Polymer-Plastics Technology and Engineering

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Aerospace Application of Polymer Nanocomposite

with Carbon Nanotube, Graphite, Graphene Oxide,
and Nanoclay

Ayesha Kausar, Irum Rafique & Bakhtiar Muhammad

To cite this article: Ayesha Kausar, Irum Rafique & Bakhtiar Muhammad (2017) Aerospace
Application of Polymer Nanocomposite with Carbon Nanotube, Graphite, Graphene Oxide,
and Nanoclay, Polymer-Plastics Technology and Engineering, 56:13, 1438-1456, DOI:
10.1080/03602559.2016.1276594

To link to this article: https://doi.org/10.1080/03602559.2016.1276594

Published online: 17 Apr 2017.

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POLYMER-PLASTICS TECHNOLOGY AND ENGINEERING
2017, VOL. 56, NO. 13, 1438–1456
http://dx.doi.org/10.1080/03602559.2016.1276594

Aerospace Application of Polymer Nanocomposite with Carbon Nanotube,

Graphite, Graphene Oxide, and Nanoclay
Ayesha Kausara, Irum Rafiquea, and Bakhtiar Muhammadb
a
Nanosciences Division, National Center for Physics, Quaid-i-Azam University Campus, Islamabad, Pakistan; bDepartment of Chemistry, Hazara
University, Mansehra, Pakistan

ABSTRACT KEYWORDS
In this review, potential and properties of carbon nanotube, graphite, graphene oxide, and clay Aerospace; challenges;
nanofiller have been deliberated with reference to aerospace application. The polymers discussed nanofiller; polymer; thermal
as matrices are polypropylene, polyaniline, polyurethane, polystyrene, and polyamide. Main focus stability
of the review is to converse space competency of polymer/carbon nanotube, polymer/graphite,
polymer/graphene oxide, and polymer/clay nanocomposite. The effect of nanofiller addition on the
desired aerospace properties of polymeric nanocomposite has been conversed. Attractive features
are high glass transition temperature, thermal stability, high modulus, chemical resistance, and
nonflammability. Toward the end, challenges in the enhancement of materials’ properties for
aerospace relevance have been considered.

GRAPHICAL ABSTRACT

Introduction The generated heat if not dissipated might potentially

influence the composite structural integrity. The poly-
The usage of polymer-based composite in aerospace
mer matrix has very low thermal conductivity due to
applications has significantly improved because of their
which they are not suitable for thermal design loads
outstanding superior specific features. The pursuit for
in aerospace applications. For thermal conductivity of
enhancement of thermal conductivity in aerospace
polymer matrix, various research studies have been
structure has gained remarkable attention. Today,
performed[1]. For the improvement of thermal conduc-
aerospace structures are integrated with electronics
tivity of polymer matrix, different fillers have been
which generated significant amount of heat energy.

CONTACT Ayesha Kausar asheesgreat@yahoo.com Nanosciences Division, National Center for Physics, Quaid-i-Azam University Campus,
44000, Islamabad, Pakistan.
Color versions of one or more of the figures in this article can be found online at www.tandfonline.com/lpte.
© 2017 Taylor & Francis

utilized[2]. The fillers may be in the form of particle or
fiber dispersed in polymer matrix. The particle-filled
composites have isotropic thermophysical features,
while fiber-filled composites have anisotropic thermo-
physical features. In current years, several studies have
been conducted where nanoparticles have been inte-
grated in polymer matrix for enhancement of thermal
conductivity[3]. The polymer composite materials with
reinforcement of at least one dimension in range of
1–100 nm is defined as nanocomposite. Most common
fillers used for polymer reinforcement are carbon
nanotube (CNT), layered silicate nanoclay, graphite,
graphene, and graphene oxide (GO). The excellent
electrical, mechanical, and thermal characteristics of
CNT render them ultimate applicant as nanofiller in
lightweight polymer composite. Nanotube-strengthened
polymer composites have become interesting structural
materials not only in the weight-sensitive aerospace
industry but also in the armor, marine, civil engineering
structures, automobile, railway, and sporting goods. All
these industries demand high specific stiffness and spe-
cific strength[4]. By the integration of CNT into a variety
of polymer matrices, such as polypropylene (PP), poly-
amides (PAs), polyimides, epoxy, and polyurethane,
various nanocomposites have been generated[5]. The
recent and future commercial utilization of CNT has
generated remarkable academic interest in polymer/
CNT composite. Moreover, CNT has been found as
an additive material in polymers mainly polycarbonates
(PCs), epoxies, polyethylenes, polyamides, polystyrene
(PS), and polyurethane[6]. Graphene-based polymer
composites have been used as an electrode for dye-
sensitized solar cells, liquid crystal devices, organic solar
cell, field emission devices, and organic light-emitting
diodes. These composites have high carrier mobility,
high electrical conductivity, and moderately high optical
transmittance in a visible range of spectrum. In several
electronic devices (solar cell, flat panel display, and
touch screen), transparent conducting films have been
used[7]. Derivative of GO and conducting polymers
were combined and used in supercapacitors such as
combination of pseudo-capacitors. For the incorpor-
ation of GO and reduced graphene oxide (rGO) sheet
in supercapacitor, conducting polymer like polyaniline
(PANI) is one of the most used polymers[8]. Epoxy/clay
nanocomposite strengthened with high-strength glass
fiber has outstanding perspective for commercial appli-
cations in automotive and aircraft industries because of
their capability to improve mechanical features and
reduced component weight. Filaments convoluted with
carbon fiber-reinforced cryotanks made with epoxy
nanocomposites has fivefold lower helium leak rate in
comparison to that of corresponding tanks made
POLYMER-PLASTICS TECHNOLOGY AND ENGINEERING 1439
without clay[9]. The significant reduction in leak rate
may be because of flow-induced alignment of clay layers
during processing. Use of these advanced, high barrier
composites would eliminate need for liner in composite
cryotanks, thereby simplifying construction and reduc-
ing propellant leakage[10]. In this review, we have con-
ferred the current potential of polymer nanocomposite
in aerospace industry. Various categories of polymers
and polymer nanocomposite used in aerospace applica-
tions have been systematically conversed. Toward the
end, challenges and potential of aerospace composite
have also been discussed for future advancement in this
field.
Aerospace relevance
In polymeric systems, utilization of inorganic fillers
has become a common research practice to form nano-
composite for aerospace constituents, sporting goods,
and automobiles. Several polymeric nanocomposites
are commercially synthesized[11]. In early 1980s, drift
in the field of nanotechnology has been assisted by the
initiation of scanning probe microscopy and scanning
tunneling microscopy. The alteration from microparti-
cle to nanoparticle produces considerable changes in
physical features of final composite[12]. A nanostruc-
tured constituent may have significantly diverse features
than the large dimensional material of same compo-
sition. There is inverse relation between material
diameter and surface area per unit volume in case of
fiber and particle. Smaller the diameter, greater will be
the surface area per unit volume[13]. Carbon fiber and
organic matrix-based composites are progressively
being used in spacecraft and aircraft industries because
of remarkably high strength, modulus, lightweight, good
fatigue life, high stiffness, and excellent corrosion
resistance. Currently, considerable amount of advanced
polymer composites has been utilized for commercial
and military aircraft and satellite constituents. Due
to their low density, low manufacturing cost, and
outstanding mechanical and physical features, these
materials have substituted metals mainly aluminum
alloys in several aerospace applications[14]. Passenger
aircraft Boeing 747 and 767 have composite parts such
as rudders, doors, elevators, spoilers, flaps, ailerons,
and fairings to reduce the weight and to enhance the
fuel efficiency and pay load. There are various property
demands (lightweight, electrical, and thermal behavior)
with respect to the type of application[15]. Consequently,
it is desirable to utilize composites with zero thermal
conductivity and good thermal and electrical conduc-
tivity. According to the application, good electromag-
netic shielding efficiency may also be required.
1440 A. KAUSAR ET AL.
Carbon fiber, coated carbon fiber, CNT, clay, graphene,
graphite fillers, iron fiber, and ferrite powders are some
of the constituents utilized to achieve advanced light-
weight aerospace composites[16]. Recent innovative
engineered constituent systems such as organic matrix
composites have numerous applications including
sporting goods, aerospace structures, high-potential
automobiles and boats. Composite aerospace structures
generally have exciting property demand for high-
potential material systems mainly nanocomposite.
Moreover, there is a strong necessity of processability,
lightweight, life cycle, and low cost in choosing new
structural constituents[17]. The multifunctional, light-
weight, and easily manufactured structural constituents
such as polymer matrix composites have been progress-
ively utilized in aircrafts. The polymer matrix composite
contradicts the enhanced fuel and cost maintenance of
commercial airplane[18]. Polymer matrix composites
are usually favored over metals due to fatigue resistance,
corrosion suppression, reduced part count, and
restrained temperature application (300°C). Future
aerospace systems and recent progressive systems
pursue to further improve both multifunctional and
mechanical features of composite by the integration
of nanoparticles. Thus, polymer nanocomposite has
a broad range of applications in aerospace and
aeronautical fields[19].
Polymer in aerospace
Considerable challenges and opportunities exist in char-
acterization and creation of engineering constituents.
For growing number of industries, polymers have
become more and more fascinating. For engineering
applications, there is increased use of polymeric consti-
tuents because of ease of processing/manufacture, low
cost, lightweight, and good chemical features[20]. After
the discovery of structural adhesives, several current
technological achievements have become probable.
Polymer adhesive industry is recently focusing
structural application such as protective coating and
reparability parts to integrate such materials in aviation,
petroleum, and aerospace production systems[21].
In this section, various aerospace thermoset and
thermoplastic polymers such as epoxy, polyamide,
polypropylene, polyurethane, and PANI have been
discussed.
Epoxy
The scrutinized fact in metal is corrosion. However, the
corrosion resistance of carbon steel has been the subject
of several scientific studies. For corrosion prevention of
carbon steel, ideal protection route has not been found
yet. The most generally used and suitable route for the
protection of metal against corrosion is application of
coating, generally organic coating[22]. The main role of
organic coating is to provide physical resistance against
oxidizing species mainly H2O, O2, and Cl. Although,
there is no permanently in impermeable organic coating
and once defect is formed, the corrosive species may
reach metal surface of and corrosion may occur[23].
Epoxy is one of the most common barrier coating
materials utilized under simple corrosion conditions
mainly in marine environment. Because of hydrophilic
chemical groups in the structure of cured epoxy resin
(carboxyl groups (C¼O), hydroxyl group (OH), and
amino groups (NH2)) comprising unpaired electrons,
epoxy attract water from environment and results in
protection for metal. Epoxy was first discovered in
1909[24]. It is defined as prepolymer containing more
than one epoxide group and have low molecular weight.
It is an important thermosetting resin, which is
hardened by using various curing agents during curing.
Its essential features are dependent on definite combi-
nation of epoxy resin and curing agents utilized. Due
to outstanding mechanical features, high adhesiveness
to various substrate and excellent chemical and heat
resistance, recently epoxy resin has been extensively
used in technical fields. Epoxy resins may act as
fiber-strengthened constituents, high-potential coatings,
general purpose adhesives, and encapsulating
constituents[25]. Epoxy resin is the most significant class
of thermosetting resin for numerous engineering
applications due to good electric behavior, high strength
and stiffness, resistance to chemicals, corrosion and
microbial organisms, good thermal features, low
shrinkage during cure in superconducting cables, space
technology, and large cryogenic engineering products
mainly International Thermonuclear Experimental
Reactor[26].
Polypropylene
First, synthetic stereoregular polymer which obtains
industrial importance is polypropylene. It is currently
an emergent fiber for technical end uses where impor-
tant features are excellent tensile strength coupled with
low cost. In 1999, PP was designed for 18% of world’s
synthetic fiber consumption (5.5 million tons)[27]. It is
used in upholstery, apparel, floor coverings, car indus-
try, hygiene medical, automotive textiles, wall coverings,
and numerous home textiles. The development of
extruded, oriented film technology led to the develop-
ment of polypropylene end uses comprising tapes/slit-
film and several fibrillated and fibrous products. The

PP monomer is generally produced by refining of pet-
roleum, as it is hydrocarbon gas. The PP chain consists
of monomer with asymmetric carbon atom at position
of C2, –CH2CH(CH3)–. Thus, PP may exist in three
types (atactic, isotactic, and syndiotactic) of molecular
configuration dependent on related orientations of side
groups of methyl. Both the syndiotactic and isotactic
forms have methyl group located frequently with refer-
ence to adjacent groups along molecular chain. It has
characters of fiber formation because of ordered struc-
ture of polymer. Recently, isotatic propylene is chief
commercially available stereoisomer for oriented fiber
tapes and films[28]. Thus, polyolefin generally poly-
propylene comprises family of most significant and
useful constituents due to fascinated set of features
and low cost. Property modification of polypropylene
is essential as large volume thermoplastic polymers of
extremely excellent commercial importance[29]. By the
incorporation of CNT, the potential of polypropylene
has been enhanced. Among the stereoisomers of
polypropylene, the most demanded form in industry is
isotactic form. For film and fiber manufacturing,
syndiotactic polypropylene is also a capable material.
Nowadays, its global production reached capacity of
∼14 million kg/year[30]. Consequently, multicomponent
polypropylene composites have been utilized in large
quantities in automotive industry (fabrication of
bumpers) and other applications. For the enhancement
of fracture and impact resistance of PP, elastomer
additives have been used[31].
Polyaniline
Polyaniline is ranked among the most studied conduct-
ing polymers. Besides its electrical features, catalytic,
optical, electrochemical, and surface features have been
considered. PANI is usually synthesized from aniline
monomer and oxidants. It has poor solubility in com-
mon solvents such as ethanol, methanol, and acetone.
PANI nanostructure may have enhanced dispersibility
in the host matrices[32]. Due to low synthetic cost,
superficial synthesis, and outstanding thermal and
environmental stability, PANI is the most extensively
studied conducting polymer. There are three main
forms of PANI, namely, the fully oxidized (pernigrani-
line) state, fully reduced (leucoemeraldine), and the
more conducting emeraldine base (half oxidized).
Emeraldine is the most conductive form to produce
emeraldine salt by doping. PANI can be easily synthe-
sized either electrochemically or chemically from acidic
aqueous solutions. The chemical route has great impor-
tance because it is successful for PANI mass production.
The most common synthesis route is the oxidative
POLYMER-PLASTICS TECHNOLOGY AND ENGINEERING 1441
polymerization with ammonium peroxodisulfate as an
oxidant[33]. PANI is one of the most extensively studied
conducting polymers due to strong bimolecular interac-
tion, superficial synthesis, and electrochemical,
electrical, and optical features. It holds great potential
in comparison to other conducting polymers due to
outstanding tunable conductivity by charge-transfer
doping and protonation[34–36]. Due to its thermal stab-
ility and conducting behavior, it has been extensively
used in electrochromic devices, electrocatalysis, and bio-
sensors. Moreover, PANI has several significances such
as excellent redox reversibility, high polymerization
yield, and high thermal and environmental stability. It
displays conductivity only in acidic media at pH < 3
in emeraldine salt state. In general, the PANI chemistry
is more complex as compared to other conducting poly-
mers due to its dependency on various oxidation states,
i.e., pernigraniline base (fully oxidized form emeraldine
base as shown in Figure 1[35].
Polyamide
Polyamide resins are broadly used as extrusion and
injected molded constituents and in textile industry.
Polyamide is widely recognized as an engineering
thermoplastic. Because of the outstanding thermal and
mechanical features, it is extensively studied in indus-
trial applications such as films, fibers, textiles, and
numerous molding products[37]. Polyamide is generally
used in fabrics, carpets, and other tough goods
applications. For example, polyamide-6 (PA-6) or
polyamide-6,6 (PA-6,6) is generally blended with
acrylonitrile butadiene styrene, styrene, polypropylene,
rubber toughening, or other polymer additives.
Polyamide-11 is utilized in gas pipelines and crude oil,
hydraulic and pneumatic hoses as optical fiber
sheathing and powder coating[38]. Polyamide-6 is
semicrystalline thermoplastic, which has been broadly
Figure 1. Different oxidation states of PANI. Note: PANI,
polyaniline.
1442 A. KAUSAR ET AL.
utilized in engineering applications because of excellent
features and processability. Moreover, PA-6 also
comprises some disadvantages, chiefly high water
absorption, low heat deflection temperature, and
dimensional instability. In response to demand for
high-potential constituents, several fiber reinforcements
such as carbon, glass, natural fiber, and liquid crystalline
polymer have been added to polyamides[39]. In general,
integration of discontinuous fiber to polyamide may
lead to considerable improvement in stiffness, fracture,
and strength toughness. Consequently, short glass
fiber-strengthened polyamides find applications for
bonnet automobile parts and in relative industries
where high-potential materials are necessary[40,41].
Polyamide has been efficiently reinforced using glass
fibers and other inorganic additives. Although, in such
composites, the additives and polymers are not uni-
formly dispersed. To overcome this problem and to
increase the features of host polymer, molecular compo-
sites of thermoplastic have been prepared. Significance
of polyamide may be limited by moisture absorption,
notch sensitivity, poor dimensional stability, and low
impact strength[42]. The aliphatic analogues of polyam-
ide are generally known as nylons. There is another
class of glassy copolymer generally recognized as
glass-clear nylons attained from the condensation of
aliphatic diamines and aromatic diacids. There are
numerous industrial applications of nylons with excep-
tional features such as thermal resistance, good trans-
parency, rigidity, and hardness. Some of their
applications need further property enhancement
through integration of inorganic nanofiller[43].
Amorphous polystyrene, being colorless and trans-
parent, is one of the most significant plastics. It has
outstanding electrical resistance and low dielectric loss.
It is stiff, hard, and very brittle. High-impact poly-
styrene is copolymer of polystyrene with elastic polymer
mainly polybutadiene. In general, brittle PS can be
converted into polymer with certain degree of flexibility
by fiberization[44]. The expandable polystyrene (EPS)
has been extensively used in numerous engineering
fields, nevertheless offers some problems at high
Figure 2. Nano-objects used as nanofiller.
temperature. Thus, by exposure to source of heat, the
polymeric constituents decompose forming volatile
combustible products, which easily turned EPS to
flammable material. The halogen-based constituents
have been integrated as an additive flame retardant in
polystyrene[45]. Hyper-cross-linked polystyrene was first
introduced in early 1970s. The unique feature of this
polymer is extremely low density in dry state. In fact,
the polymer in nonclassical physical state is hyper-
cross-linked polystyrene[46]. The two basic features
such as swelling tendency and porosity account for
remarkable adsorption property of hyper-cross-linked
polymers[47].
Nanofiller for aerospace material
Filler is one of the most important raw materials used in
materials science. The production of filler is known to
be 50 million tons per year. They are generally used
in composite constituents to decrease the consumption
of expensive binding material and for enhancement of
physical features. They can be of various shapes such
as spherical particles, rod, disk flakes. In general, the
particle size, geometry, functionalization, and chemical
coating instigate the features of filler materials. In
construction sector, fillers are extensively utilized in
coating and paints, adhesive and sealants, in plastic,
rubber, and concrete. In advanced composites, they
are tiny particle which may enhance the appearance
and mechanical properties. The integration of nanofiller
in polymer matrix may considerably influence the
properties of materials such as controlled rheological
features, and enhanced thermal, optical, electrical,
mechanical, and nonflammability properties[48]. The
composite property may be greatly affected by nanofiller
to organic matrix ratio. In general, nanofillers can be
categorized as 1D nanofillers (nanofibers and nano-
tubes), 2D nanofillers (platelets, shell, laminates), and
0D, or 3D nanofillers (silica, and beads) (Figure 2).
Various types of nanofillers (CNT, graphite, graphite
oxide, and clay) with end application in aerospace have
been discussed.
 POLYMER-PLASTICS TECHNOLOGY AND ENGINEERING 1443

Carbon nanotube ceramics, and metal-reinforced composite[55]. There-

fore, CNT has been used in numerous applications such
Carbon nanotube is a minute hollow cylinder with
as aerospace, radar-absorbing material, electromagnetic
diameter ranging from 0.4 to 2.5 nm[49,50]. An ideal
interference (EMI) shielding, sporting goods, fuel cells,
single-walled carbon nanotube (SWCNT) is formed by
wind turbine blades, automobiles, and electronics.
rolling of graphene sheet, which is exclusively
comprised of carbon atoms. Principally, their length is
unrestricted ranging from 10 to 100 µm. Most of the Graphite
precisely formed CNTs are multiwalled carbon nano-
Graphite and diamond are well-recognized allotropes of
tube (MWCNT), which are comprised of two or more
carbon. The investigation of carbon nanostructure
concentric cylinders of SWCNT with different
became very significant with the discovery of fullerenes
diameters. The diameter of MWCNT is up to several
and CNT[56,57]. Carbon is polymorphic. Three main
hundred nanometers[51]. In general, MWCNT is com-
forms in which carbon exists is graphite, diamond, and
prised of disturbed wall form and texture which are
fullerenes. The chief difference in graphite and
then called bamboo MWCNT or herring bone. In
diamond is that the bonding of carbon in diamond
general, irregular shaped CNT may be chemically more
involves sp3(tetrahedral) hybridization, while in
active as compared to ideal[52]. The variations in CNT
graphite, carbon bonding involves sp2 hybridization
morphology may occur due to different synthesis meth-
(trigonal). The carbon layers of graphite are called
ods. The outstanding features of CNT offer potential for
graphene[58]. Graphite is anisotropic and excellent
fabrication of polymer composites with considerably
thermal and electrical conductor because of in-plane met-
enhanced features such as strength, conductivity,
allic bonding. The electrical conductivity permits graphite
elasticity, durability, and toughness. CNT has been used
to be utilized as electrochemical electrodes and as electric
in sporting goods (such as rackets, tennis), aerospace,
brushes because of in-plane covalent bonding and weak
and aircraft industry. Textiles of polymer/CNT com-
perpendicular to layers. As a result of anisotropy, layers
posite comprise of tear proof or conductive fibers[53].
of carbon may slide easily with respect to one another,
The future application of polymer/CNT is displayed in
thus making graphite a good pencil material and
Table 1. Recent research has displayed the probability
lubricant[59]. Because of anisotropy, graphite is capable
of utilizing CNT films in highly flexible solar cells,
to undergo chemical reactions by permitting the reactant
which may potentially be utilized as replacement for
called intercalate between graphene layers. Such reactions
brittle and expensive conductors recently used in solar
are called intercalation. In graphite intercalation com-
cells[54]. CNT is a very capable nanofiller material in
pounds (GIC), there is charge transfer between graphite
composites having exceptional thermal, electrical,
and intercalate to form electrically conductive material
mechanical, and magnetic features. CNT-strengthened
in comparison to that of graphite. For EMI shielding,
polymer composites have fascinated much attraction
conductivity may lead to high effectiveness. Most GIC
due to better compatibility of polymer and nanofiller.
can be exfoliated on heating. The mechanical interlocking
Properties are also found better than the inorganic,
due to compression of exfoliated graphite flakes may
form graphite gasket materials without binder[60].
Table 1. Application areas of carbon nanotube.
Industry sector Application material Graphene oxide
Medicine and Medical application (e.g., drug delivery)
life sciences Medical diagnosis (e.g., lab on a chip) Graphene comprises several fascinating physical features
Chemical sensor of high chemical stability and large surface area
Cosmetics (antiaging creams)
Filter for water and food treatment (∼2,600 m2/g) for potential applications in transistors,
Energy Hydrogen storage, energy storage (super capacitor) lithium secondary batteries, and graphene sheet super
Fuel cell
Solar cell capacitors. For the modulation of electrical features of gra-
Superconductive material phene, chemical doping is significant[61]. Graphene is an
Material and Polymer/CNT composite (heat conducting polymer)
chemistry Coating (e.g., conductive surfaces) atomically thin layer of sp2 hybridized carbon atoms pre-
Ceramic and metallic CNT composite scribed in honeycomb lattice. Boehm et al[62]. in 1986
Tip of scanning probe microscopes (SPM)
Membrane and catalysis
referred to graphitic single layer as graphene. Graphene
Electronics Molecular computing and data storage is most frequently highlighted by physicist due to huge
Microelectromechanical system (MEMS) carrier mobility and range of unusual phenomenon rising
Microelectronics: Single-electron transistor
Ultrasensitive electromechanical sensor from linear energy dispersion[63]. The development in gra-
Lighting elements, CNT-based field emission display phene applications have been resulted from remarkable
1444 A. KAUSAR ET AL.
thermal, mechanical, optical, and chemical features. The
strong oxygenation of graphite oxide has been performed
by highly hydrophilic constituents. It may readily exfoliate
in water to achieve stable dispersion comprising of single-
layered sheet known as graphene oxide[64]. Chemically
derived graphene has become a generic term to describe
rGO and its derivatives. GO can also be recognized as che-
mically modified graphene, functionalized graphene,
reduced graphene, or chemically converted graphene.
The chemical exfoliation of graphite by oxidation may lead
to covalent functionalization, which considerably changes
the graphene structure[65]. The existence of functional
groups also cause modification of electronic structure of
graphene. Consequently, GO chemical composition which
can be thermally, chemically, or electrochemically
engineered permits tenability of optoelectronic features[66].
Nanoclay
Clay is generally found in large amount recognized as
kaolin (aluminum silicate). This clay is displayed by for-
mula Al2O3·2SiO2 2H2O. For polymer nanocomposites,
clay minerals such as kaolin, bentonite, talc, and mica
have been utilized as inorganic fillers. Clay reinforce-
ment may offer remarkable features such as hardness,
electrical insulation, thermal stability, brightness, and
opacity[67]. Montmorillonite (MMT) clay is generally
formed by deposited volcanic ash in lakes. It is mineral
of colloidal layered silicate. MMT is the soft clay related
to phyllosilicate group of minerals. It is a member of
smectite family. Its platelets are composed of octahedral
sheet, which are covered by tetrahedral sheet on both
sides just like a sandwich. Its basic structure is MgOA-
l2O2·nSiO2 H2O[68]. Kaolinite is a clay mineral with
chemical composition of Al2Si2O5(OH)4. It is a layered
mineral of silicate, having one tetrahedral sheet linked
through oxygen atoms to one octahedral sheet of alu-
mina octahedral. Rocks in which sufficient kaolinite is
found are recognized as kaolin or china clay. The
impure form of clay is bentonite comprising of MMT.
It has absorbent aluminum phyllosilicate forming paral-
lel sheets of silicate tetrahedral with Si2O5[69]. The clay
mineral utilized for the synthesis of polymer/clay nano-
composite can be categorized into three groups, i.e., 2:1
type, 1:1 type and layered silicic acids.
Various categories of polymer
nanocomposite in aerospace
Polymer/carbon nanotube nanocomposite
Due to distinctive features of CNT, they are being
extensively studied as constituent of composite material.
For electrical, mechanical, and space applications,
CNT-based composite materials are progressively being
considered. CNT has been studied for suitability and
applications in aerospace and aeronautical fields. In
aerospace, prospective is the improvement in electrical
properties of composite made from epoxy resin and
CNT. The significance of CNT has been increased
since their scientific introduction in the advanced
materials[70]. The prospective applications of CNT have
been amplified by manifold in different scientific disci-
plines, such as in mechanical systems, energy storage
biological applications, sensing, and field emission. As
aerospace engineering is considered to be one the fore-
front disciplines of the future, these materials may play
a game-changing role in this industry. The probable
implementation of CNT and benefits thereof are evident
with the development of Space Shuttle[71]. Due to
remarkable features such as thermal, electrical, and
mechanical features, the significance of using CNT in
aerospace applications has increased. Highly conductive
and strong composite fibers based on cellulose and
MWCNT with multiple hydrogen bonding moiety
(MWCNT-MHB) have been reported[72]. The com-
posite fiber with MWCNT-MHB showed high tensile
strength of 156–278 MPa, strain of 3.7–7.0%, and initial
modulus of 11.3–13.9 GPa. The electrical conductivity
of the composite fiber was increased from 10 8 to 100
S/cm with an increase in MWCNT-MHB content. For
both military and commercial aircraft and future space
vehicles, the weight of vehicle plays considerable role
and it directly influences the cost of operation[73]. The
challenge that aerospace industry continuously faces is
the introduction of spacecraft or light aircraft, without
artificial structural integrity. Gohardani et al[74]. recog-
nized that the two leading factors are propulsive and
total weight, which may influence the future commer-
cial aircraft-distributed propulsion technology. In
addition, dispersed propulsion nanotechnology was
commercialized in subonic fixed wing aircraft[75,76].
Therefore, the material with implantation of CNT
seemed to be essential in aerospace space industry for
future designation[77]. The tensile test was performed
by Allaoui et al. to limit extensometer strain by 25%[78].
Figure 3 shows the stress–strain curve. The resin
achieved was very ductile. The maximum stress level
reached was 30–50 MPa. The stress level was enhanced
by the addition of CNT. With the addition of 1 wt%
CNT, strength and Young’s modulus was doubled.
The mechanical properties of composite are shown in
Table 2. For brittle constituent like PS, bending
measurement was a suitable route to test its mechanical
features. The storage modulus of neat PS and composite
comprises different concentrations of SWCNT. Three
 POLYMER-PLASTICS TECHNOLOGY AND ENGINEERING 1445

Figure 3. Tensile test stress–strain curves of the resin and its

composites[78].

Table 2. Young’s modulus and stress at different strain

levels[78].
Young’s Yield strength,
CNTs (wt%) modulus (MPa) r0.2% (MPa) r10% (MPa)
0 E0 ¼ 118 1 4
1 236 (2*E0) 3 8
4 465 (3.9*E0) 6 10
CNT, carbon nanotube.

samples for each concentration was synthesized and

measured to average out of possible error from prep-
aration of sample. Thus, remarkable data scattering
was displayed by moduli of composites. The overall
tendency displayed only an uncertain enhancement
with SWCNT loading in comparison to that of neat
PS. With the addition of 2 wt% annealed CNT, the flex-
ural modulus was enhanced by 20–30% (Figure 4)[79].
The tan d peak of neat PP and its composites with
1 wt% materials is shown in Figure 5. The displacement
Figure 5. (a) Tan d for pristine PP and its composites filler
(with) 1 wt% and (b) Tan d as a function of single-walled nano-
tube content[80].
of peak was observed at higher temperature by nano-
tube addition[80]. Young’s modulus was gradually
improved by an increase in polymer content. It was
concluded that the reinforcing effect of SWCNT was
pronounced in comparison to that of carbon black
(Table 3). Song et al[81]. prepared covalently functiona-
lized CNT wrapped in intumescent flame retardant.
The diameter of functionalized CNT was controlled

Table 3. Properties of PP–SWCNT and PP–CB[80].

Young’s Yield Maximum
modulus strength strength Deformation
Materials (MPa) (MPa) (MPa) at break (%)
PP 855 24.5 30.8 493
PP–SWCNTs 1,020 29.5 35.7 447
(0.25%)
PP–SWCNTs 1,101 30.5 35.9 420
(0.5%)
PP–SWCNTs 1,187 31.0 35.5 410
(0.75%)
PP–SWCNTs 1,087 29.3 33.8 402
(1%)
PP–CB (0.25%) 868 24.7 30.5 452
PP–CB (0.5%) 892 28.0 32.3 422
PP–CB (0.75%) 938 28.4 33.7 419
Figure 4. Dependence of the flexural modulus on concen- PP-CB (1%) 962 28.7 29.8 397
tration of the annealed single-walled nanotube[79]. SWCNT, single-walled carbon nanotube.
1446 A. KAUSAR ET AL.
Figure 6. Stress–strain curves of PU and its composites with
2 wt% carbon nanotube[85].
∼20–90 nm. Functionalized CNT showed better
dispersion in polypropylene matrix due to in situ
compatibilization. Flame-retardant-wrapped CNT
improved flame retardancy and mechanical properties
of polypropylene. CNT has also been used along with
other nanofillers to improve the flammability properties
of composite. The effect of CNT with graphene and GO
has been investigated on intumescent flame-retardant
polymer nanocomposite[82,83]. Similarly, the effect of
incorporating three types of nanoparticles, i.e., CNT,
reduced graphene nanoplate, and nanoclay have
been studied in polypropylene[84]. In Figure 6, the
stress–strain properties of PU and the composites are
displayed. At breaking point, the strength at break of
composite was evidently higher in comparison to that
of PU[85]. Model of MWCNT inserted in hard segment
of polyurethane is shown in Figure 7. The chemical
route for the preparation of PU/CNT composite is
shown in Figure 8. It was displayed by the results that
the CNT in polymer matrices played dynamic role in
Figure 7. Model of multiwalled carbon nanotube inserted in the hard segment of polyurethane of TDII and PTMO.
load transfer. The nanocomposite has been the field of
interest in aeronautics because of the combination of
reinforcing effect and large surface area of nanofiller.
The nanoparticle integration and adhesion at particle
matrix interface are the framework of remarkable
importance with instant influence on mechanical
features[86]. Studies relative to aircraft have been
performed in heavy aircraft category with reference to
Federal Aviation Administration[87].
Polymer/graphite nanocomposite
Polymer graphite composites have long been utilized in
structural and aerospace application[88]. Electrically
conductive polymeric composites are generally used as
temperature-dependent resistors, heating elements,
sensors, switching devices, self-limiting electrical
heaters, and antistatic materials for EMI shielding of
electronic devices[89]. The significance of thermal con-
ductivity in polymer composites is linked to the need
for considerable level of thermal conductivity in circuit
boards, appliances, heat exchangers, and machinery[90].
The thermal conductivity of constituents is also essen-
tial for modeling of optimum conditions during
material processing as well as for the analysis of heat
transport in materials during practical applications.
The availability of graphite constituents has important
influence on mechanical behavior of filled polymer[91].
The dependence of Young’s modulus (E) of composite
on graphite content is shown in Figure 9. There was a
significant enhancement in Young’s modulus with an
increase in graphite content. The improvement was
more prominent for low-density polyethylene (LDPE)/
graphite composite. The absolute value of Young’s
modulus of composite was higher in the case of high-
density polyethylene (HDPE)/graphite composite.
Since, in comparison to LDPE matrix, HDPE had

Figure 8. Preparation of PU/carbon nanotube nanocomposite.
greater Young’s modulus[92]. Thermal conductivity of
HDPE, PS/graphite composites versus graphite content
are displayed in Figures 10 and 11. With an increase
in graphite content, a nonlinear improvement in
thermal conductivity was observed. Thermal conduc-
tivity was not dependent on the size of particle. More
conductive paths were generated as a result of higher
agglomeration of graphite particles Klassic Stage (KS),
Figure 9. Young’s modulus (E) of the graphite-filled LDPE
(squares) and HDPE (circles) as a function of the volume filler
content (φf)[92].
POLYMER-PLASTICS TECHNOLOGY AND ENGINEERING 1447
similarly to the electrical conductivity shown above[93].
Thus, with highly enhanced features and ease of proces-
sing, polymer nanocomposites may replace the conven-
tional composites. Indeed, these enhancements have
been achieved at low filler content[94]. Consequently,
polymer nanocomposites are the capable candidates
for the applications in high-potential structural compo-
sites involved in aircraft production, marine,
Figure 10. Thermal conductivity (kc) of graphite EG, and
graphite KS-filled HDPE versus the volume filler content (φy)[93].
1448 A. KAUSAR ET AL.

Figure 11. Thermal conductivity (kc) of graphite EG and graph- Figure 12. Thermal conductivity (Kc) of PA6 and PA6/PC/
ite KS-filled PS graphite on the volume filler content (φy)[93]. graphite composites as a function of graphite content[95].

automotive, sporting goods, and spacecraft composites. conductivity of system exceeded 30 wt%. In comparison
Some of the potential applications of layered polymer to unfilled system, the thermal conductivity of flake
nanocomposites are shown in Table 4. Investigation graphite-filled immiscible system reached 4.75 W/K
on polyamide-6 filled with graphite has also been per- which was 16.3 times higher. Consequently, composite
formed. Over a wide range of filler loading, the thermal has potential applications in aerospace due to remark-
conductivity of PA6 and immiscible PA6/polycarbonate able thermal, electrical, and mechanical properties[95].
composites filling with graphite were prepared. In
Figure 12, the thermal conductivity data (kc) of two
composite systems are displayed. Increase in kc of Polymer/graphene oxide nanocomposite
PA6/PC/graphite composite occurred almost linearly
Graphene oxide is the carbon-based constituent with
as the function of graphite content below 30 wt%
outstanding potential and low cost. The polymer/GO
(17.97 vol%). As compared to low filler content, when
comprises superior tensile strength and Young’s modu-
graphite loading fraction exceeds 30 wt%, the thermal
lus. They are utilized in several mechanical, civil, and
aerospace applications. Carbon fiber composites have
Table 4. Potential application of graphene and nanoclay in been extensively used since 1950s. They also have highly
industry. significant mechanical features and at the same time,
Filler Area Applications they are lightweight and easy to manufacture[96]. In
Graphene Automotive Benefits to electric vehicles to offset polymer composite systems, GO is used as a filler for
adding weight of batteries
Next-generation lithium ion batteries enhancement in mechanical properties of polymer
and bipolar material. Epoxy/GO systems have capability to produce
Electrostatic spray painting in body
parts
strong and lightweight materials with many significant
Electronics Transparent electrodes, LCD screen, properties. The influence of GO on rubber epoxy matrix
and integrated circuit was also studied. Thus, addition of 6 vol% GO greatly
Aerospace and Provide electrostatic discharge and
aviation electromagnetic interference improved Young’s modulus, impact strength, and
shielding components as well as microhardness of the composite. Moreover, the route
weight saving
Transparent electrodes LCD screen for mixing and solution preparation did not sufficiently
and integrated circuits disperse the GO in epoxy matrix. A microscopic
Sporting goods Strength, lightweight
Nanoclay Automotive Making engine covers, timing belt examination showed agglomerates of several tens of
covers, structural seat backs, and micrometer large after maxing[97]. It was shown by
fuel system components
Aerospace and Cryogenic storage system
the results of tensile tests that an improvement in load
aviation transfer, tensile strength, and Young’s modulus was
Packaging Food, drink, and beverage packaging occurred by GO addition. The fracture strain was
Flame retardants Use as coating system to reduce
flammability in computer and seemed to decrease. Figure 13 shows that the GO
monitor housings addition to epoxy matrix induced an improvement in
 POLYMER-PLASTICS TECHNOLOGY AND ENGINEERING 1449

Figure 15. Tensile testing[98]. © Creative Commons license

Figure 13. Tensile strength of graphene oxide/epoxy com- from Housing and Building National Research Center.
posite at different contents of GO[98]. © Creative Commons
license from Housing and Building National Research Center.
PVA/3 wt% GO composites was greater. Furthermore,
Note: GO, graphene oxide.
the decomposition rate of PVA/3 wt% GO was also con-
siderably slower in comparison to other. The movement
tensile strength from 7 to 13 MPa. The maximum of polymer segment and PVA and GO interface was
strength was 13 MPa by the addition of GO content of inhibited by strong interaction. PVA is semicrystalline
1.5 vol%. Further increase in GO content beyond this polymer and its mechanical properties are strongly
amount caused decrease in tensile strength to 7.5 MPa. dependent strongly on its crystallinity. Young’s modu-
To further study the effect of GO addition on mechan- lus and tensile yield strength were measured to be
ical features of composite, variables were measured both
independently and in terms of their mutual interaction,
oxidative treatment, structure, and concentration level.
The tensile test of samples at different GO contents is
shown in Figures 14 and 15. By the addition of GO
content between 0 and 6 vol%, the modulus was con-
siderably increased from 115 to 206 MPa. Because of
the compatibility between GO and epoxy matrix, there
was an improvement in interfacial adhesion. It was
observed that at GO content of 1.5 vol%, the maximum
applied load (tensile strength) to epoxy/GO matrix was
234 N[98]. For the characterization of thermal features of
polyvinyl alcohol (PVA) and PVA/3 wt% GO composite
films, thermogravimetric analysis and derivative ther-
mogravimetric were used (Figure 16). In comparison
to pure PVA, the peak degradation temperature of

Figure 16. (a) TGA and (b) DTG curves of PVA and PVA/3 wt%
Figure 14. Tensile sample at different vol% contents of GO[98]. GO composite films[99]. Note: TGA, thermogravimetric analysis;
© Creative Commons license from Housing and Building DTG, derivative thermogravimetric; PVA, polyvinyl alcohol; GO,
National Research Center. Note: GO, graphene oxide. graphene oxide.
1450 A. KAUSAR ET AL.
Figure 17. Polymer/clay nanocomposite: (a) conventional miscible; (b) partially intercalated and exfoliated; (c) fully intercalated and
dispersed; and (d) fully exfoliated and dispersed.
3.6 � 0.2 GPa and 81 � 3 MPa, respectively[99]. The
effect of graphene and layered double hydroxide
addition on intumescent flame-retardant poly(methyl
methacrylate) composite has also been studied[100].
The poly(methyl methacrylate) composite filled with
1 wt% graphene and 5 wt% layered hydroxide achieved
limiting oxygen index value of 28.2% and UL-94 V1
grade. Exfoliated graphene and polypropylene nano-
composite have also been reported[101]. The inclusion
of 0.42 vol% graphene led to ∼75% increase in yield
strength and ∼74% increase in Young’s modulus of
PP composite.
Polymer/nanoclay nanocomposite
Polymer/clay nanocomposite materials have been used
extensively in diverse applications such as construction
materials, transportation vehicles, electronics, sporting
goods, consumer products, and aerospace applications.
The different types of polymer/clay nanocomposites
are shown in Figure 17. The polymer composite
properties are greatly influenced by microstructure
and dimensions of dispersed phase. Polymer/clay nano-
composite may increase the mechanical strengthening,
high temperature resistance, improved barrier features,
and decreased flammability[102]. Polymer/clay nano-
composite has been used by Toyota research group. It
was investigated by transmission electron microscopy
and X-ray diffraction. The individual layers of clay
particles were exfoliated in polymer matrix (nylon 6).
Intercalated polystyrene/clay nanocomposite has been
prepared. The intercalation of polystyrene in stearyltri-
methylammonium cation-exchanged MMT was
reported by Ogawa et al[103]. The intercalated poly-
styrene/clay nanocomposites have been synthesized by
using organic solvent (acetonitrile)[104,105]. The partial
intercalated and exfoliated nanocomposites are shown
in Figure 18. The sodium ions of MMT were ion
exchanged with vinylbenzyltrimethylammonium. Inter-
calated polystyrene/clay nanocomposites with the
largest basal spacing of 2.45 nm were achieved. There
was no characterization of thermal and mechanical
properties for these intercalated nanocomposites. The
synthesis of clay hybrid polymer film is shown in
Figure 19 [106]. The combustion behaviors of the tested
samples are quite different. All the samples turned soft
and generated volatile gases at the continuous heat flux
of 35 kW/m2. Pure PP had boiling surface and melted
before ignition, while from the beginning, all the PP/
clay composites did not melt and charred. The perfor-
mance of PP/poly(propylene-g-maleic anhydride) blend
was analogous to that of pure PP. The pictures of sam-
ples before ignition and their residues in the cone
calorimetric experiment are shown in Figure 20.
Figure 18. Partial intercalation and exfoliation of platelet
system.

Figure 19. Synthesis of polyimide/clay hybrid film.
Ignition occurred as the mixture of oxygen and volatile
gases exceeded the flammability limits under continu-
ous spark. Some irregular dark floccules were formed
on the surface of PP/clay composites during
combustion.
Future perspective
Due to the distinctive features of CNT, they are being
extensively studied as a constituent of aerospace
composite material. For electrical, mechanical, and
space applications, CNT-based composite materials
are progressively being considered. For the suitability
and application in aerospace and aeronautical fields,
CNT has been studied for the improvement in electrical
properties of epoxy resin and CNT composite.
The significance of CNT has been increased due to
scientific introduction in epoxy matrix for advanced
applications[107]. The prospective application of CNT
has been amplified by manifold in different scientific
disciplines such as mechanical systems, energy storage,
sensing, and field emission. In aerospace engineering,
polymer/CNT is considered to be one the forefront
disciplines of the future. For aerospace industry,
CNT-based materials can play a game-changing role.
POLYMER-PLASTICS TECHNOLOGY AND ENGINEERING 1451
The probable implementation of CNT, for both
aeronautical and aerospace industries, is evident with
the tire of the Space Shuttle and commercial aircraft
(such as Boeing 787 and AirbusA380)[108]. Some of
the challenges for the utilization of CNT in aerospace
applications comprise of uniform CNT dispersion in
composite structure, large-scale production method,
adhesion and alignment issues in resistant polymers,
and complete understanding of toxicity level. In terms
of visual and thermal signature, lightweight, increased
speed, and maneuverability, next-generation aircraft,
rotorcraft, unmanned aerial vehicles, and missiles have
severe concerns. These requirements, however,
stimulate a need for advanced materials and systems.
To meet these demands, CNT is an ideal candidate as
it can be integrating in different technologies. For
the application of nanotechnology in aeronautics, a
number of key technologies are identified[109,110].
Research for the combined excellence of performance
and cost-effectiveness in aerospace manufacturing has
been considered. Probable applications of epoxy/GO
composite comprise coating, adhesives, electronic
packaging, sport equipment, and advanced composites.
For future automotive applications (interior and
exterior panels, gas tanks) and aircraft application
1452 A. KAUSAR ET AL.
Figure 20. Photographs of the samples before ignition (left) and their residues after combustion (right)[106]. Sodium montmorillonite
(Na-MMT); protonic montmorillonite (H-MMT); organic montmorillonite (OMMT); octadecyltrimethyl ammonium chloride [C18H37Nþ
(CH3)3Cl , denoted with C18].
(flame-retardant panels, high-performance parts), these
nanocomposites are a solution. Epoxy nanocomposites
have also been reported as potential candidates by
NASA for cryogenic storage applications[111]. For the
production of high-performance fiber composites in
aircraft and spacecraft industries, tetrafunctional epoxy
resin tetraglycidyl-4,4′-diaminodiphenyl methane cured
with aromatic diamine 4,4′-diamonodiphenylsulfone
has been widely used. Attractive features of this thermo-
setting resin are high glass transition temperature
combined with good thermal and chemical resistance.
Moreover, its low density combined with high tensile
strength and modulus are important properties. In
advanced aerospace composites, epoxy/GO has shown
commercial importance. Hence, to this application,
weight reduction is supposed to be primary driving
factor. In aerospace applications, electrically conductive
composites are crucial for moderate electrical charge in
space vehicles. On the other hand, thermal conductivity
is important for dissipation of tremendous heating in
elastomeric products (vehicle track pads) used in
dynamic loading environment. The nanocomposite
not only enhances service life of thermoset polymer
but also decreases the effect of thermosetting waste on
environment[112]. In automotive application, one of
the most important examples of polymeric nanocompo-
sites is nylon-6/clay nanocomposite utilized for making
belt covers (the Toyota Company). The introduction of
nylon-6 for engine covers on Mitsubishi engines has
been performed by Unitika Japan. The thermoplastic
polyolefin nanocomposite was developed by Chevrolet
Impalas. Automotive companies have used PP/clay
nanocomposite for structural seat backs and clay-12
nanocomposite[113,114]. Organically reformed clays
integrated in nylon-6-polymer matrix considerably
enhanced the barrier features and dimensional stability.
Based on the barrier features, nanocomposite of
polyethylene terpthalate has been studied as exchange
for conventional polymer films[115,116]. Moreover,
graphite platelets are among principle nanoscale filler

in research and development of commercial aerospace
projects[117].
Conclusion
In this review, numerous prospects (thermal, mechan-
ical, and electrical) of CNT, graphite, GO, and nanoclay
nanofiller have been discussed. Consequently, the effect
of these fillers on different types of polymer matrices
(polypropylene, polystyrene, polyurethane, polyamide,
and PANI) has been deliberated. Remarkable enhance-
ment in thermal, mechanical, and flame-retardant
features of polymer may occur with the nanofiller
addition. In this regard, carbon nanofiller has been
considered as an excellent material for aerospace
reinforcement. It has been observed that even very small
nanofiller loading may cause considerable improvement
in desired property. Consequently, the main focus of
the review was on potential of various polymer nano-
composites for aerospace applications. With the techno-
logical advancement, these nanocomposites have been
frequently utilized in a broad range of applications from
electronics to automobile and aerospace parts.
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