity also represents the

enhanced rigidity of cellulose with more tightly bondings, which is beneficial for

producing high-strength and thermally-stable composite. In comparison, the NFC of

higher aspect ratio than CNC is more desired to sustain the improved mechanical

properties of nanocomposites under elevated temperature condition likely by its mutual

entanglement with matrix. However, the CNC of higher crystallinity than NFC tend to

offer better reinforcing effect on mechanical properties of nanocomposites under room

77
temperature condition mainly owing to its stronger nucleating effect and lack of

amorphous regions which is non-beneficial to nanofiller-matrix interaction. It can be

concluded that the improved mechanical-thermal properties of cellulose-based composite

is generally advantageous for various application potential/areas, however this movement

would be only available on NCs without losing its essentially high aspect ratio and

crystallinity index even in polymer matrix. The existence of cellulosic fillers in forms of

reduced aspect ratio and crystallinity might raise a number of challenges in terms of poor

dispersability of fillers, physicochemical incompatibility, phases separation and lack of

filler-matrix interface as well as primary contact sites for nucleating action. The brilliance

of this review is the in-depth overview of several factors decreasing the aspect ratio and

crystallinity of NCs as well as inhibiting the ability of NCs to reinforce polymer. Without

relating to intrinsic conditions of NCs, the impurities problem like bubbles, water, and

degraded material also have been recognized as additional factors of weakening the

performance of cellulose-based composites. Along with overcoming these problems,

numerous attempted efforts have been dedicated by researchers on preventing

agglomeration and facilitating uniform dispersion of NCs in polymer composites. These

works will generally need surface modifications of NCs, altered drying steps of NC

suspension and processing steps of composites, so that they can contribute to competitive

performance of nanocomposites for the viability of such commercialization. Based on the

present review ultimately, one can propose that the organic NC has a meaningful

potential to be developed as reinforcing filler for various polymer, with a big desire to

assure a faster adaptation to pilot/industrial scale equipment.

78
 ACKNOWLEDGEMENT

The authors are grateful for the financial support from Universiti Tunku Abdul Rahman

Research Fund 6200/T54.

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Table 1. Various techniques of preparing purified cellulose fibers from plant sources

Methods Main processing conditions Principles/Mechanisms Effects References

Alkaline i) Aqueous alkali i) The hot alkaline i) Removing certain [4,14,44,47, 48,52,78,112,123]

treatment solution: KOH/NaOH treatment able to dissolve amount of hemicellulose

solution with low non-cellulosic constituent and lignin.

concentration through the mechanism of:

ii) digester/autoclave: hydrolyzation of highly Partially remove

used for alkaline retting branched hemicellulose and impurities covering the

treatment or alkali cooking depolymerisation of part of external surface of fiber:

iii) anthraquinone the lignin. pectin, wax, oils and

solution (selectively): solubilised impurities

used for enhancing the Disruption of OH bonding in ii) to increase

delignification rate and the fiber network structure amount of cellulose

protecting the fibers from by ionizing the hydroxyl exposed on the fiber and

alkali degradation groups of various materials the surface roughness

95
 in fibers to become alkoxide

ii) Fiber-OH +

NaOH→ Fiber-O-Na+

(alkoxide) +H2O,

Bleaching The oxidants could be i) Delignification i) The progressive [4,24,25,33,52,61,64,78,85,123]

treatment liberated from bleaching mechanism is initiated removal of non-

agent in an acidic condition cellulosic amorphous

or under the presence of ii) The liberated oxidant polysaccharides

buffer salts created by (like ClO2) has ability to ii) Upon alkali

acetate buffer solution oxidize the lignin left in the treatment, the further

fibers by attacking the removal of residual

Bleaching agent: aromatic ring of the lignin cementing material

i) Sodium chlorite could result in further

(NaClO2) solution iii) The bleaching fibrilation of the alkali-

ii) sodium process is necessarily treated fibers

96
hypochlorite (NaOCl) repeated with numbers of iii) The loss of lignin

solution times until the permanent facilitating the CNC

iii) hydrogen peroxide white tissues/fabrics are extraction and NFC

(H2O2) achieved based on the ability individualization

of bleaching to destroy iv) Enabling

Buffer solution: natural color matter of fiber amorphous region along

i) acetate buffer the fibrils is more

solution (mainly made up susceptible to hydrolysis

of NaOH + glacial acetic reaction.

acid).

ii) Providing acidic

condition of pH 4~4.8

97
Steam The cellulose were treated Since pressurized steam i) After steam [25,61,117]

explosion in an autoclave or digester penetrates through the space explosion, the middle

treatment with following procedures:. between the fibres, the large lamella and the fibre

i) The fibers is first pressure drop could induce adherent substance

subjected to highly the steam explosion becomes soft and water

pressurized steam for short simultaneously, resulting in soluble that can be easily

time with increased substantial break down of the removed.

temperature lignocellulosic structure,

ii) Pressure was then hydrolysis of the Water soluble fraction of

immediately released. hemicellulose fraction and hemicelluloses can be

depolymerization of the removed by water

The pressure in autoclave lignin components. extraction.

is then dropped rapidly ii) The low

(decompression) by molecular weight

opening the steam lead the fraction of lignin could

98
 material exposed to normal be also extracted

atmospheric pressure subsequently; leaving

iii) The fibers were cellulose moieties intact.

removed from the

autoclave and subsequently

washed in water.

electron- EBI was carried out in i) EBI treatment is i) Compared to raw [118]

beam electron-beam irradiator capable of isolating the fiber, the cellulose

irradiation after being subjecting raw cellulose fibers from raw chains of cellulose fiber

(EBI) fiber to cooking treatments fiber bundles by decreasing were purer and more

in an autoclave using of the content of the lignin and separated

only water without hemicellulose merely ii) The cellulose

chemicals for removing the through water cooking and contents of cellulose

lignin and hemicellulose. bleaching process. fiber were increased

• The irradiation dose ii) It has been used to piecemeal compared to

99
 could be up to 300 kGy decrease cell wall those of alkali cooked

constituents, or degrade and fibers without EBI.

delignify cellulose based

fibers.

Ionic Ionic liquids (ILs): i) Upon the ILs i) Certain amount [17,79]

liquids [emim][OAc] (1-ethyl-3- dissolving lignocellulosic of cellulose and other

(ILs) methylimidazolium biomass at high carbohydrates might be

treatment acetate) (≥95%) temperatures, the cellulose lost in recovered in

rich materials are readily to cellulose rich materials.

Taking an experiment for be obtained by the addition ii) Partial

example: of a variety of precipitating delignification of

0.4 g wood chips (110-550 solvents. cellulose fiber.

M) and 4.0 g IL were ii) Lignin can then be

placed in a flask and heated separated from cellulose rich

at 80 °C in an oil bath with materials by removing the

100
 magnetic stirring for 1 h. residual ILs.

Enzymatic Celluloses enzymes: i) Selective hydrolysis enzymatic hydrolysis is [36,42]

treatment • Cellobiohydrolases of non-crystalline cellulose less aggressive than acid

• Endoglucanases ii) Cellulose enzyme hydrolysis

tends to degrade the lignin

and hemi-celluloses contents

while maintaining the

cellulose portion in cellulose

fibers

Acid • Sulfuric Acid (H2SO4) The acid treatment could Removal of certain [64,69]

Hydrolysis • hydrochloric acid (HCl) hydrolyse some cementing amount of lignin,

materials by breaking down hemicelluloses and

the polysaccharides into pectins in the cellulose

simple sugars. fibers.

101
Table 2. General strategies for preparation of cellulose nanocrystals or nanofibrillated cellulose from purified cellulose fibers

Main processing Principles/Mechanisms Effects References

conditions

(1) Pre-treatment prior to production of NFC

TEMPO mediated 2, 2, 6, 6- The oxidization iii) Contributing [23,25,71]

catalytic oxidation tetramethylpiperidine- process would be to loosen the inter-

1-oxy radical carried out on C6 microfibrils

(TEMPO) with: primary hydroxyl cohesion.

i) NaBr groups of fiber which iv) this will

(Catalyst) selectively converted greatly enhances the

ii) NaClO/NaClO2 into carboxylate ease of mechanical

(Oxidant) groups via aldehyde nanofibrilation.

mechanism

Carboxymethylation • Monochloroacetic Making the surfaces of v) leads the [36,42,95]

acid (MAC) MFC negatively fibrils easier to

102
 charged by the liberate

formation of carboxyl vi) facilitates the

groups with anionic defibrillation of

charges cellulose fibers

Sulfonation Materials required: Generating anionic The negatively [42,50]

i) Periodate charge on the surface surface charges

ii) Bisulfite of microfibrils by could promote

using the periodate and nanofibrillation

bisulfite

Refining using refining discs in As the disks are The closer the fiber [22,36,97]

the presence of water grooved, narrow gape material gets to the

spray. treatment could edge of the disk, the

gradually peel off the finer the pulp can be

external cell wall obtained

layers (P and S1

103
 layers) for exposing

the S2 layer and

loosening the fiber

wall.

Enzymatic Using cellulose Cellulose enzyme iii) Certain [36,42]

treatment enzyme like tends to selectively amount of cellulose

Cellobiohydrolases or hydrolyze the non- and other

C-type crystalline cellulose carbohydrates might

Endoglucanases. like lignin and hemi- be lost under

celluloses contents intensive enzymatic

while maintaining the degradation.

cellulose portion in iv) Partial

cellulose fibers. delignification of

cellulose fiber.

Acetylation using acetic anhydride The grafted acetyl making the fibrils [36,99]

104
 which could provide groups could reduce easier to liberate and

acetyl moieties the hydrogen bonding lee energy required

between the for mechanical

microfibrillated treatment..

cellulose

(2) Production of nanocellulose-CNC

Acid hydrolysis This treatment is i) The acid i) Upon [38,41,49,61,64,78,106,104,120,123]

performed under molecules have main protonation of

strictly controlled ability of releasing oxygen elements,

conditions of hydronium ions (H+) glycosidic bonds of

temperature, agitation, which preferentially amorphous chains

and time. attack the amorphous are cleaved

phases along the following by the two

The concentrated cellulose microfibrils anhydroglucose units

strong acid solutions ii) Above are separated and

105
could be prepared by statement can be even the splitting of

using: supported by the two fragments with

• H2SO4 oxygen elements on shorter chains

• HCl the glycosidic bonds

• Oxalic acid between two ii) After the

• HNO3 anhydroglucose units digestion of

along the lateral amorphous domains,

amorphous portions the high-purity

are highly susceptible individual crystallites

to the hydrolytic are eventually

reactions of H+. liberated with

iii) Breaking down nanometric

the hierarchical dimension

structure of microfibril

bundles into

106
 crystallites intact

(2) Production of nanocellulose-NFC

Homogenization • High-pressure i) Once samples i) promoting the [22,36, 39, 62,70]

homogenizer passed through very delamination and

small-diameter nozzle fibrillation of the

The cellulose slurry of chamber, the rapid pretreated cellulose

is pumped at high change in pressure fibers

pressure for passing causing the large ii) resulting in

through a spring- pressure drop MFC with the higher

loaded valve ii) It is followed specific surface area

assembly in by generation of high and with the lower

homogenizer shear rates associated water vapor

with integral effect of transmission rate

turbulence and iii) high energy

cavitation for consumption.

107
 delaminating the

pretreated cellulose

fibers

Fluidization using Microfluidizer As the pulp slurry i) Able to [36, 42,72,103]

passed through a thin deagglomerate the

Y- or Z-shaped cellulose fibers and

interaction chamber to reduce their

under high pressure, median particle size.

the fibers could be ii) formation of

defibrillated by shear very thin cellulose

and impact forces. nanofibers

Grinding • ultra-fine fraction i) The shearing i) the grinding [35,36, 42,62,93]

grinder forces would be process apparently

Passing the generated by the requires fewer passes

pretreated pulp grinding stones. than homogenizer

108
 between a static grind process to obtain

stone and a rotating The hydrogen bond in MFC.

grind stone in ultra- cellulose fiber or even ii) grinding

fine fraction grinder cell wall structure process can easier

would be broken down degrade the pulp

by shearing forces, fibers and decrease

ii) resulting in the their length, which

cellulose nanofibers might affect the

that compose the cell reinforcement and

wall in a multilayer physical properties

structure are thus of MFC

individualized from

the pulp.

Blending Using high-speed After blending, the However, the [36]

blender at specific pulp show the same obtained MFC

109
 stirring speeds degree of fibrillation suspensions lack of

with less damage than good homogeneity

is obtained with the and pulp fiber is not

grinder treatment and fully defibrillated.

the blender allows to

keep the crystallinity.

Cryocrushing Using liquid nitrogen By using liquid liberating nanofibers [2,36,48,85]

and mortar with a nitrogen, cellulosic

pestle. fibers are frozen. Then

the frozen pulp is

crushed in a mortar

and pestle by high

impact. The exerted

pressure by ice crystals

transferred from

110
 crushing would slash

the cellular wall

High-intensity Using ultrasonic The transfer of sound Making the MFC are [42,62,121,122]

ultrasonic treatment wave cell crusher energy into the kinetic decomposed to NFC.

with some ice energy through

surrounding the cavitation in the form

beaker containing of liquid jet which

pulp slurry. applied on the

cellulose chains of the

microfibrils would

cause the breakage of

weak interfaces among

the nanofibers in MFC.

Kneading Using twin-screw Under high shearing reducing the particle [36,50,51,87]

extruder with forces, the highly size of purified

111
 combination- efficient pulverization cellulose fibers

available twin-screw effect generated from approaching to size

elements screw elements are of nanofibers

desired to separate

individual nanofibers

from the pretreated-

cellulose-fibers

particles in the

presence of water

(3) Post-treatment on acid-hydrolyzed

products

Dialysis. using regenerated the acid sulfate groups Apart from removing [10,36,38, 41, 106]

cellulose dialysis are necessary to be the free acid

membranes (or removed through molecules and non-

tubes), generally with dialysis against ultra- reactive sulfate

112
 12-14 kDa molecular pure water, until the groups, the salts and

weight cut off neutral pH is reached, soluble sugars also

towards recovering the could be removed by

thermal stability of dialysis

CNC

alkali-neutralization* Diluted strong bases The neutralization is The step of removing [49,106]

solution like NaOH another proposed acidic sulphated

solution method used to save groups by dialysis or

the long time of neutralization could

dialysis. The acid be skipped in case of

sulphate groups could another strong acid

be neutralized by (like HCl) is used.

diluted strong bases

solution to obtain the

neutral pH

113
Homogenization By subjecting the Under strong Undesired large size [9,10,101]

CNC suspensions mechanical shearing of acid-hydrolyzed

into homogenizer. effects, the aggregated cellulose crystals can

nanocrystals could be be further reduced

effectively into more uniform

homogenized into a length

homogeneous

suspension.

Microfluidics/ subjecting the Similar to Higher efficiency [9,10,36,101]

fluidization samples into homogenization, it is than homogenization

microfluidizer with able to deagglomerate but requires more

several passes the aggregated passes

nanocellulose fibers

and to reduce their

median particle size

114
ultrasonic treatment Submitting the CNC The sustaining the [30, 41, 106,122]

suspension to impact/hydrodynamic repulsion among the

ultrasonic treatment forces originated from CNCs in suspension

in an ice bath ultrasonic waves could

disrupt the weak

bonding among the

solid aggregates of

crystalline cellulose

The post-treatments are less necessary upon production of NFC considering the size of produced NFC could be further reduced by

more mechanical passes to have higher degree of mechanical fibrillation which required to increase the aspect ratios and even surface

area of NCs available for contact with the matrix [52]. However, some post treatment also has been attempted involving alkali

treatment methylation, acid hydrolysis and enzymatic + mechanical treatment (shredder or refiner) [36].

115
Table 3. Comparisons of nanofibrillated cellulose and nanocrystalline cellulose

Cellulose nanocrystals Nanofibrillated celluloses

Terminologies • nanocrystalline cellulose (NCC) • the designation of “nanofibrillated cellulose (NFC)” is

• cellulose nanowhiskers (CNW). used to label these long flexible nanofibers [121].

• “whiskers”, “monocrystals” and “cellulose • “nanocellulose fiber’’, “microcrystallites’’,

nanofibers” [67,121]. “microcrystalline cellulose”, “cellulose nanofibrils’’,

• The term “whiskers” is derived from its elongated “microfibrillated cellulose” and “microfibrils’ [67].

rod-like appearance

Chemical • The nanocrystals (whiskers) are formed by the • The interconnected nanofibrils consisting of alternating

composition/ intermolecular hydrogen bonding among the cellulose crystalline cellulose and amorphous cellulose strings

structure chains in an ordered manner [121]. [65,121]. This is due to cellulose nanocrystals are bonded

• FTIR: Cellulose peak typically located at 900-895 together by amorphous segments to form the nanofibrils in

cm-1 (related to C-H rocking/deformation vibrations) the cell wall structures of vegetable plants [121].

which is representing -glucosidic linkage between • Less amount hydroxyl groups due to lack of hydroxyl

glucose units in cellulose [2, 49]. groups present on amorphous regions [9,30,40,43].

116
 • FTIR: The stronger absorption intensity of cellulose • FTIR: Similar to CNC [30,40,43].

peak in the spectra indicating higher cellulose content

in CNC [56,104].

Morphology/ • CNCs are typical slender of entirely crystalline fibers • the NFC is normally held by hydrogen bonds to form a

appearance [121]. fine and uniform woven network or a continuous web-like

• Cellulose nanocrystals with needle shaped and network of interconnected nanofibrils with overlapping

network morphologies also have been explored by acid each other [26].

hydrolysis [41,104]. • It can also be existed in form of irregular fibril structure or

• Freeze drying provides a ribbon-like material separated cellulose fibrils, but the continuous network may

assumed to be the product of a significant lateral be more stable than separated nanofibrils during the solvent

aggregation [54]. evaporation by preventing the formation of aggregates [54].

• The spray-dried CNC samples are spherical particles. • Drying the NFC droplet by spray-drying may forms small

If the rough surfaces are observed for the spherical spherical particles configured much the same as with CNC

particles, revealing the agglomeration of needle-shaped [54].

single CNC [54]. • Freeze drying formed ribbon-like structures of the

117
 • The CNCs are mostly existed in aqueous suspension cellulose nanofibrilss with nano-scale thicknesses [54].

with high homogeneity due to the presence of sulfate

groups on the surfaces could create electronic

stabilization among the charged CNCs [41].

Aspect ratio Depending on the cellulosic plant source, purification • Since nanofibers have been designated to size <100 nm in

pre-treatment and controlled conditions of acid diameter with minimum 5 nm across and >1000 nm in

hydrolysis, length up to several micrometers long, the longer lengths of

• Their diameter range between 3–20 nm wide, NFC than CNC usually brings about higher aspect ratio, the

• Their lengths vary between 50–2000 nm long [27,67]. aspect ratio of cellulose nanofibrils is estimated to be much

• Resulting in aspect ratio of 10–100 [46] higher than CNC with at least few thousands

• Due to the small diameter, the aspect ratio (L/D) of [26,62,27,43,45].

CNC is high but lower than NFC, thus CNC has lower • With higher aspect ratio, fibrillated nanofibrils are more

ability to form highly uniform network structure for easily interconnected to form rigid web-like fibrils

inducing reinforcements to a greater degree in networks [22,24,67].

polymers [62, 66]. • However, this formation of network structure might be

118
 • Specific surface area would be increased with disadvantageous to the dispersion of NFCs in a polymer

increasing aspect ratio, estimated to be greater than 100 matrix during extrusion compounding.

m2 g−1 and even up to several hundreds of m2 g−1 • This is because of the ease of coaggregation and strong

[4,64,53]. entanglement among the long nanofibrils via strong

• the CNCs which have a large surface-to-volume ratio hydrogen bonding, and hence, restraining the well-

could increase contact surface with polymer matrix for dispersion of fillers [87,102].

improving surface reactivity at nano-regime [26,119]. • With higher surface area-to-volume ratio than CNC, NFC

normally expected to provide greater reinforcement and

stronger reinforcing effect by increased interfacial

interaction between filler-matrix [62].

Crystallinity • CNCs are found to be very high crystallinity • The diffractogram show a main peak at 2 = 22.5º and

nanoparticles while the crystallinity of CNC is shoulders in the region 2 = 14-17º, high crystallinity index

normally higher than NFC, about 65%~95% • Representing typical Cellulose I (native cellulose)

crystallinities in CNC [55]. diffractogram [61].

• The highly crystalline structure is based on each • Since NFC consists of crystalline parts which linked to

119
 monomer in cellulose chains bearing three hydroxyl amorphous domains, NFC are found to be lower crystalline

groups have ability to initiate extensive intra- and ratio than CNC as deduced from XRD diffraction patterns

inter-molecular hydrogen bonding with each others, • This is due to the existence of amorphous portion without

allowing the crystalline packing of cellulose chains performing crystalline packing, such less-order or para-

into highly ordered crystal structures [27; 32]. crystalline system would lower the overall crystallinity ratio

• The tightly-packed crystalline structure or a denser consequently [43,65].

packing of crystalline regions is responsible for the • However, the XRD pattern of NFC is still similar to CNC

increased crystallinity ratio of cellulose nanocrystals due to the common presence of typical Cellulose I (native

[54,76]. cellulose).

Mechanical • The cellulose nanocrystals have a perfect crystalline • The low microfibril angles like in S2 (with microfibril

performance structure which is high strength, rigidity and modulus orientation almost parallel to the fiber axis) give rise to a

[1,64,123]. large modulus of elasticity, while large angles lead to

• The modulus along the chain axis of the perfect higher elongation at break [22,65].

crystal of native cellulose microfibrils is estimated to • However, the modulus of elasticity (MOE) of native

lie between 130 GPa up to 250 GPa, close to the cellulose microfibrils has comparably lower value than

120
 theoretical modulus of a perfect crystal of native CNC which is estimated to lie between 70 GPa-138 GPa,

cellulose (167.5 Gpa) [12,22,46,65]. depending the numbers of cellulose molecules [1,65,123].

• Based on its fibrillar structure and the large amounts • This can be explained by the the disordered amorphous

of hydrogen bonds, CNCs also own a high tensile segments existed in NFC that is not contributable to the

strength. It is therefore the CNC has high strength of mechanical properties

about 7.5~10 GPa [22,35,65]. • cellulose amorphous regions with imperfect axial

• Thus, CNCs are found to be more preferable as orientation and spaghetti-like arrangement leading to a

strengthening/stiffening agent due to their greater lower density compared to nanocrystalline regions with a

strength and stiffness [23; 52; 41; 82]. lower stiffness [27,65,93,95].

Thermal • Higher decomposition temperature of CNC than NFC • Based on TGA and DTG curve, the first step for NFC has

stability at around 300-350 ºC, mainly contributed crystalline a higher weight loss which originated from elimination of

system with higher ratio is more compact and denser to higher amount water since the chains in the amorphous

resist heat flow [43,75,81,121]. regions are further apart with more available for hydrogen

• For the acid hydrolysis without post treatment to bonding with water molecules [43].

remove the sulfate groups in the outer surface of the • In the second degradation step, it is beginning from

121
 CNC, it has been proved that the thermal stability of ~250 °C while the degradation mainly caused by the

the CNCs would be reduced by the sulphate groups advanced depolymerisation of cellulose, dehydration and

through the dehydration reaction of cellulose decomposition of glycosyl units with the formation of char

[10,38,41,64]. [81].

• However, there are lower mass loss and higher • Although NFCs have been purified from thermally labile

residual mass than NFC due to the flame retardants constituents (lignin and hemicellulose), the lateral

behaviour of acid sulfated groups which is beneficial to amorphous portions might act as structural defects to lower

the char formation towards protecting materials from the overall thermal stability [43,65,81].

degradation when encountering intensive heat sources

[3,29,85,106].

Barrier • FTIR: In the region 1650-1630 cm−1 which attributed • FTIR: In the spectra of NFC, the transmittance peaks

properties to the O-H bending of the adsorbed water, the intensity observed in the region 1650-1630 cm−1 are attributed to the

of transmittance peaks is lower as compared to NFC O-H bending of the adsorbed water [104].

spectra, meaning lower water content [104]. • This is due to the chains are further apart in the disordered

• This is due to the CNCs lack of amorphous phase amorphous regions, water can penetrate into amorphous

122
available for absorption of water molecules regions of NFC [43,54,116].

[9,30,40,43]. • Less tightly-packed crystalline regions to resist water

• Moreover, the tightly-packed crystalline region with entrance.

inter-chains hydrogen bonding in the CNCs is thought • Water molecules would impose detrimental effect on the

to be less inaccessible to water [32,43]. reinforcing ability of NFC.

123
Table 4. Various drying techniques applied on NC suspensions

Techniques Drying mechanism Factors motivating the usage Issues of discouraging the usage

Oven-drying Upon exposing the NCs suspensions in a i) Simply to operate i) The combined capillary and

conventional forced air-circulating oven at ii) Well established diffusion forces resulting from the

high temperature: industrial processes high temperatures and removal of

1) Initially, the external NC surface iii) Saving drying time water would drive the molecular

undergoes water evaporation by heat until the iv) Low cost, high contact of NCs by initiating strong

shrinkage of suspension. conveniency Van der Waals forces and

2) Formation of vapor primarily takes intermolecular hydrogen bondings

place over the NC surfaces, while the among them [54].

existence of vapor–water interfaces would ii) The Van der Waals forces

induce attractive capillary pressures among are expected to hold the fibrils

adjacent NCs. together without hydrogen bondings,

3) Once the capillary tension reaches a merely leading to the formation of

maximum value, vapor diffusion begins to bulk material as long as NCs are

124
 take over. close enough.

4) The circulating air would make the iii) The strong intermolecular

water diffusion rate on the surface become bonding would develop the

faster than interior water transferring during formation of rigid solid aggregates

the last drying period. with ivory-like or stone-like

5) Water of NC suspension could be properties [53,54].

fully removed as the water in the interior NC

suspension is fully evaporated.

Spray-drying This is similar to oven-drying by applying i) The formation of NCs i) The re-aggregation among

high temperature evaporation but the target is droplets could prevent the adjacent NCs might be induced by

droplets of NCs suspension: formation of bulk material by strong hydrogen bonding between

1) The formation of NCs droplets by hydrogen bonding when being the individual NCs [32,54].

fluid atomization of NC suspension. subjected to dehydration. ii) In an attempt to avoid re-

2) The momentum transfer between hot ii) a scalable continuous aggregation, the additional step of

gas and suspension film disrupts the NCs drying process with chemical arrangements on CNC

125
suspension film into ligaments and then into controllable particle size surface is necessary prior to spray-

droplets with diameters from several to tens iii) It is suitable to dry drying.

of micrometers. cellulose nanofibril iii) By the TEMPO-mediated

3) The heat source is mainly supplied by suspensions. oxidation, the ionized carboxylic

flowing hot gas on NC droplets. iv) low labor and groups (-COO-) on NCs could create

4) The waters of NCs droplets maintenance costs demonstrate anion-anion repulsive electrostatic

evaporated by heat source as they fall that spray-drying can be used forces for preventing NCs

through the dryer chamber. for those applications [54]. agglomeration [71,85].

iv) The specific product

characteristics are required

126
Freeze- Freeze drying (FD) is a three-step operation: i) Unlike oven-drying and i) Freeze drying is 5–10 times

drying Freezing stage: NC suspensions are spray-drying, the capillary more expensive than spray-drying

frozen in vials or ice-tray by refrigeration or forces could be minimized [54].

liquid nitrogen (N2) to separate NCs from since the frozen water is ii) NC agglomeration may occur

free water and making the freezing bound directly sublimated into vapor during the second drying stage since

water to be far away from the hydroxyl without any water flowing. the non-freezing bound water could

groups of NCs. be evaporated into water vapor. The

The solidified ice cubes could subsequent diffusion of water vapor

Primary drying stage: Frozen suspensions are entirely maintain the distance might induce structural changes and

then transferred to a freeze dryer equipped by between NCs during drying displacement of NCs, resulting in

vacuum pump which could initiate process, making the distances larger bundles of NCs [41,54].

depressurization for sublimation of frozen among NCs are not close iii) The self-assembly of NCs

water or separated ice crystals. enough to induce molecular might be induced during freeze-

contact by hydrogen bonding drying since hydrophilic affinity

The lyophilization time is normally lasting [41,54]. among CNCs is still high [41].

127
 for 48h~72h ii) The easily dispersive iv) However, the aggregations of

1) Secondary drying stage: Desorption behaviour of freeze-dried NC is freeze-dried NC are loosely packed

of non-freezing bound water (that did not highly favourable in versatile and easily separated by water or

freeze) by heating the product under vacuum. processing or surface organic solvents [41].

While non-freezing bound water is water modification of NCs in organic

reacting with hydroxyl groups of cellulose solvents.

molecules [41,54,120].

Supercritical This process consisted of solvent exchanges i) Unlike oven- or spray- i) The complete ethanol/water

drying and decompression: drying, capillary pressure exchange is non-feasible to CNC

(SCD) 1) Dehydration of aqueous suspension problem among the vapor– suspensions since ethanol is difficult

with ethanol solutions until water is water interfaces might be to disturb the intrinsically strong 3D-

completely replaced with ethanol excluded since the water has hydrogen bonding between water-

2) Replacement of ethanol with liquid been substituted by CO2 CNCs.

CO2 ii) Replacement of water

128
3) Liquid CO2 and the cellulose mixture with liquid CO2 in SCD desired NFC aggregates might be observed

is pressurized and heated to the supercritical to reduce the lateral during ethanol dehydration.

conditions agglomeration of NCs as well

4) The compressed liquid CO2 is as the bulk solid NCs Solvent replacement is a

eliminated by decompression to the iii) SCD appears to be the complicated process

atmosphere [54]. best technique to preserve the ii) High expenses and time

5) As the liquid CO2 is naturally nano-dimensions of CNF. consuming process [54].

transformed into CO2 gas, the dried iii) SCD might be impractical to

fibrillated cellulose could be obtained industry since only small amount

NFCs is available for drying [54]

129
Table 5. Several strategies for modification of nanocellulose

Techniques Main Conditions Principles/mechanisms Effects

(1) Introduction of electrostatic charges

Anionization of i) sulphuric acid Through acid treatment i) The hornification among NCs

NC surface ii) hydrochloric acid [32]. i) sulphuric acid could leave could be prohibited by introducing

sulfate esters moieties on NC stable charged entities, supporting by

surface the negative or positive electrostatic

ii) hydrochloric acid could groups enabling to block cooperative

leave hydroxylated groups with low hydrogen bonding of the cellulose

surface charge on NC surface chains [53].

2, 2, 6, 6-tetramethylpiperidine- The yields of carboxylic acid rich ii) Tends to stabilize the

1-oxy radical (TEMPO) with: surface through the TEMPO- nanocelluloses dispersion in matrix

iii) Catalyst-NaBr mediated oxidation is another through the surface negative

iv) Oxidant-NaClO/NaClO2 method developed to introduce charge. Suspensions of cellulose

negative charge [32]. nanocrystals are often stabilized by

130
 negative surface charges from carboxyl

or sulphate ester groups on their

surface [114].

Cationization of epoxypropyltrimethylammonium Through the grafting of Leading to a stable aqueous suspension

NC surface chloride epoxypropyltrimethylammonium of NC with unexpected thixotropic

chloride, the original surface charge gelling properties while preserving the

could be reversed into positive original morphology integrity of the

charge [32]. crystal. [32].

(2) Surface transformation by adsorption

The use of Surface active agent [53,32]: i) The typical surfactant i) The generation of hydrophobic

adsorbing • stearic acid molecule is made up of a polar layers on NC could restrict

surfactants to • acetyltetramethylammonium heads (hydrophilic) and hydrophobe agglomeration driven by their affinity,

perform bromide, xyloglucan (hydrophobic tails) [35,45, 53]. stabilizing the dispersion of NCs in

noncovalent • xyloglucan block copolymers ii) After the adsorption of non-polar system [27,53].

surface • mono- and di-esters of surface active agent, the hydrophobe ii) Greater adhesion properties of

131
modification by phosphoric acid with could be coated on the surface of NC to the non-polar matrix by their

using layer-by- alkylphenol tails NCs to form a thin hydrophobic reduced surface energy [53,97,99].

layer deposition. layer of about 15 Å [53,97,99].

(3) Chemical modifications

Compatibilizer or • Maleic anhydride (MAH) Maleic anhydride (MAH) is the i) Compatibilizing agent act as

compatibilizing • Peroxide usually used compatibilizer. third material to induce interface

agent Maleated coupling using peroxide as compatibility between two

an initiator has been widely applied incompatible phases since their

to strengthen nanocellulose- functionality has properties

reinforced composites intermediate between those of the NCs

• kraft lignin (from alkali i) The lignin treatment is and the non-polar matrix

treatment), containing –OH carried out by coating NCs with the ii) They are capable of

groups optimal amounts of kraft lignin bridging/bonding the –OH groups of

• Acid hydrolysis lignin [12]. NCs with the matrix material, thus

ii) The lignin treatment also strengthening the filler-matrix interface

132
 could compensate the removal of [44,111].

lignin during bleaching, intending to iii) By improving the interfacial

recover the NC’s hydrophobicity bonding between hydrophilic CNCs

and thermal stability [48]. and hydrophobic polymer matrix,

Using PVOH PVOH acts as a carrier polymer for uniform dispersion of NCs within the

CNCs through hydrogen bonding, hydrophobic matrix could be resulted

when CNCs-PVOH compounded [6,25,44,87].

with polymer, the PVOH forms

CNCs-rich domains in the

continuous polymer matrix [33].

Using partial hydrolyzed PVA The hydroxyl groups of the partial

hydrolyzed PVA could be well-

compatible with the hydrophilic

CNC while the residual vinyl

acetate groups could react with the

133
 hydrophobic matrix [56].

Coupling agent Organofunctionalsilanes : i) Actually there is no reaction i) The bifunctional groups present

• Amino-propyl-tri-ethoxy silane happens between organosilanes and on the coupling agents could induce the

• Isopropyl dimethylchlorosilane OH groups of cellulose, but covalent bonding between the matrix

The generic chemical structure reactions can be initiated after the and the NCs, mitigating the difference

of Organofunctionalsilanes : hydrolysis of alkoxy groups of in the functional groups of both phases

R(4n)M(R’X)n organofunctionalsilanes by water. [44].

(n = 1, 2) and R is alkoxy group, ii) Drawbacks: the surface

M is tetravalent base metal (Si Thus the silane coupling agents is silylated CNCs only became readily

/Zr), first added into deionized water to dispersible in organic solvents of

X represents an become silanols medium polarity, silylated CNCs is

organofunctionality, and R’ is an ii) The silanol able to react with incapable to be dispersed in solvents of

alkyl bridge connecting the base the hydroxyl groups of the CNC very low polarity

metal and the through chemisorption, forming

organofunctionality stable covalent bonds to the

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 crystalline cellulose [44].

Titanate coupling agents: i) Titanate coupling of titanate ii) This surface chemical

i) monoalkoxy- and modifier alkyl chain with the modification changes the hydrophilic

neoalkoxy-type titanium-derived hydroxyl groups on the surface of character of NC to hydrophobic

coupling agents the NCs is completed by alcoholysis without affecting their crystalline

ii) Lica 38 i) Through alcoholysis, the structure [27].

monoalkoxy- and neoalkoxy-type iii) Endow the NC with the most

Different to silane coupling, titanium-derived coupling agents hydrophobic surface or more

titanate coupling is thought to could react with the hydroxyl hydrophobic surface than silane,

occur via alcoholysis, surface groups on the NC surface to form a possibly due to the lower polarity of

chelation or coordination monomolecular layer which desired the titanate modifier alkyl chain [36].

exchange. to reduce the surface energy of NCs iv) The improvement of the

[22,53]. mixability and the interfacial bonding

between hydrophilic NCs and

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 hydrophobic matrices results in

uniform dispersion of NCs in

composites.

Esterification Reagents which could supply i) Several methods had been i) Acetylation of the NC could

acetyl groups: employed to achieve the weaken the hydrophilic nature by

• acetic or propionic acid esterification processes of CNCs decreasing the surface energy between

• alkenyl succinic anhydride while acetylation is a representative adjacent NC particles and thereby

(ASA) method [32]. effectively suppressing the cluster

• acetyl chloride ii) Taking Fischer esterification formation [99].

• acetic anhydride as an example of acetylation, the ii) Hydrophobic tendency of

• acetic anhydride acetic acid enable to replace the acetylated NCs could allow for better

hydroxyl groups on NC surface with dispersibility in an apolar polymeric

ester/acetyl groups that have a more matrix and enhance the chemical

hydrophobic nature [53]. affinity between MFC and a nonpolar

iii) The main advantage of solvent [36,44].

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 esterification is the absence of iii) Able to improve the thermal

solvent and high efficiency could be degradation resistance of cellulosic

reachable without affecting the fibers [22].

crystalline core [27,32,44].

Surface grafting • Aliphatic grafting agents: “Grafting-onto” technique: By using i) Could impart high hydrophobic

• n-octadecyl isocyanate isocyanate which can generate behaviour to NC to reduce hydrophilic

• hexamethylene diisocyanate covalent bonds with –OH groups of nature of NCs.

• The available grafted polymer NCs, the existing pre-synthesized

chains: polymer chains can be directly NCs with a surface layer of moderate

• Polycaprolactone grafted onto -OH groups at the hydrophobicity can effectively improve

• waterborne polyurethane cellulose surface [22,32,53]. the adhesion in NCs-composites.

• thermo-responsive polymers However, the reaction is slow due to

steric hindrance and high viscosity Advantages: the absence of secondary

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 of the medium [32]. products and the chemical stability of

The polymer can be fully the urethane linkage,

characterized before grafting ii) The homogeneity of the ensuing

enabling to have controllable nanocomposite is found to increase

properties of resulting material. with the length of the grafted chains

[111]

• Monomers: As initiated by immobilized i) The “grafting from” could be

• acrylic monomer initiators, the polymer chains could used to transform polysaccharide

• styrene with N,N-dime- be grown from cellulose substrate nanocelluloses into a co-continuous

thylaminoethyl via the atom transfer radical material under controlled conditions,

• N,N-di- methylaminoethyl polymerization (ATRP) or Ring- the long chains modified

methacrylate opening polymerization (ROP), nanocelluloses could improve the

• glycidyl methacrylate [36] called “grafting-from” technique interfacial adhesion between the filler

When the ROP is performed, [32,53]. and the matrix [27].

Sn(Oct)2 is normally used as a • Advantages: the reaction is fast ii) ATRP technique enables to

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 catalyst [32]. and easy because there is no steric very precise control over the grafting

hindrance and the viscosity of the process, allowing obtaining the desired

reaction medium remains low length of polymer chains grafted on the

• Drawback: the grafted polymer is surface of the nanoparticles

not initially fully characterized [32]. iii) By using ring-opening

techniques, it is difficult to control the

length of the grafted chains

(4) Physical modifications

Corona treatment Corona discharge equipment By applying electric discharge, i) It could change the original

surface oxidation activation could surface energy of cellulosic substrate.

be induced on the surface of treated- ii) Improvement of the

cellulosic material through the compatibilization between NCs and

excitation of ionized gas [6,43]. hydrophobic matrix.

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Cold plasma • Cold plasma can be generated Abstraction of protons and creation i) The property of plasma is

treatment under atmospheric pressure in of unstable radicals that convert exploited by the method to induce

the presence of helium functional groups on the surface of changes on the surface of a

• High-frequency cold plasma cellulosic material by utilizing the material. Surface modification is

can be produced by microwave positive or negative charged achieved by the reduction of surface

energy molecules such as electron, ion, energy and the development of

radical, excited molecules produced hydrophobicity on

by electrical discharge technique nanofibers. Improving the NC-

[43,44,93,95]. matrix adhesion

Dielectric-barrier high-energy electrons By applying dielectric-barrier Obviously, the surface energy of

discharge discharge, the released high-energy treated cellulosic substrate has been

electrons could break the original changed by the newly formed charged

chemical bonds on the surface of particles.

cellulosic material, for allowing the

creation of the ions, free radicals

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 and other species [124].

Ultra-sonification • Ultra-sonicator Without any surface chemical It has been utilized to enhance the

modification or surfactant coating, dispersion of CNCs in organic solvents

the ultrasonicated NC suspension [27].

could be used for ensuing solvent

solution casting [27].

Gamma • Gamma irradiation device At the suitable dosage, the active Numbers of functional sites and

Irradiation • Gamma rays functional groups created on NC crosslinking points created at the filler-

during exposure to -radiation could matrix interface could be favourable to

provide numbers of functional sites the covalent bonding and fine linking

and crosslinking points [11,61]. between the matrix and filler.

Mechanochemical Pan-mill mechanochemical i) The mechanochemical i) The intra-/inter-molecular

treatment reactor activation of cellulose is achieved hydrogen bonds between cellulose are

through fairly strong shearing and broken up with desired to reduce the

compressing forces generated from polar nature of NCs.

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 pan-mill mechanochemical reactor

ii) This activation on cellulose The new reactive hydroxyl groups

can break up the intra-/inter- exposed on NCs are able to establish

molecular hydrogen bonds between new stronger interactions with polymer

cellulose and expose new reactive molecules

hydroxyl groups [102]. ii) It has been used to solve the

problem of stronger filler-filler

interaction than filler-matrix interaction

[102].

(5) Bacterial Modification

The cultivation of Bacterials: i) After cultivation, the i) Coating of fiber-based cellulose

the cellulose i) Acetobacter xylinum successful coating of the bacteria- with bacterial cellulose results in an

producing (or Gluconacetobacter xylinus) cellulose on fiber-cellulose surfaces improved interfacial adhesion between

bacteria in the ii) Streptomyces albaduncus can be attributed to the strong the fiber-based cellulose and the matrix

presence of fiber- hydrogen bonding between the -OH [43].

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cellulose groups present in bacterial-cellulose ii) The good interfacial interaction

and fiber-cellulose [43]. between coated cellulose and matrix

ii) Upon highly crystalline could facilitate the homogeneous

bacteria nanocellulose attached to dispersion of nanocellulose within the

the surface of fiber-cellulose, the matrix

creation of “hairy fibers”

subsequently is beneficial to

establish interactions with

hydrophobic matrix through

mechanical interlocking [43].

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Figure 1. Schematics of cellulosic fiber structure with emphasis from the (a) cellulosic plant sources [36] and (b) cellulose fiber [36]

to the (c) microfibrillated cellulose consisted of the crystalline and amorphous regions [35], and to the (d) cellulose nanocrystals

prepared by acid hydrolysis [35] (e) nanofibrillated celluloses prepared by mechanical nanofibrillation [47].

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Figure 2. The main steps involved in the preparation of nano-sized cellulose.

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Figure 3. (a) Cellulose nanofibrils and (b) Cellulose nanocrystals/nanowhiskers.

146
Figure 4. Schematic representation of (a) cellulose nanofiller percolation network and (b) cellulose nanofiller aggregation within a

polymeric nanocomposite, where TPU is thermoplastic polyurethane [67].

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Figure 5. (a) Temperature dependence of the storage modulus of NFC/PLA composites with different NFC fiber contents [1] (b) tan

curves of CNW-poly(propylene carbonate) nanocomposites with different CNW contents [58].

148
Figure 6. Representation of an entanglement leading to a contact between two fibrils; and a simple fibril/fibril contact [88].

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Figure 7. Second heating run thermograms for (a) neat PLA and PLA reinforced with CNW at (b) 2.5 wt%, (c) 7.5 wt% and (d) 15

wt%, and isocyanate-CNW at (e) 2.5 wt%, (f) 7.5 wt% and (g) 15 wt% [9].

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Figure 8. (a) Typical TGA curves (remaining weight% vs temperature) of pure polymer and relative nanocomposites; associated with

inset T5 and T50 decomposition temperatures as function of NCs concentration [25] (b) Typical DTG curve (mass loss rate vs

temperature) for polymer and nanocomposites [7].

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Figure 9. Schematic overview of reinforcing system of NCs on polymer.

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Figure 10. General schematic diagram strategies used for preparation of cellulose based nanocomposites by (a) solution casting;

formation of solid nanocomposite via casting-evaporation [27,111] (b) formation of nanofiber network followed by impregnation [110]

and (c) one of the representative LBL technique by assembling anionic CNC and cationic polymer in a strong magnetic field [114].

153