Materials and Design 46 (2013) 391–410

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Materials and Design

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Review

Potential materials for food packaging from nanoclay/natural fibres filled

hybrid composites
K. Majeed a,b, M. Jawaid c, A. Hassan a,⇑, A. Abu Bakar a, H.P.S. Abdul Khalil d, A.A. Salema e, I. Inuwa a
a
Enhanced Polymer Research Group (EnPRO), Department of Polymer Engineering, Faculty of Chemical Engineering, Universiti Teknologi Malaysia, 81310 UTM Skudai,
Johor, Malaysia
b
Department of Chemical Engineering, COMSATS Institute of Information Technology, Lahore, Pakistan
c
Laboratory of Biocomposite Technology, Institute of Tropical Forestry and Forest Products (INTROP), Universiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia
d
School of Industrial Technology, Universiti Sains Malaysia, 11800 Penang, Malaysia
e
Faculty of Mechanical Engineering, Universiti Teknologi Malaysia, 81310 UTM Skudai, Johor, Malaysia

a r t i c l e i n f o a b s t r a c t

Article history: The increasing demand for new food packaging materials which satisfy people requirements provided
Received 14 August 2012 thrust for advancement of nano-materials science. Inherent permeability of polymeric materials to gases
Accepted 25 October 2012 and vapours; and poor barrier and mechanical properties of biopolymers have boosted interest in devel-
Available online 3 November 2012
oping new strategies to improve these properties. Research and development in polymeric materials cou-
pled with appropriate filler, matrix-filler interaction and new formulation strategies to develop
Keywords: composites have potential applications in food packaging. Advancement in food packaging materials
Food packaging
expected to grow with the advent of cheap, renewable and sustainable materials with enhanced barrier
Nanoclay
Natural fibres
and mechanical properties. Nanoparticles have proportionally larger surface area and significant aspect
Hybrid composites ratio than their micro-scale counterparts, which promotes the development of mechanical and barrier
properties. Nanocomposites are attracting considerable interest in food packaging because of these fas-
cinating features. On the other hand, natural fibres are susceptible to microorganisms and their biode-
gradability is one of the most promising aspects of their incorporation in polymeric materials. Present
review article explain about different categories of nanoclay and natural fibre based composite with par-
ticular regard to its applications as packaging materials and also gives an overview of the most recent
advances and emerging new aspects of nanotechnology for development of hybrid composites for envi-
ronmentally compatible food packaging materials.
Ó 2012 Elsevier Ltd. All rights reserved.

1. Introduction exhibit attractive advantages such as low cost and low density per
unit volume, reduced tool wear and acceptable specific strength
Agricultural residues available in nature can be used as a source beside their renewable and degradable characteristics. There are
of raw material for renewable materials, particularly to plastic wide range of natural fibres which can be applied as reinforcement
industries. Different parts of plants and fruits of many agricultural or fillers. Bio-fibres are in most cases cheaper than synthetic fibres
crops have been found to be viable source of raw material as fillers and cause less health and environmental hazard problems for peo-
for composite industries. Development and progression in these ple producing the composites as compared to glass fibre based
bio-based materials will not only benefit eco-system, but would composites [2]. It may lead to the production of high durable con-
lead to economic development for farming and rural areas in sumer products from natural fibres that can be easily recyclable
developing countries as well, owing to non-food commercial appli- [3]. Natural fibres can be used for development of highly thermally
cations of these underutilized renewable materials. It is well stable and acoustic insulator materials. Fig. 1 shows different types
known that natural fibres have been used in the preparation of of natural fibres used in biodegradable polymer composites [1,4].
composites since historical times. In recent years its application Natural fibres have poor water resistance, low durability, and poor
as bio-filler/reinforcement materials in composites increased due fibre/matrix interactions. The poor interfacial bonding between
to its availability as renewable materials and ecological concern highly polar natural fibres and non-polar organophilic polymer
[1]. Natural fibres as bio-fillers have been focus of attention as they matrix can lead to a loss in final properties of the composites
and ultimately hinders their industrial usage. Different strategies
have been applied to complement this deficiency in compatibility,
⇑ Corresponding author. Tel.: +60 7 5537 835; fax: +60 7 5581 463. including the use of coupling agents and/or surface modification
E-mail address: [email protected] (A. Hassan). techniques [5,6]. Surface modification of natural fibre can be

0261-3069/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.matdes.2012.10.044
392 K. Majeed et al. / Materials and Design 46 (2013) 391–410

market, Packaging industry is a major user of these plastics

(Fig. 2) [12]. Polymer industry greatly contributed to the develop-
ment of the food distribution system and their production and
usage have been enormously increased. However, despite their
versatility and performance, they alone are hardly useable in food
packaging because of their inherent permeability to gases and va-
pours, including oxygen, carbon dioxide and organic vapours. Fur-
thermore, the use of these non-biodegradable materials has led to
disposal problems. Presence of oxygen is a major detrimental fac-
tor for food deterioration. Oxygen deteriorates food in a number of
ways including direct oxidation and indirect action. Direct oxida-
tion reaction leads to browning of food, flavour rancidity. Indirect
deterioration is caused by microorganisms. Both direct and indirect
oxidative reactions have equally adverse effect on odour, colour,
flavour and nutritional quality.
Most of the petroleum based plastics being used for food pack-
aging are non-degradable and it causes many environmental prob-
Fig. 1. Various types of nanoscale materials (with permission) [10]. lems associated with their disposal, including damage to the
environment eco-system, water supplies, and sewer systems as
achieved by mechanical, chemical, and/or physical means. The use well as to the rivers and streams. Moreover, they are non-renew-
of maleic anhydride grafted copolymer and alkaline treatment of able; and their price is rising and unstable with impending deple-
the natural fibre are the most used techniques with the aim to im- tion of petroleum resources. In view of these serious issues posed
prove the fibre–matrix interfacial bonding [7]. by synthetic plastics, there has been an expanding search for alter-
Nanoscale particles are classified into nanoparticles, nanotubes, native packaging materials in place of synthetic ones that can com-
and nanolayers depending on their dimensions [8,9]. Isotropic sil- pete effectively with their non-renewable and non-biodegradable
ica nanoparticles have three dimensions in nanoscale range; on the counterparts in terms of both the overall cost and physical proper-
other hand, nanotubes and whiskers have two dimensions in nano- ties [14]. Biodegradable polymers constitute a loosely defined fam-
scale range while third one is beyond this range, thus forming ily of polymers that are designed to degrade through the action of
fibre-like structures (Fig. 1) [10]. The difference between nano- living organisms. Typical biodegradable polymers such as polycap-
tubes and Nano-whiskers is that nanotubes are hollow while rolactone (PCL), poly(lactic acid), polyhydroxyalkanoates, poly(eth-
nano-whiskers are filled materials. Natural clays are inexpensive ylene glycol), and aliphatic polyesters, such as poly(butylene
naturally occurring materials as aluminium silicate primarily com- succinate) and poly(butylene succinate-co-butylene adipate) are
posed of fine-grained minerals; and various clays or clays minerals commercially available [15]. These biodegradable polymers could
are catalysts of Fenton-like reactions [11]. Currently, nanoclay are contribute to the solution of waste disposal problem. For the pro-
the most commercially used nanoparticles and nearly 70% of the duction of fully renewable and biodegradable packaging materials,
total market value [12]. Layered silicates, having at least one both the matrix and the reinforcing filler must be derived from
dimension in nanoscale range, are found in the form of sheets/ annually renewable resources [1]. However, the costs of these fully
platelets of one to a few nanometre thick to hundreds to thousands degradable materials derived from renewable natural resources are
nanometre long [8]. The nanoclay generally used is montmorillon- comparatively higher than non-degradable polymeric plastics. The
ite (MMT), consisting of two tetrahedral sheets of silica fused to an costs of these biodegradable polymers in comparison to non-
edge-shared octahedral sheet of alumina. Fillers with high aspect degradable polymers are shown in Table 1 [16].
ratio (ratio of largest to smallest dimension) are particularly inter- Food packaging is the largest growing sector within the domain
esting as they result in better reinforcement of the nanocomposite of plastic packaging market and is an integral part of food process-
material [13]. ing operations [17,18]. Its main objective is to maintain the quality
Fossil-fuel based plastics have brought many benefits to man- and safety of the food-stuff it contains from the time of packaging
kind and they have replaced conventional packaging materials to its delivery to the ultimate consumer. Another important func-
(glass, metals, and ceramics). It is due to their high specific tion of packaging is to protect the food from physical, chemical
strength, lightness, resistance to water and water-borne microor- and biological hazards (oxygen, moisture, light, microbial contam-
ganisms, along with their long durability. In the polymer global ination, insects, etc.) during storage and distribution [19]. More-
over, the other functions of packaging include containment,
convenience, source of information regarding the food and aesthet-
ically pleasant. Beside these aforementioned primary functions of
food packaging materials, the secondary issues of increasing
importance that packaging technology must consider are energy
and material costs, recyclability, sustainability, stringent regula-
tions on pollutants and the disposal of packaging material. Thus
the goal of food packaging is to maintain food safety and minimizes

Table 1
Average cost of biodegradable polymers and traditional thermoplastic [16].

Polymer Cost (euro/kg) Biodegradable polymer Cost (euro/kg)

HDPE 0.92 PLA 3–4
LLDPE 0.82 Starch 2–4
PP 0.80 Polyester 3.5–5
PS 1.08 BAK 5.58
PVC 0.78 PCL 8.3
Fig. 2. Polymer global market (with permission) [12].
 K. Majeed et al. / Materials and Design 46 (2013) 391–410 393

environmental impact. Furthermore, there must be a balance be- bon comes from contemporary (non-fossil) biological sources. Nat-
tween the principal role and the after-use issues of packaging ural fibres are one of abundant and renewable bio-based materials
materials. in nature and they can be classified into different types as shown in
The approach is produce low-cost degradable packaging mate- Fig. 3 [2]. The natural fibres can generally be classified according to
rials from renewable resources by using natural fillers (bio-fillers) their origin as bast, leaf, fruit, and seed-hair fibres. The natural fi-
as load bearing constituents in composite materials. Recently pub- bres that have been reported in literature to reinforce different
lished review paper on utilization and development of bio-fibres polymer matrices include wood [28–30], cotton [31], bagasse
for packaging applications have described some of the key chal- [32,33], rice straw [33–35], rice husk [36–39], wheat straw [40–
lenges [20]. Although, these natural fibre filled polymer composites 42], flax [43], hemp [44–46], pineapple leaf [47], coir [48], oil palm
cannot replace synthetic polymers in every packaging applications [48–52], date palm [53], doum fruit [54], ramie [55], curaua
due to their dominant hydrophilic character, degradability, low [56,57], , jowar [58], kenaf [59], bamboo [60–64], rapeseed waste
mechanical properties, particularly under humid environments, [65], sisal [66] and jute [67–71]. Some of these lignocellulosic fill-
however, they can be employed in applications where recovery ers along with their typical pattern of reinforcements used in the
of plastics is not economically feasible, viable, and controllable lignocellulosic based biodegradable composite are shown in
such as plastic items for one-time use as food packaging. Nanoclays Fig. 4 [1].
have been reported to reinforce polymeric materials and to reduce Natural fibres play an important role in fulfilling the specific
the permeability of gases [12,21–23]; while packaging materials requirements of the composites as engineered materials and have
manufactured by incorporating nano-sized materials is a recent received attention from scientists and researchers owing to their
phenomenon to enhance properties of available conventional advantages over most of the other fillers. Their utilization as rein-
packaging materials. Several studies reported application of forcing component in polymer composites is an effective way to
nano-materials as potential packaging materials [12,13,24]. Nano- produce light weight, low cost, ecofriendly, hygienic, naturally
clay are already used in multilayer film packaging; beer bottles, degradable and CO2 neutral materials without adversely affecting
carbonated drinks, and thermoformed containers for industrial the rigidity of the composites [72–75]. Furthermore, owing to their
purposes [12]. It is also reported that nanoclay in plastic bottle susceptibility for living organisms, they are biodegradable and
keep juice fresh and high shelf life up to 30 weeks. Natural fibre their use in the preparation of composites or hybrid composites
are also one of the potential materials used as packaging materials does not cause environmental problems which are associated with
in our daily life. Natural fibre based packaging materials have the disposal of most of the fossil based plastics. The incorporation
many advantages over synthetic packaging materials such as stiff- of these natural fibres in matrix polymers have been found helpful
ness vs. weight ratio and recyclability [25]. It is also reported that in biodegradation of the composite materials [76–78]. Beside these
use of renewable polymer will help in the production of high per- aforementioned advantages, their poor compatibility with hydro-
formance materials which contribute towards demanding food and phobic polymer matrices, higher moisture uptake and their vari-
pharmaceutical packaging applications. In a recent study, research- ability in structure makes them less attractive for commercial
ers concluded that bioboased content and biodegradability are applications.
essential elements for single use, short-life disposable packaging
and consumer plastics [26]. In recent years several companies took 2.1. Chemical constituents, physical and mechanical properties of
initiatives to produce recycle packaging materials for examples; natural fibres
Placon Corp., has introduced EcoStar™ HS 1000, a PET-based eco-
friendly recyclable material, Toray Plastics America has developed The chemical composition of natural reinforcing filers has a
solvent-free polyester LumiLidÒ lidding films [27]. vital role and an unavoidable impact on the final properties of
Food packaging with enhanced functions is constantly sought in natural filler/polymer matrix composite [72]. Furthermore, the
response to the consumer concerns for food safety, market global- natural reinforcing materials present strong variations in terms
ization and growing environmental awareness. With the recent of their constituents composition compared to synthetic fibres.
advancement in nanocomposite technology, compounding of poly- These variations among the different types of natural fibres ac-
mers with biofibre/nanoclay hybrid fillers is a technique that can counts for some of the variations in fibre properties [79]. Chemical
complement the draw backs of conventional polymers and prom- compositions, physical and mechanical properties of different
ise a new crop of stronger, high barrier, short life, disposal, and natural fibres used in composites are presented in Table 2
environmentally compatible food packaging materials. It is in- [2,33,40,57,80–83]. Cellulose, hemi-cellulose, and lignin are the
tended that use of biofibre/nanoclay based hybrid materials will three main constituents of all the natural fibres and found in differ-
contribute to sustainability and reduction in environmental haz- ent proportions even within the various components of the same
ards associated with disposal of synthetic polymer based packag- plant [34]. Beside these structured main components, some other
ing materials. This paper gives an overview of recent scientific non-structural components, like waxes, pectin, inorganic salts
and technological advances in the field of polymer nanocomposites and nitrogenous salts are also present [84]. Cellulose is the main
for food packaging applications. Beside reinforcement aspects of structural constituent of the natural fibres and the mechanical
nanocomposites, their permeability to vapours and gases will also properties of these fibres are dependent on this constituent [85].
be discussed. An important consideration in this review involves Lignin is an amorphous natural polymeric material that regulates
the physical and chemical treatments of lignocellulosic materials the transport of liquid in the plant and is composed of phenylpro-
for producing biodegradable packaging materials with enhanced pane derivatives. It is found together with polysaccharides in the
barrier and mechanical properties. biomass in the amount 20–30% lignin to 60–80% polysaccharides
[86].
Fibre’s strength is an important factor to choose fibre that is
2. Bio-based natural fibres as reinforcement materials specific for certain usage. Table 2 gives data on length, diameter
and microfibril angle of various natural fibres. The individual fibre
Bio-based materials have been defined as ‘materials derived show different characteristics according to shapes, sizes, orienta-
from renewable sources’ [18]. A standard definition for Bio-based tions, thickness of the cell walls and other [1]. The Rigid cellulosic
materials can be found in ASTM: D7075-04. Bio-based materials: microfibrils, which are composed of b-glucans, have been found
materials containing carbon based compound(s) in which the car- fixed firmly in an ordered manner in a comparatively soft matrix
394 K. Majeed et al. / Materials and Design 46 (2013) 391–410

Fig. 3. Classifications of fibres (with permission) [2].

of hemicellulose and lignin. These ordered structures are stabilized stiffness natural fibres such as hemp, flax, jute, kenaf and sisal are
by inter molecular and intra molecular hydrogen bonding. Elemen- becoming increasingly important in composites production.
tary fibrils, known as crystallites, are made up of up to 100 glucan
chains forming long thin structures of about 5 nm width. Further 2.2. Treatment of the natural fibres
grouping of these crystallites leads to the formation of microfibrils
having dimensions of 8–50 nm in diameter and a few microns in The key issue related with development and production of nat-
length. The crystallites which are elementary building material ural fibre reinforced composites is the interfacial adhesion be-
for cellulose and responsible to give strength to the plant stem, tween the filler and the polymer matrix [72]. Most of the
their size depends upon the source of cellulose [87]. The variability thermoplastic polymer matrixes are non-polar, hydrophobic com-
in fibre constituents, which can be attributed to growth conditions pounds while, on the other hand, natural fibres are polar, hydro-
such as botanical origin, soil characteristics, and weather circum- philic compounds. Because of this inherent dissimilarity, natural
stances, can contribute differently to the performance characteris- reinforcing filler/polymer matrix composites are not compatible
tics of the natural fibre reinforced composites [34]. The chemical and interfacial adhesion in these composites tends to be poor. To
composition, structure, microfibril angle, and cell dimension of render this poor interface compatibility and to produce bio-filler
the fibres are most important variable that determine the overall filled composites with enhanced performance properties, pre-
properties of the fibres [88]. Table 2 shows the mechanical proper- treatment of natural fibre and/or matrix are often required and ap-
ties of important natural fibres, glass fibre, and wood fibres that plied. These treatments help to improve the stress transfer be-
can be utilized for composites. Specific modulus of natural fibre tween the two components that influence the properties of the
show the value that are comparable to or even better than glass fi- natural fibres and results in high-performance composites from
bres [2]. It is also clear from Table 2 that natural fibres such as coir, bio-fibres. Several strategies have been investigated to improve
pissava, pineapple leaf, sisal fibres show significant better elonga- the fibre properties and to increase the bondability and wettability
tion at break as compared to glass fibres and it will translate in bet- between the cellulosic materials and the matrix polymer.
ter composite damage tolerance. However, for better strength and Researchers generally used fibre surface modification by physical,
 K. Majeed et al. / Materials and Design 46 (2013) 391–410 395

Fig. 4. Lignocellulosic reinforcements. (a) Banana; (b) sugarcane bagasse; (c) curaua; (d) flax; (e) hemp; (f) jute; (g) sisal; (h) kenaf. Typical pattern of reinforcements used in
the hybrid LC based biodegradable composite synthesis. (i) Jute fabric; (j) ramie–cotton fabric. (k) jute–cotton fabric (with permission) [1].

chemical or mechanical means. The treatments involved in these the cellulosic material take place [91] with smoother surfaces, re-
modification methods can also be used as precursors to the other duced stiffness and more concentrated distribution [1]. It is impor-
technique [1]. tant to note that the selection of appropriate temperature of the
steam and treatment time of the bio-material is important and
have a vital role on the chemical composition and ultimate perfor-
2.2.1. Physical treatments mance properties of the material under concern [41,91]. Han et al.
Physical methods involve treatments by ionized gas (plasma or
have reported the effects of steam treatment of wheat straw under
corona), laser or steam explosion. Plasma treatment of the bio-fi- different pressures and treatment times. They found that the treat-
bres results in cleaning and modification of the surface of fibre
ment causes an improvement in dimensional stability and a reduc-
by imparting different functional groups and changes in surface tion in lignin, ash and extractives content; and sorption behaviour
energies. The plasma discharge can be generated by either corona
(Table 3). Furthermore, tensile strength of the straw treated at a
treatment or cold plasma treatment and the functionalization im- steam pressure of 1 MPa for 5 min was more than twice higher
parted depends on the selection of plasma gas and operating than that of the control samples.
parameters. Both methods are considered as a plasma treatment
when ionized gas has an equivalent number of positive and nega-
tive charged molecules that react with the surface of the present 2.2.2. Chemical treatments
material. The distinguishing feature between the two categories Natural cellulosic fibres are highly polar owing to the presence
of plasmas is the frequency of the electric discharge. High-fre- of hydroxyl groups. These hydroxyl groups are readily available for
quency cold plasma can be produced by microwave energy, chemical bonding (hydrogen bonding) with compatible polymer
whereas a lower frequency alternating current discharge at atmo- matrices and physical interlocking (wetting) with the non-polar
spheric pressure produces corona plasma [5,89]. Plasma and laser matrices. However, the presence of pectin and waxy materials
treatments of the cellulosic material have been found attractive along with hydroxyl groups impede their bonding and wetting
to improve the surface of bio-material and to enhance its interfa- with the polymer matrices and make them less attractive for rein-
cial adhesion with the polymeric matrices [1,90]. forcement purposes [48,92]. Several chemical treatments have
Steam treatment of the lignocellulosic material can be accom- been investigated by a number of researchers having potential to
plished by application of high pressure steaming, involving heating remove waxes, oils from the surface and make it rough, activate
of the materials at high temperatures and pressures followed by readily available hydroxyl groups or the introduction of new reac-
mechanical disruption of the pretreated material by violent dis- tive sites/groups; and to stop water uptake [5,6,68,92–95]. These
charge (explosion) into a collection tank [1]. The explosion results treatments aimed at improving fibre–matrix adhesion have
in destruction of the cellular material and thereby the fibrillation of achieved various levels of success in improving fibre strength, alle-
 396
Table 2
Physical, mechanical and chemical composition properties of different natural fibres as compared to glass and wood. Sources: Jawaid and Abdul Khalil [2]; Habibi et al. [33]; Alemdar and Sain [40]; Silva and Aquino [57]; Dittenber et al.
[80] ; Abdul Khalil et al. [81]; Georgopoulas et al. [82]; Ludeuna et al. [83].

Fibre type Density (g/ Length Diameter Tensile strength Tensile modulus Elongtn at break Cellulose Hemi-cellulose Lignin Pectin Waxes Microfibrilar angle
cm3) (mm) (lm) (MPa) (GPa) (%) (wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (deg)
E-glass 2.5–2.59  <17 2000–3500 70–76 1.8–4.8      
Abaca 1.5   400–980 6.2–20 1.0–10 56–63 20–25 7–13 1 3 
Alfa 0.89   35 22 5.8 45.4 38.5 14.9  2 
Bagasse 1.25 10–300 10–34 222–290 17–27.1 1.1 32–55.2 16.8 19–25.3   
Bamboo 0.6–1.1 1.5–4 25–40 140–800 11–32 2.5–3.7 26–65 30 5–31   
Banana 1.35 300–900 12–30 500 12 1.5–9 63–67.6 10–19 5   

K. Majeed et al. / Materials and Design 46 (2013) 391–410

Coconut   100–450 131–175 4–13  36–43 0.15–0.25 41–45 3–4  
Coir 1.15–1.46 20–150 10–460 95–230 2.8–6 15–51.4 32–43.8 0.15–20 40–45 3–4  30–49
Corncob       26.1 45.9 11.3   
Cotton 1.5–1.6 10–60 10–45 287–800 5.5–12.6 3–10 82.7–90 5.7 <2 0–1 0.6 
Curaua 1.4 35 7–10 87–1150 11.8–96 1.3–4.9 70.7–73.6 9.9 7.5–11.1   
Flax 1.4–1.5 5–900 12–600 343–2000 27.6–103 1.2–3.3 62–72 18.6–20.6 2–5 2.3 1.5–1.7 5–10
Hemp 1.4–1.5 5–55 25–500 270–900 23.5–90 1–3.5 68–74.4 15–22.4 3.7–10 0.9 0.8 2–6.2
Henequen 1.2   430–570 10.1–16.3 3.7–5.9 60–77.6 4–28 8–13.1  0.5 
Isora 1.2–1.3   500–600  5–6 74  23  1.09 
Jute 1.3–1.49 1.5–120 20–200 320–800 8–78 1–1.8 59–71.5 13.6–20.4 11.8–13 0.2–0.4 0.5 8.0
Kenaf 1.4   223–930 14.5–53 1.5–2.7 31–72 20.3–21.5 8–19 3–5  
Nettle    650 38 1.7 86 10   4 
Oil palm EFB  0.89–0.99 19.1–25    65.0  19.0   
Oil palm  1.52–1.59 19.7    56.03 27.51 20.48   
fronds
Olive husk       40.56 18.10 23.43   
Piassava 1.4   134–143 1.07–4.59 7.8–21.9 28.6 25.8 45   
PALF 0.8–1.6 900–1500 20–80 180–1627 1.44–82.5 1.6–14.5 70–83  5–12.7   14
Ramie 1.0–1.55 900–1200 20–80 400–1000‘ 24.5–128 1.2–4.0 68.6–85 13–16.7 0.5–0.7 1.9 0.3 7.5
Rice husk       25–35 18–21 26–31   
Rice straw       59.1 18.4 5.3   
Sisal 1.33–1.5 900 8–200 363–700 9.0–38 2.0–7.0 60–78 10.0–14.2 8.0–14 10.0 2.0 10–22
Soy hulls       56.4 12.5 18.0   
Wheat straw       43.2 34.1 22.0   
Eucalyputs       37.6 32.9 19.1   
wood
Hardwood  3.3 33    31–64 25–40 14–34   
Softwood  1.0 20    30–60 20–30 21–37   
 K. Majeed et al. / Materials and Design 46 (2013) 391–410 397

Table 3
Effect of steam conditions on the chemical composition of wheat straw [41].

Steam pressure (MPa) Treatment time (min) Holocellulosea (%) Lignin (%) Ash (%) Phenethyl alcohol extractives (%)
Untreated – 66.46 22.75 4.99 5.80
0.4 5 76.63 15.36 3.39 4.66
0.6 10 78.68 14.24 3.28 3.81
a
The listed hollocellulose contents may include hollocellulose and other reconstituted compounds that cannot be distinguished by the test method used in this study.

Fig. 5. The function of the compatibilizing agent in the lignocellulosic filler–polyolefin composite system [99].

viating water absorption and enhancing fibre–matrix adhesion in aqueous solution of a strong base so as to produce great swelling
natural fibre reinforced composites. with resultant changes in the fine structure, dimensions, morphol-
The enhanced interfacial adhesion is usually accomplished ogy, and mechanical properties; ASTM:D1695-07. The treatment of
through the use of regents having functional groups that are capa- the cellulosic material causes changes in physical structure and
ble of bridging and bonding the hydroxyl groups of the lignocellu- crystallinity of the fibres owing to its bleaching action [100,101].
losic materials with the matrix material. To overcome inherent Bleaching removes the waxy and cementing substances like hemi-
shortcomings associated with the natural fibre, among all the cellulose and lignin, resulting in the development of rough surface
available treatment, the use of compatibilizer is common and topography and breaking down of the composite fibre bundle into
effective method to improve fibre/matrix interface bonding [75]. smaller and thinner fibres. The reaction scheme is shown by Eq. (1)
Owing to their functionality; and compatibility with both, the filler [5].
and the matrix, they are termed as compatibilizer. The compatibi-
lizer is usually graft co polymers of the polymeric matrix and an Fibre—OH þ NaOH ! Fibre—O Naþ þ H2 O ð1Þ
anhydride such as MA [75]. These regents are compatible with Researchers observed a reduction of 22–12.90% in hemicellu-
the polymer matrix and the hydroxyl groups of the lignocellulosic lose content of jute fibre on treatment with 5% NaOH for 2 h
material, forming covalent bonds [96]. It is widely used method for [102]. Furthermore, the removal of these inert materials leads to
the production of natural fibre reinforced polyolefin composites new reactive sites that result in better interfacial adhesion [5,67].
[55,72,97,98]. Fig. 5 depicts the function of compatibilizing agent Many studies have been focused on alkali treatment of the natural
in the lignocellulosic fibre reinforced polyolefin composite [99]. fibres to enhance the interfacial adhesion between the fibre and
Strongly polarized hydroxyl groups make the cellulosic materi- matrix polymer [32,56]. In another interesting study, researchers
als hydrophilic and chemically incompatible with the hydrophobic investigated the effect of alkali treatment on the physical and
polymer matrices [5]. Furthermore, the presence of wax, natural mechanical properties of bamboo fibres and noticed a steady in-
fats and cementing materials which may hide reactive sites and crease in mechanical properties of bamboo strips with increasing
represents a hydrophobic blockage for fibre wetting and they must concentration of NaOH, showing a maximum change between
be removed. Alkali treatment, also called mercerization is the pro- 15% and 20% and then exhibiting a gradual fall [101]. Treatment
cess of subjecting a natural fibre to the action of fairly concentrated of bagasse fibre with 1% alkali solution resulted in increased tensile

Table 4
Mechanical properties of untreated and alkali treated bagasse fibre composite [32].

Fibre loading (wt.%) Treatment Tensile strength (MPa) Flexural strength (MPa) Flexural modulus (MPa) Impact strength (kJ/m2)
20 Untreated 16.52 31.19 1136.87 4.12
Alkali treated 18.58 34.71 1321.72 6.07
35 Untreated 18.60 38.37 1451.81 6.82
Alkali treated 21.35 43.96 1622.36 8.29
50 Untreated 21.09 40.16 1841.34 8.17
Alkali treated 23.07 46.05 2031.37 9.52
65 Untreated 23.47 43.87 2292.02 8.82
Alkali treated 26.77 50.86 2673.73 11.27
398 K. Majeed et al. / Materials and Design 46 (2013) 391–410

strength, form 70.9 MPa to 83.4 MPa [75]. Mechanical properties of been some studies reporting the enhanced mechanical properties
the biocomposite prepared by the incorporation of untreated and and reduced water absorption of the natural fibre reinforced bio-
alkali treated bagasse fibre are shown in Table 4. Moreover, there composites, on incorporation of silane treated fibres, resulting
have been studies reporting changes in crystallinity of the bio- from the improved adhesion between the fibre and matrix [110–
material owing to alkali treatment [69,100,103]. 114]. It also reported that thermal stability of the composites im-
The use of oxidizing agents, such as hydrogen per oxide (H2O2) proved after silane treatment [49].
is another effective way to remove the cementing materials from Acetylation of the natural fibre is another effective way to im-
the natural fibre that hinders its adhesion with polymer matrices. prove its hydrophobic characteristics and thus an enhanced inter-
The reaction scheme are shown in Eqs. (2)–(4) [104]. Alkali treat- facial adhesion with the matrix and reduction in moisture uptake
ment of the natural fibre may lead to formation of alkali resistant of the cellulosic material. It involves the use of acetic or propionic
linkage between lignin and hemicellulose. This linkage impedes acid at elevated temperatures with or without an acid catalyst [5].
the removal of lignin. The use of H2O2 can break this linkage and Acetylation of the cellulosic material results in the substitution of
delignify lignocellulosic fibre to enhance its interfacial adhesion the hydroxyl groups of the cell wall with acetyl groups. As a result,
with the polymer matrix [93,105]. In another study, researchers hydrophobic tendency of the natural fibre improved and increase
used H2O2 treatment as precursor to NaOH treatment and found compatability with polymer matrix and decreasing its water
that the treatment has reinforced the fibre and consequently im- absorption tendency.
proved its crystallinity and strength [104]. They proposed that Chemical and/or physical treatment of the natural fibre results
the treated fibrous material could be used as fibrous filler in com- in chemical and structural changes on the fibre surface and the
posites owing to their high strengths, heat resistance and low cells; with a consequence improvement in the performance prop-
shrinkage; and to lower the cost of the composite prepared. In an erties of the natural fibres reinforced composites [115].
alkaline condition, the hydroxyl ions (OH) produced by the
perhydroxyl ion HO +
2 , hydrolyzes the hydrogen ions (H ), thereby
promoting the liberation of more perhydroxyl ions. 3. Natural fibre reinforced polymer biocomposites

H2 O2 ! Hþ þ HO2 ð2Þ A typical composite consists of a discontinuous reinforcing

HO2 ! OH þ ½O ð3Þ phase embedded into a continuous matrix phase. Composite mate-
½O þ I ! IO ð4Þ rials comprising of one or more phase(s) derived from a biological
origin are considered as biocomposites [84]. There are increasing
where I = Impurities. demands to develop eco-friendly materials which do not burden
The use of coupling agents is another effective way to mitigate the eco-system. This demand has provided much of the impetus
inherent dissimilarities and to enhance interfacial adhesion be- for a new area of research of biocomposites and these biocompos-
tween the fibre and the polymer matrix. In general, they have ites with suitable development have potential to enter new mar-
bifunctional groups that are capable of reacting respectively with kets. The use of natural fibre reinforced plastic composites is an
the fibre and the matrix material. Organofunctionalsilanes belong effective way of improving performance properties. They have
to the most widely used group of coupling agents having a generic been used in the preparation of composites since historical times,
chemical structure R(4n)M(R0 X)n (n = 1, 2) where R is alkoxy with one of their particular applications in air craft as early as
(hydrolysable) group, M is tetravalent base metal (Si or Zr), X rep- the 1940s [1]. The most interesting aspect about natural fibres is
resents an organofunctionality, and R0 is an alkyl bridge connecting their positive environmental impact [76,116]. They are CO2 neutral
the base metal and the organofunctionality [106,107]. Chemical i.e. they do not return excess CO2 into the atmosphere when they
treatment of the cellulosic bio-material with organofunctionalsi- are composted or combusted [88]. Furthermore, they are light
lane coupling agents result in the formation of covalent bonds with weight and lower cost. Moreover, there have been some extensive
the hydroxyl groups of the cellulosic material [5]. Alkoxy groups studies in the last few years to evaluate the possibility and suitabil-
are hydrolysable and they undergo hydrolysis in the presence of ity of the natural fibres as load bearing constituents in composite
moisture which causes the formation of silanols. The silonal then materials and produced encouraging results [40]. Table 5 compares
react with the hydroxyl groups of the fibre, forming stable covalent the some specific tensile properties and cost of natural fibres and
bonds to the cell wall that are chemisorbed onto the fibre surface synthetic fibre.
[5,49,108]. This chemisorption usually improve the degree of cross Natural fibres have been reported to improve mechanical
linking in the interface region and improve chemical affinity to properties of biocomposites, making their use feasible. Mechanical
organophilic polymers [5]. Furthermore, the presence of hydrocar- properties of natural fibre reinforced polymer biocomposites as a
bon chains owing to the modification of natural fibre with silanes function of fibre loading can be seen in Table 6 [15,34,55,
influence the wettability of the fibre and reduces its water uptake 59,72,75,117]. In general, the incorporation of natural fibre in a
because of the crosslinking due to covalent bonding between the polymer matrix leads to significant improvements of tensile mod-
matrix and the fibre. Researchers modified the surface of cellulosic ulus. Researchers fabricate copolyester based biocopmposites by
substrates with two different fluorine-bearing alkoxysilane cou- the incorporation of kenaf fibres as filler [118]. They reported that
pling agents, namely: 3,3,3-trifluoropropyl trimethoxysilane (TFPS) biocomposites show 70% higher Young’s modulus as compared to
and 1H, 1H, 2H, 2H, perfluorooctyltrimethoxysilane (PFOS) [109].
On the basis of contact angle measurements of the chemically trea-
ted samples, they concluded that the modification has resulted in a Table 5
change from highly hydrophilic polar surfaces to hydrophobic-to- Comparison of some specific tensile properties and cost of natural cellulosic fibres and
synthetic fibres [1].
tally non-polar surface. It is also observed that the impact of silane
treated fibre on the performance properties of biocomposite can be Fibre Specific tensile Specific tensile Cost
further enhanced by treating the fibre with alkali solution prior to strength (GPa) modulus (GPa) (US$/ton)
the use of silane coupling agents. Cellulosic fibre 1.60–2.95 10–130 200–1000
As the pre-treatment with NaOH solution have been found very Glass 1.35 30 1200–1800
Kevlar 2.71 90 7500
attractive to create voids and reactive sites owing to the removal of
Carbon 1.71 130 12500
waxes and cementing materials from the fibre surface. There have
 K. Majeed et al. / Materials and Design 46 (2013) 391–410 399

Table 6
Mechanical properties of various Biocomposites.

Biocomposites Fibre loading Tensile Strength Impact strength (kJ/ Tensile Modulus Ref.
(wt.%) (MPa) m2) (MPa)
Aliphatic polyester bionolle 3020/maleic anhydride grafted bionolle 0 23.3 [15]
3001(5 wt.%)/ 30 33.5
HDPE/rice husk 0 29.5 3.89 [34]
30 19 3.95
PP (3 wt.% PP-g-MA)/ramie fibre (melt intercalation) 0 35 2.8 1300 [55]
10 42 3.0 1400
20 51 4.2 1600
30 66 4.7 2250
LDPE/PEG (7 wt.%)/kenaf cellulose 0 11 0.61 [59]
30 11.5 041
40 9 0.42
50 11 0.20
HDPE/PP-g-MA (2 wt.%)/date palm trunk fibre 0 17.5 475 [72]
20 17 750
30 18 975
40 20 1500
LDPE/bleached date palm leafs fibre 0 7.6 130 [75]
7 6.5 220
15 5.8 235
28 6.8 390
PP/bleached date palm leafs fibre 0 27.5 800 [75]
7 23.5 700
15 21 650
28 17 675
Polycarbonate/alkali treated pineapple leaf fibre 0 67.5 1100 [117]
5 67.0 6.5 1150
10 66.0 4.0 1450
20 71.0 4.0 2000

copolyester, which was further improved to 140% after the mercer- ity with enhanced thermal stability in comparison with the virgin
ization of fibre following by silane treatment. In another research matrix [110]. In another stuidy, researchers analysed the impact of
they investigated the mechanical and thermal properties of the incorporation of wheat straw into an aromatic copolyester,
LDPE/natural fibre biocomposite, using stearic acid as compatibi- polybutyleneadipate-co-terephthalate through thermal analysis
lizer and maleated low density polyethylene/natural fibre biocom- [124]. They also found that fillers degradation temperature is high-
posites [33]. They also reported an increase in Young’s modulus for er enough to be compatible with the processing temperatures
both type of biocomosite systems. It is worth noting that the chem- (extrusion and injection moulding). Moreover, the biocomposites
ical bonding between the anhydride and the hydroxyl groups re- are thermally more stable as compared to the matrix polymer. Kia-
sulted in better stress transfer from the matrix into the fibres in ni et al. [123] prepared polyvinyl chloride based iocomposites
comparison to stearic acid compatibilized LDPE/fibre biocompos- using pulp fibre (PF) and/or wood flour (WF) as filler, by melt
ite, leading to a higher tensile strength. The influence of three dif- blending followed by injection mouldin. They concluded that the
ferent types of coupling agents on the tensile properties of luffa thermal stability of the composites increases after using PF and
fibre/polypropylene biocomposites was reported by Demir et al. further increases after addition of WF. An enhancement in thermal
[112]. They observed a decrease in elongation at break and tensile stability of the polymeric matrix upon addition of natural fibre
strength while an increase in Young’s modulus of the biocompos- have also been reported as well [119].
ites, with the incorporation of the untreated fibre. Furthermore,
the composites were more flexible at low fibre content, with higher
tensile strength than at higher contents. It is worth mentioning 4. Nanoclays
that an increase in tensile strength of the biocomposites only ob-
served with the incorporation of silane treated biofibre at low fibre Nanoclays are naturally occurring aluminium silicate, primarily
content. The decrease in flexibility with increasing fibre content composed of fine-grained minerals having natural structure with
has also been observed by several researchers [66,119–122]. sheet-like geometry. The sheet-structured hydrous silicates are
The thermal stability of lignocellulosic filled polymer matrix generally referred to as phyllosilicates. The clays are naturally
composites is of paramount importance and the incorporation of occurring inexpensive and eco-friendly materials and have found
natural fibres used as filler or reinforcement to the matrix poly- multifarious application. These clay minerals have been widely
mers have resulted in the change of thermal stability. It is very studied in practical applications such as in geology, agriculture,
important parameter for the processing and usage of composite construction, engineering, process industries, and environment
materials in different applications. The manufacture of such com- applications. They provide an attractive alternative for the decon-
posites requires the mixing of fibres and matrix at high tempera- tamination of soils, underground waters, sediments and industrial
tures, so the degradation of the bio-material can produce effluents [125]. They are also widely used materials in drug prod-
undesirable effects on the properties. Thus, the determination of ucts like as excipients and active agents [126,127]. Millions of tons
thermal degradation profile of bio-fibres and biocomposites is of these materials are used annually and their applications will
inescapable [123]. Studies of thermal properties of bamboo fibre continue to grow at a rate equivalent to the growth of national
reinforced PP biocomposites reported a decrease in melting tem- products [128]. Table 7 summarizes the sheets arrangement for
perature, melting enthalpy, crystallization enthalpy and crystallin- the layers of various clay minerals along with their member min-
400 K. Majeed et al. / Materials and Design 46 (2013) 391–410

Table 7 ability and good performance. Carbon based materials like carbon
Classification of phyllosilicates and their major groups [129]. nanotubes and grapheme nanosheets are also being developed
Layer Tetrahedral- Group name with member minerals Layer [133,134].
type octahedral sheet charge
combination
1:1 T:O Kaolinite (kaolinite, dickite, nacrite) <0.01
4.1.1. Structural and physical properties of layered silicates
2:1 T:O:T Smectite (montmorillonote, 0.5–1.2 Layered silicates are crystalline materials of very fine particle
pyrophyllite, talc, vermiculite, 1.4–2.0 size. They belong to the family of 2:1 phyllosilicates, and more spe-
saponite, sauconite, nontronite, cifically to the smectite group. The term smectite is used to de-
etc.) Illite (illite)
scribe a family of expansible 2:1 phyllosilicate silicate minerals
2:1:1 (T:O:T)O Chlorite (amesite, chamosite, Variable
cookeite, nimite, etc.) having a general formula (Ca, Na, H)(Al, Mg, Fe, Zn)2(Si, Al)4O10(-
OH)2–xH2O, where x represents varying level of water attached
T = tetrahedral, O = octahedral.
to the mineral. They comprise natural clay minerals such as mont-
morillonite, hectorite, and saponite; and also synthetic layered
minerals, fluorohactorite, laponite or magatiide. Two main build-
erals and layer charge. Clay minerals are fundamentally built of ing blocks for these clay platelets are two tetrahedral sheets of sil-
tetrahedral sheets and octahedral sheets; and may be divided into ica and an octahedral sheet of alumina or magnesia. The octahedral
three major classes depending on the number and arrangement of sheet of alumina is fused to two silica tetrahedral sheets in such a
octahedral sheets and/or tetrahedral sheets. These include 1:1, 2:1 way that the oxygen ions of the octahedral sheet also belong to the
and 2:1:1 arrangement. 1:1 clay would consist of one tetrahedral tetrahedral ones. The thickness of each three-sheet layer is around
sheet and one octahedral sheet and 2:1 clay would have one octa- 1 nm with lateral dimensions ranging from 300 Å to several mi-
hedral sheet sandwiched between two tetrahedral sheets per layer crons, depending upon a number of factors, including source of
while 2:1:1 clay would contain one octahedral sheet adjacent to a clay, method of preparation and particulate clay [135]. These layers
2:1 layer [129]. have a tendency to organize themselves to form stacks of parallel
lamellae, like pages of a book. This stacking result in regular van
4.1. Layered silicates as nanofillers for polymer–clay nanocomposites der Waals gaps between the layers called interlayer or gallery.
The parallel layers are held together by weak electrostatic forces
Nano-fillers have a vital role to enhance composite performance and the interlayer space can be penetrated by water, organic cat-
by improving their properties such as mechanical strength, ther- ions or polar organic liquids, causing the lattice to expand
mal stability, and barrier properties. The characteristic parameters [135,136]. The ability of these layers to accept change and/or mod-
that contribute greatly in modifying the properties of various com- ification in their surface chemistry through ion exchange reactions
posites are the filler loading; their size and shape; and their affinity with organic and inorganic cations; and to disperse/delaminate
towards matrix material. Nanoclay filled polymer matrix based into individual lamellae resulting in high aspect ratio are two par-
nanocomposites have generated a significant amount of attention ticular characteristics of these silicates that have been exploited
within the materials industry for their enhanced performance. This and play an important role in the creation of high performance
area emerged with the recognition that exfoliated clays could exhi- nanocomposites. Chemical formula and other characteristic
bit superior strength, modulus and higher barrier properties in parameters of natural clay minerals are given in Table 8 [137].
comparison to virgin polymer matrix [130]. With the recent Montmorillonite (MMT) is the most promising and widely used
advancement in nanotechnology, the correlation of material prop- nanoscale filler in the preparation of nanocomposites. Their high
erties with filler size has become a point of great interest. Nanopar- surface area (700–800 m2/g) and large aspect ratio (50–1000)
ticles have attracted a great deal of interest owing to their make them effective reinforcement filler [13,133]. They have high
extraordinary potential to exhibit novel characteristics that cannot strength and stiffness; and can be regarded as rigid, impermeable
be achieved with their traditional micro-scale counter parts. There fillers. The structure of MMT consists of a 1-nm-thick layer made
have been various studies on the incorporation of different of an inner octahedral sheet of alumina or magnesia sandwiched
nanoparticles into the matrix [131,132], however, the packaging between two tetrahedral sheets of silica as shown in Fig. 6 [22].
industry has recently focused its attention mainly on nanoclay The isomorphic substitution of Al3+ in the octahedral layer by
particulates due to their easy availability, low cost, easy process- Mg2+ or Fe2+, and Mg2+ by Li1+ gives each three-sheet layer an over-

Fig. 6. Structure of Na–MMT [22].

 K. Majeed et al. / Materials and Design 46 (2013) 391–410 401

Table 8 ment of the nanocomposite materials. Researchers studied the ef-

Chemical structure and characteristic parameter of commonly used 2:1 phyllosili- fect of organophilization of layered silicates and concluded that
cates [137].
the surface energy of untreated layered silicates is large; thus,
2:1 Chemical formula CEC Particle the forces keeping the layers together is very strong [139]. The sur-
Phyllosilicate (mequiv/ length (nm) factants lower the surface energy of the platelets, resulting in an
100 g)
increase in the layer spacing (d-spacing). Due to hydrophilic sur-
Montmorillonite Mx(Al4xMgx)Si8O20(OH)4 110 100–150 face of layered silicates, they are only miscible with hydrophilic
Hectorite Mx(Mg6xLix)Si8O20(OH)4 120 200–300
Saponite MxMg6(Si8xAlx)Si8O20(OH)4 86.6 50–60
polymers such as poly (vinyl alcohol) and poly (ethylene oxide)
and are incompatible with the wide range of hydrophobic poly-
M: monovalent cation; x: degree of isomorphous substitution (between 0.5 and mers. To make them compatible with organophilic matrix, one
1.3); CEC = Cation exchange capacity.
must convert the hydrophilic silicate surface to organophilic.
Therefore, a chemical surface modification is essential to achieve
all negative charge because of the difference in valences. This over-
exfoliation for enhanced performance of composite, and can be
all negative charge is counter balanced by metal cations (Na+, Ca2+)
readily achieved by exchanging cations of hydrophilic silicate sur-
located between the platelets or in the galleries, which increases
face (Na+, K+) with organic cations, such as those from an ammo-
the hydrophilic character [22,135,138]. Many analysts have shown
nium salt. MMT is usually treated with alkylammonium ions,
that the charge imbalance in smectite because of isomorphic sub-
although sulfonium and phosphonium can also be used
stitution is about 0.66 per unit cell [128]. The excessive negative
[135,140,141]. The ammonium cations may also have hydrocarbon
surface charge of layers is quantified as cation-exchange capacity
tails. Because of their amphiphilic nature, they are referred to as
(CEC) and varies from layer to layer; thus, an average value over
surfactants. These organic modifiers mostly exchange the alkali
the whole crystal is considered [8]. CEC is expressed as mequiv/g,
cations present in the interlayer, called exchangeable cations with
usually in the range of 80–150 mequiv/100 g for smectites
bulky ions such as ammonium cations (polar head) connected to
[135,136]. CEC depends on the nature of isomorphic substitutions
hydrocarbon chains (non-polar tail) as shown in Fig. 7. Primary,
in the tetrahedral and octahedral layers.
secondary, tertiary and quarternary alkylamonium cations or
phosphonium cations having various substituents can be em-
4.1.2. Organophilization of layered silicates ployed as surface modifier (surfactants). Fig. 8 shows the chemical
A major issue associated with the preparation of nanocompos- structure of various surfactants that are being employed to modify
ites by using layered silicates is the intercalation of matrix chains MMT.
between the layers of clay. Delamination/exfoliation of these lay- Several pristine and modified clays are available commercially
ered silicates in continuous phase has a crucial role and a uniform from a number of suppliers. Table 9 lists a number of commercially
dispersion of these layered silicates in the matrix is essential to available nanoclays along with their organomodifier and other
realize large filler aspect ratio which results in better reinforce- characteristics [138,142–146]. Proper selection of organoclay de-

Fig. 7. Organophilization of montmorillonite.

CH2CH2OH CH3

+ +
CH3 N Tallow CH3 N CH2

(a) CH2CH2OH (b) Hydrogenated Tallow

H2N
(c)
Fig. 8. Chemical structure of organomodifiers: (a) methyl, tallow, bis-2-hydroxyethyl, quaternary ammonium, (b) dimethyl, benzyl, hydrogenatedtallow, quaternary
ammonium, and (c) octadecylamine.
402 K. Majeed et al. / Materials and Design 46 (2013) 391–410

Table 9
Commercially available clay minerals along with surface modifiers [138,142–146].

Supplier/commercial Clay Surface-modifier Modifier concentration (meq/100 g d001

designation clay) (Å)
Southern clay products (USA)
CloisiteÒNa+ MMT – – 11.7
CloisiteÒ10A MMT Dimethyl, benzyl, hydrogenatedtallow, quaternary ammonium 125 19.2
CloisiteÒ15A MMT Dimethyl, dihydrogenatedtallow, quaternary ammonium 125 31.5
CloisiteÒ20A MMT Dimethyl, dihydrogenatedtallow, quaternary ammonium 95 24.2
CloisiteÒ25A MMT Dimethyl, dehydrogenated tallow, 2-ethylhexyl quaternary 95 18.6
ammonium
CloisiteÒ93A MMT Methyl, dihydrogenatedtallow ammonium 95 23.6
CloisiteÒ30B MMT Methyl, tallow, bis-2-hydroxyethyl, quaternary ammonium 90 18.5
NanofilÒ15 MMT Dimethyl, dihydrogenated tallow alkyl quaternary ammonium 93 28
NanofilÒSE3000 Bentonite Dimethyl, dihydrogenated tallow alkyl quaternary ammonium – –
Nanocor Inc.(USA)
NanomerÒ1.30P MMT Octadecylamine (ODA) 120 22
NanomerÒ1.44P MMT Dimethyl dialkyl ammonium halide – –
Laviosa chimica mineraria (Italy)
DelliteÒ43B MMT Dimethyl benzylhydrogenated tallow ammonium 32–35 18.6
DelliteÒ72T MMT Dimethyl dihydrogenated tallow ammonium – –

pends mainly on the type of polymer matrix used. Researchers ota corporation in 1986 [149]. However, studies on the develop-
investigated the effect of structure of organomodifier on the dis- ment of PCNs based food packaging materials have been
persion of MMT in a series of EVA based copolymers [142]. They re- published only since the late 1990s [150]. By far the most promis-
ported that the surfactant consisting of two alkyl tails is more ing nanocomposite systems are organic polymers and inorganic
effective than the surfactant having one alkyl tail in forming exfo- clay minerals. Several nanoparticles have been recognized as pos-
liated nanocomposites, provided one of these substituents must be sible additives to enhance polymer performance. Among all the po-
a long carbon chain of 12 or more atoms to organophilize the pris- tential nanofillers, the prototypical clay utilized in food contact
tine clay mineral. An increase in the number of long alkyl chains on applications is montmorillonite, MMT [24,150]. The clay structure
the surfactant improves exfoliation of the clay in polyolefin. On the is formed by hundreds of platelets or sheets stacked into particles
other hand, nanocomposites formed from polyamides exhibited like pages of a book. To realize the large filler aspects ratio and to
complete opposite trend. For polyamides, surfactants with a single take full advantage of the reinforcement or tortuosity clay particles
long alkyl tail give the best exfoliation and an increase in alkyls can provide to the nanocomposites, they must be exfoliated into
leads to unfavourable polyamide–alkyl interaction, resulting in de- single platelets, distributed homogeneously and oriented in the
crease in exfoliation [147]. In summary, increase in d-spacing de- appropriate direction into the continuous phase. The exfoliation/
pends on the cation-exchange capacity of layers, content and delamination is affected by the affinity of clay platelets toward
structure of surfactant and on the way the surfactants organize polymer matrix while their alignment is influenced by the type
themselves in the clay. of processing used to prepare nanocomposite test samples, e.g.,
mixing, extrusion, injection moulding, etc. Table 10 summarizes
5. Polymer/clay nanocomposites the commonly used polymeric materials, their typical properties
and application in food packaging [151].
Polymers have replaced conventional materials (glass, ceramics, Reinforcing materials are often used for compounding with
metals, paper and board) in food packaging owing to their polymeric materials in order to improve their mechanical or ther-
functionality, light weight, low cost and ease of processability. mal properties. According to some studies conducted to improve
However, their strength and capability to resist deformation are the physical properties of polymer–clay nanocomposites, a small
lower as compared to metals and ceramics [148]. Furthermore, amount of clay was added to a nylon6–clay nanocomposite and
their inherent permeability to gases and vapours is another limit- various improvements were achieved: higher polymer strength,
ing property in food packaging [133]. To meet the increasing higher heat resistance, enhanced thermal stability, enhanced gas
expectations of consumers and to address the aforementioned barrier properties and so on [152]. Polymer clay nanocomposites
shortcomings of polymeric materials, there have been extensive are actually developed to reduce the permeability of gases, like
investigation of suitable packaging materials with enhanced per- oxygen and carbon dioxide; organic vapours and moisture that
formance properties; and manufacturing high performance materi- are hazardous to packaged material [12]. There have been many re-
als is the dream of material scientists and engineers. In last two searches involving the use of nanoparticles as rigid impermeable
decades, a new and an emerging class of clay filled polymers, called fillers in the development of nanocomposites to improve barrier
polymer clay nanocomposites (PCNs) has been developed and performance pertaining to gases and vapours [153–159]. These
much research activity has been dedicated to the development of studies have demonstrated that the polymer clay nanocomposites
PCNs that could improve the performances of polymers for food can retard the migration of potentially harmful additives into pack-
packaging by adding nanoparticles. Polymer clay nanocomposites aged food. In general, the clay platelets are impermeable and their
prepared by different methods, including polymerization of a incorporation into the matrix polymers results in creation of tortu-
monomer in the presence of clay (in situ polymerization), polymer ous pathway for a permeant diffusing the nanocomposite. The
intercalation in solution, emulsion polymerization in the presence presence of clay fillers results in longer mean path rather than a
of layered silicates and by dispersing the nanoclay into the molten straight line for the diffusion of permeant as shown in Fig. 9 [24].
polymer. It is important to note that the length of tortuous path is a function
The concept of PCNs was developed after the first successful of the high aspect ratio of the clay filler and the volume% of the clay
application of nylon-6/MMT hybrid material developed by the Toy- filler in the composite.
 K. Majeed et al. / Materials and Design 46 (2013) 391–410 403

Table 10
Most commonly used commodity polymers and their applications in food packaging [151].

Polymer Abbreviation Recycling Properties Applications

name symbol/code
Polyethylene terephthalate PET
Low permeability to gases and vapours; good resistant to heat, Bottles for carbonated drinks; containers;
mineral oils, solvents and acids. trays; blister packs

High density polyethylene HDPE

Stiff, strong, tough, resistant to chemical and moisture, easy to Bottles for milk, juice and water; margarine
process tubs, cereal box liners

Polyvinyl PVC Stiff, medium strong and transparent material; resistant to Bottles, packaging films and blister packs
chloride chemicals, grease and oil; good flow characteristics and stable
electrical properties

Low density polyethylene LDPE

Flexible, strong, tough, easy to seal, resistant to moisture Film applications, like bread and frozen food
bags, flexible lids, squeezable food bottles

Poly PP Harder, denser, transparent, resistant to heat and chemicals. Yogurt containers and margarine tubs,
propylene microwavable packaging

Poly styrene PS Clear, hard and brittle material; Foaming produces an opaque, rigid, Egg cartons/trays, containers, disposable
lightweight material with impact protection and thermal insulation plastic silverware, lids, cups, plates, bottles,
properties and food trays

Various theoretical models have been proposed to explain the diction that have been experimentally verified [160]. It is worth
improved barrier properties of polymer/clay nanocomposites. The mentioning that the Nielsen’s model predict permeability of nano-
impermeable clay layers force a tortuous pathway for a permeant composite systems for small filler loading percentages. While on
and this tortuosity is usually the primary way by which nanofillers the other hand, at higher loading levels, the experimental data
influence the barrier properties. The simplest and most widely deviates from predicted results owing to the particle agglomera-
known model, firstly proposed by Nielsen, assumes that the fillers tion, which reduces mean particle aspect ratio [160]. Most of these
are of rectangular platelets of uniform size and are evenly dis- models are based on the assumptions that the impermeable clay
persed throughout the matrix. Furthermore, the diffusion rate of platelets are randomly distributed in parallel arrays with their
the penetrant is only influenced by the tortuosity of the path. From main direction perpendicular to the diffusion direction. It is worth
the model, it can be predicted that the barrier effectiveness is ex- noting that the orientation and length of clay platelets influence
pected to increase with an increase in the filler aspect ratio, a pre- the permeability of the nanocomposites [161]. As complete exfoli-

Fig. 9. Diffusion path for a permeating molecule through (a) Polymer film, and (b) Nanocomposite film having exfoliated impermeable clay platelets [24] reproduced from
Trimothy by permission of Elsevier Science Ltd., UK.
404 K. Majeed et al. / Materials and Design 46 (2013) 391–410

Table 11
Barrier properties of some representative polymer/clay nanocomposites for different clay loadings.

Nanocomposites Clay content (wt.%) P(O2) P(H2O) Ref.

EVA(15.5 % VA)/OMMT (melt compounding followed by blow film) 0 145.8 [23]
2 106.8
5 76.6
7 81
LDPE(25 % LLDPE & 5 % LLDPE-g-MA)/OMMT (melt belnding and blow film) 0 3.41 [140]
2.91 1.71
4.76 1.38
LDPE(6% EVA)/oMMT (solution casting) 0 3.4 [167]
4 1.9
HDPE (15% HDPE-g-MA)/OMMT 0 67.25 0.127 [168]
5 23.92 0.053
PP (5 % MAPP)/OMMT (melt blending) 0 480 – [169]
5 374
PET/Na-MMT supported with chlorotitaniumtriiospropoxide (melt polycondensation) 0 857 22 [170]
1 76 26
2 61 21
5 55 19
Polyamide 12/oMMT (melt mixing and compression moulding) 0 – 243 [171]
2.71 151
LLDPE(15 %oxidized polyethylene)/oMMT 0 5.36 [172]
4.76 2.42 –
PP/EPDM/oMMT (solution casting) 0 9.03 [173]
3 4.94 –
5 3.89
PS/OMMT (solution casting, solvent CCl4) 0 3.15 [174]
2 – 2.44
10 1.98
PMMA/OMMT (in situ polymerization) 0 0.811 177 [175]
1 0.631 136
3 0.532 117
5 0.442 104
PMMA/OMMT (solution dispersion) 0 0.951 236 [175]
1 0.933 206
3 0.777 204
5 0.726 191
PU/OMMT 0 6.3 1.9 [176]
6 4.7–8.6 1.1–1.2
⁄
It is important to note that polymer processing and clay incorporation method, as well as polymer molecular weight, organic modifier type, temperature, humidity and film
thickness all varied significantly from one study to the next.

ation of clay platelets into the polymer matrix is not always the Clays have also been reported to reinforce polymeric materials
case, many deviations can be explained by factors such as less than substantially even with a low level of filler loading, usually 1–
complete exfoliation or poor clay orientation. 5 wt.%. A research programme conducted by U.S. army soldier sys-
The effects of the interfacial regions have been found to be par- tems centre, Natick, found that 100% increase in Young’s modulus
ticularly important in polymer matrices that possess very high na- of low density polyethylene could be achieved by incorporating
tive gas permeabilities, such as polyolefins [162]. In order to chemically treated clay platelet [150]. Cui and Paul [142] synthe-
predict permeability of polymer nanocomposites, Beall proposed sized PCNs by melt blending various organoclays with two series
a new model which provides a correction factor applicable to Niel- of ethylene based polymers, ethylene vinyl acetate (EVA) copoly-
sen’s model. In the said model, polymer–clay interface acts as a mers (VA contents from 0–40) and sodium ionomers of ethylene
governing factor in addition to the tortuous path [163]. The use methacrylic acid (EMAA) copolymers (neutralization levels from
of compatibilizers or surfactants to incorporate the filler into the 20–70%). In the case of EVA copolymers, clay exfoliation improved
matrix uniformly and efficiently, can also affect the diffusivity of with the increase of the VA content of the matrix polymer, increas-
permeants [24]. Another mechanism by which nanoparticulates ing the relative modulus of nanocomposites. For EMAA copoly-
influence the barrier properties is by causing changes to the matrix mers, the addition of organoclay to the matrix resulted in better
polymer at the polymer–nanofiller interface. In nanocomposites, exfoliation at elevated neutralization level which leaded to signif-
the polymer chains located in close proximity to nanofillers can icant improvements in stiffness of the nanocomposite. Researchers
be partially immobilized provided the polymer–nanofiller interac- prepared LDPE/OMMT (cloisite 15A) nanocomposites via melt mix-
tions are favourable. This immobilization results in the attenuation ing in an internal mixer using EVA copolymer as a compatibilizer.
of permeant diffusing through these interfacial zones as observed They found that the reinforcing effects of organoclay mainly apply
by positron annihilation lifetime spectroscopy (PALS) [164–166]. to the modulus instead of to the strength [167].
Many studies have reported the effectiveness of clay platelets in Increasing the clay content usually results in an increase in the
improving the barrier properties of the nanocomposites, as can matrix Young’s modulus and in a significant loss of ductility,
be seen in Table 11 for a number of different polymer clay especially at clay contents above about 3 wt.% [22,23,167,177–
nanocomposites [23,140,167–176]. Barrier properties of some rep- 181]. Alexandre et al. [171] reported that polyamide 12/OMMT
resentative polymer/clay nanocomposites for different clay (C30B) nanocomposites were found to have improved relative
loadings. Young’s modulus as compared to virgin matrix polymer. Tabuani
 K. Majeed et al. / Materials and Design 46 (2013) 391–410 405

Table 12
Tensile strength and modulus of various polymer/clay nanocomposites.

Nanocomposites Clay content Tensile modulus Tensile strength Elongation Ref.

(wt.%) (MPa) (MPa) (%)
PP(5 wt.% PP-g-MA)/OMMT 0 1520 221 [182]
7.7 2680 3.6
PU/OMMT 0 7.6 14 170 [187]
1 7.9 10.9 132
3 9.4 13 141
5 10.3 14.5 149
PVC/OMMT (solution blending followed by melt compounding and injection 0 930 24 130 [192]
moulding)
0.99 1190 23.5 145
1.96 1540 28 170
4.76 1620 27.5 160
9.09 1440 25 90
a-PA(20 wt.% EOR-g MA)/OMMT (melt compounding followed by injection 0 1800 54 143 [193]
moulding)
1.60 2250 59 97
3.29 2770 64 59
PI/OMMT 0 2850 131 30 [194]
3 3130 120 22
5 3340 117 16
7 3650 110 13
PP/Na-MMT 0 1430 33.6 30.8 [195]
1 1620 34.1 16.3
3 1860 33.9 13.1
5 1880 32.8 7.2
PP(2 wt.% PP-g-MA)/OMMT (melt compounding followed by injection 0 675 29.4 20 [196]
moulding)
2 845 32.3 12.5
Red algae/Na-MMT (solution casting) 0 – 9.1 34.65 [197]
1 – 10.33 40.92
3 – 10.89 41.29
5 9.78 40.07
Red algae/OMMT (solution casting) 0 – 9.1 34.65 [197]
1 – 9.2 38.72
3 – 10.85 40.49
5 – 9.77 39.91

et al. [182] Melt mixed polypropylene with various nanofillers clay loading is only 2 wt.%. Finally, the reinforcement aspects are
(montmorillonite, hydrotalcite, sepiolite and boehmite) owing to a major part of the nanocomposite investigations reported in
their different chemical nature and organic modification with poly- the literature and Table 12 shows the tensile properties of various
propylene to investigate the influence of nanofillers’ nature on polymer/clay nanocomposites [182,187,192–197]. Higher tear
material properties. They concluded that dispersion and chemical strength [186], higher dynamic mechanical properties [198],
nature of the filler play a fundamental role on mechanical proper- increased flammability resistance [182,199,200]; reduced coeffi-
ties of the nanocomposites. Furthermore, they observed that the cient of thermal expansion; and enhanced thermal stability
nanocomposites derived from OMMT with the PP-g-MA exhibited [143,144,172,174,201–203] are among other benefits that have
improved modulus as compared to other nanofillers, but it drasti- been reported on the performance of a variety of polymers as
cally decreased elongation at break by giving a fragile material. resulting from using clay nanoparticles.
Similar trends were are also seen for nylon-6/OMMT nanocompos-
ites [183], for HDPE and PS blend melt mixed with sodium mont-
morillonite [184] and PE-g-MA [168] for the nanocomposite films 6. Natural fibre/nanoclay hybrid composites
prepared by melt blending HDPE, OMMT and HDPE grafted maleic
anhydride; and also for nanocomposites prepared using melt pro- Hybrid composites are materials made by combining two or
cessing techniques from a sodium ionomer of poly(ethylene-co- more different types of fibres in a common matrix [204,205].
methacrylic acid) [185] and a series of organoclays. However, Although several fillers can be incorporated into the hybrid system,
exceptions to this general trend have been found in some studies a combination of only two types of the fibre would be more
reporting similar or even higher elongations at break than the vir- beneficial. By careful selection of the reinforcing fillers/fibres, the
gin matrix [143,144,169,186–190]. Hemati and Garmabi [143] re- performance properties of the resulting composite can be signifi-
ported a significant increase in elongation at break with the cantly improved while the material cost can be substantially
incorporation of nanoclay in maleic anhydride modified linear reduced. Hybrid composite materials are attractive as they result
low density polyethylene compatibilized LDPE/LLDPE nanocom- in a balance between performance properties and the cost of
posite. In another study researchers reported an increase of both the composite that cannot be obtained with a single kind of
the tensile stress and elongation at break in the case of EVA/OMMT reinforcement [73,74,205]. Previously, there have been studies
nanocomposites [191]. The enhancement is maximum when the regarding the hybridization of natural fibre with another natural fi-
406 K. Majeed et al. / Materials and Design 46 (2013) 391–410

bre [206], glass fibre [73,205,207,208], carbon [209], and mica respectively [212]. In addition to improvement in tensile proper-
[210]; and have produced encouraging results. The properties of ties, hybridization of nanoclay with reed flour also lowered the
the hybrid composite mainly depend upon the fibre content, length water absorption and thickness swelling.
of the individual fibres, orientation, arrangement of both the fibres,
extent of intermingling of the fibres and fibre to resin adhesion
7. Conclusions
[205,211]. In another work on hybrid composites, researchers
studied the effect of coupling agent on physical and mechanical
Polymer/clay nanocomposites represent one of the most prom-
properties of reed flour/PP/nanoclay hybrid composite [212]. They
ising classes of materials of the last decades and have received
reported a positive effect of coupling agent on the physical and
much attention due to significant increase in the mechanical and
mechanical properties of reed flour/PP/nanoclay hybrid composite.
barrier properties of food packaging. The enhanced properties are
In another related work researchers investigated the effect of fibre
due to synergistic reactions between the matrix polymer and
lengths and fibre loading on the mechanical performance of hybrid
nanoclay at the nanoscale level; and can be obtained by incorpora-
composites [211,213]. They found that there is optimum fibre
tion of small amount of nanofiller in polymer matrix. However, the
loading beyond which properties of hybrid composites started to
nonbiodegradability behaviour of these materials creates many
decrease.
environmental problems. In recent decades much research activity
The incorporation of nanoclay to the HDPE/rice husk system in-
has been dedicated to natural fibre reinforced biocomposites; and
creased their tensile strength, tensile modulus, storage modulus
the environmental, economic and performance issues have pro-
and loss modulus [214]. It was found that the composites contain-
vided much of the impetus to the progression and utilization of
ing 2 phc (parts per hundred contents) of the nanoclay had the best
these materials in several applications. The prospective benefits
morphology (intercalated structures) among the rest formulations.
of the natural fibre reinforced composites depend mainly on the
Furthermore, the addition of nanoclay to the rice husk flour rein-
behaviours and properties of natural fibres as reinforcing fillers.
forced HDPE composite increased crystallization temperature,
The most interesting aspect about natural fibres is their positive
crystallization enthalpy and crystallinity level. The author sug-
environmental impact with respect to ultimate disposability. How-
gested that a fully exfoliated morphology can be obtained by
ever, the poor interface quality between the fibre and matrix poly-
enhancing the compatibilizer loading. In another study [215], the
mer results in poor stress-transfer efficiencies; and water
hybrid effect of nanoparticles and hemp fibre, not only increased
absorption properties of natural fibres is another issue hindering
the stiffness but also flexibility of the PP based hybrid composites.
their industrial applications. Fossil fuel based polymers are non-
This study also reported a significant decrease in water absorption
degradable and non-renewable while renewable polymers are gen-
and thickness swelling with the increase in nanoparticles loading.
erally sensitive to moisture and do not provide effective gas barrier
However, an improvement was reported in the dynamic mechani-
properties. Hybrid filler filled composites have shown great poten-
cal behaviour, dimensional stability, and fire retardancy of the hy-
tial in making up to overcome some of these shortcomings. Recent
brid composites. In another interesting work, researchers studied
researches on the properties of a novel class of hybrid composite
the effect of compatibilization and organoclay incorporation on
materials indicate that bio-based nanocomposites are poised to
thermal and mechanical properties of wood flour/HDPE compos-
play a positive role in the development of stronger, high barrier
ites [216]. The addition of compatibilizer improved mechanical
and eco-friendly food packaging materials. Furthermore, develop-
properties and reduced thermal expansion coefficients of wood
ment of these materials will not only benefit food packaging indus-
flour/HDPE composites. They also observed that the incorporation
tries but would also lead towards new markets such as electronic
of organoclay in wood flour/HDPE composites further reduced the
and pharmaceutical packaging.
thermal expansion and enhanced the mechanical properties. It is
worth noting that in the presence of nanoclay, more compatibilizer
is required to enhance mechanical properties. Future developments
Hybridization of 5 wt.% of nanoclay with micro-crystalline cel-
lulose increased Young’s modulus from 1.040 to 1.240 GPa of the Natural fibre/nanoclay reinforced polymeric materials are the
micro-crystalline cellulose reinforced ethylene–propylene (EP) subject of many scientific and research projects. When natural fi-
co-polymer [217]. The addition of nanoclay to the cellulose con- bres are mixed with nanoclay particles, the resulted hybrid mate-
taining composites resulted in 15% decrease of water absorption rials will exhibit improved barrier properties, and it can be
of the composites. Furthermore, the addition of nanoclay increased composted and returned to the soil. Obtaining the optimum prop-
their thermal degradation onset temperature indicative of an en- erties for the hybrid composites will usually require excellent dis-
hanced thermal stability. X-ray diffraction (XRD) and transmission persion of the filler and its good compatibility with the matrix.
electron microscopy (TEM) results revealed that the composites Hybrid packaging material from natural fibre/nanoclay reinforced
prepared by incorporating nanoclay are intercalated structures. polymer materials can be developed at lower cost while increasing
In another study, they reported the effect of nanoclay dispersion sustainability and functionality. Such materials have become indis-
on physical and mechanical properties of the wood–plastic–nano- pensable in a wide range of applications and the drive towards
clay hybrid composites [204]. Polypropylene-wood flour compos- green products and sustainable manufacturing will increase de-
ites were reinforced with glass fibres and nanoclay while PP-g- mand of hybrid materials for food packaging. Mechanically stron-
MA was used as coupling agent. An increase in the tensile strength ger and higher barrier materials are also highly desirable for the
and modulus of the composites was observed with an increase in packaging of other vapour and gas sensitive materials, including
the glass fibre contents. Tensile strength and modulus of the nano- electronic and pharmaceutical packaging. However, despite their
clay filled hybrid composites increased with an increase in the attractive degradation characteristics and significant demand for
nanoclay loading up to 4 phc and then start decreasing. Hybridiza- such materials, the lack of compatibility and interfacial adhesion
tion of the wood flour with glass fibre minimized the water absorp- between the filler and matrix phase prevents them from having
tion of the composite and XRD results showed that the dispersion widespread commercial impact. Modification of the resin systems
of clay in the hybrid composite is better at 4 than at 6 phc of clay. in the hybrid composites can help to develop and design food pack-
The addition of 4 phc nanoclay with MAPP as compatibilizer to the aging materials for different applications either to be stable or bio-
reed flour/PP biocomposite increased the tensile strength and degradable. An additional demanding area is the potential of
Young’s modulus from 14.6 and 1390 MPa to 28.7 and 2630 MPa, nanoparticles (from packaging material) to migrate to packaged
 K. Majeed et al. / Materials and Design 46 (2013) 391–410 407

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