Interfacial Aspects Ofc Arbon Composites

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Interfacial aspects of carbon composites
Article in Composite Interfaces · March 2018

DOI: 10.1080/09276440.2018.1439632
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Rajib Paul & Liming Dai
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Composite Interfaces, 25:5-7, 539-605, DOI: 10.1080/09276440.2018.1439632
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Composite Interfaces, 2018
VOL. 25, NOS. 5–7, 539–605
https://doi.org/10.1080/09276440.2018.1439632

Rajib Paul and Liming Dai
Department of Macromolecular Science and Engineering, Case Western Reserve University, Cleveland, OH,
USA
ABSTRACT ARTICLE HISTORY

Carbon-based composites bring great promise for various practical Received 5 September 2017
applications ranging from aviation industry to advanced biomedical Accepted 25 September 2017
sensors. The interface chemistry and the ultimate conductivity of KEYWORDS
these composites are responsible for their functional applicability. Composite; carbon
The interfaces can be modified by various chemical and physical fiber; carbon nanotubes;
techniques. This article reviews the synthesis methods of carbon graphene; polymers;
composites and discusses how the interface properties dictate their interfaces
applicability.
CONTACT Liming Dai liming.dai@case.edu

© 2018 Informa UK Limited, trading as Taylor & Francis Group
540 R. PAUL AND L. DAI
1. Introduction
Composite material is composed of two or more distinct phases (matrix phase and dis-
persed phase) which are chemically & physically different. Composites are used because
the overall properties of the composites are superior to those of the individual com-
ponents. The primary phase, having a continuous character, is called matrix. Matrix is
usually more ductile and softer phase. It holds the dispersed phase and shares a load with
it. The second phase (or phases) which is embedded in the matrix is called dispersed
phase. Dispersed phase is usually stronger than the matrix, therefore it is called rein-
forcing phase. The artificial composites are of three types based on the reinforcement of
two phases, namely, particulate-reinforced, fiber-reinforced and structural composites. A
detailed classification of composite materials is presented in Figure 1. While a focussed
research has been carried out to improve the overall properties of composites, optimiza-
tion of interfacial properties has been more elusive because of the difficulties associated
with the exact detection of interfaces and characterization difficulties. For example, the
interfacial mechanical property within glass fiber-epoxy composite dictates its ultimate
mechanical characteristics. Nevertheless, the ratio between the interfacial surface area
and the material volume in a typical composite reinforced with 60 vol.% of fibers of 6 μm
in diameter is ≈ 2 × 105 m2/m3. As such, in composites, the mechanical damage often
begins by interfacial fracture [1]. For nanocomposite materials, the interfaces are the most
active parts for various catalytic, sensing, adsorption, adhesion and electrochemical as
well as biomolecular activities [2–5].
The trapped charges, defective states and grain boundary regions at the interfaces are
believed to be the cause behind such activities. Therefore, interfaces in a composite mate-
rial needs to be taken care with great importance. In fact, it is an important task to design
interfaces in composites for improved performance.
What is an interface? Interface is the place or area at which different materials meet
and communicate with or affect each other. Carbon based materials have been serving
the research community for decades with its fascinating properties in context of electrical,
thermal, mechanical, chemical and electrochemical as well as various physical properties,
such as adsorption etc., for domestic and industrial purposes [6]. Furthermore, following
the inventions of different carbon allotropic materials, such as buckyballs, carbon nano-
tubes, graphene and their hybrids, the applicability of carbon based materials in form
of nano-metric and macro-metric structures has drastically increased for technological
advancement. Among those advancements, efficient electronics and optical devices, flexible
Figure 1. Schematic presentation of classification for composite materials.

COMPOSITE INTERFACES 541
and transparent energy storage systems, extensively mountable sensors, opto-electronics

and photo-voltaic gadgets are least to be mentioned [7]. As such, carbon based materials
have become reliable in different biomedical, automobile and aviation industries [8,9].
To increase the applicability in different chemical, mechanical and thermal conditions,
carbon materials are often composited with various resins, polymers and metals. Such
carbon composites have demonstrated improved thermal, chemical and electrochemical
properties as compared to carbon or compositing agents themselves. However, the prop-
erty transition in carbon based composite materials are not straightforward and/or well
understood. The functionality of carbon based composites are dependent on the overall
crystallinity or the connectivity of carbon materials within a composite, its porosity, the
interfacial area and the relative interfacial properties. The interfaces between carbon mate-
rials and compositing resin or polymer or metal play an important role in dictating the
fate of carbon composites.
For example, carbon nanotubes (CNTs), irrespective of their wall thickness (single-
or multiwalled), have exceedingly grabbed the attention of researchers and business
leaders within the polymer composite community. The vast potential afforded by the
unprecedented combination of mechanical, electrical, and thermal properties within
one nanoscale additive opens new vistas for commodity plastics, elastomers, adhesives,
and coatings, as well as new specialty systems with never-before-realized combinations
of material properties. Furthermore, the mechanical performance of nanometer-size
reinforcement (<100 nm in dimension) is superior to its micrometer-size counterparts.
The nanocomposites differ from conventional composite materials due to exceptionally
high surface to volume ratio of the reinforcing phase. The reinforcing material can be
made up of particles (e.g. minerals), sheets (e.g. exfoliated clay stacks) or fibers (e.g.
CNT or electrospun fibers). Moreover, the area of the interface between the matrix and
reinforcement phase(s) in nanocomposites is typically an order of magnitude greater
than for conventional composite materials. The matrix material properties are signifi-
cantly affected in the vicinity of the reinforcement [10]. For example, nanotube stiffness
and strength are close to theoretically predicted values because fewer defects are present
in the molecularly precise nanotube structure. But in addition, nanotube flexibility
(and thus, strain to failure) is substantial and may lead to super-tough nanocomposite
materials having large interfacial area. Therefore, an increasing attention and interest
are observed recently in evaluating the role of interfaces in functionality of carbon
composites. Such efforts are prescribing for technologically challenging but interesting
applications of composite materials both in nano-scale and micro or macro-scales. In
this report, we have reviewed the recent research works on the carbon composites for
various advanced applications with an emphasis on the functionality of carbon inter-
faces in composites.
2. Synthesis of carbon composites

Carbon fiber reinforced polymer composites have been serving research community for the
past several decades. Other carbon based allotropic structures like, buckyballs, CNTs and
graphene have joined the club following carbon fiber for betterment of the composite prop-
erties. Various methods have been adapted to make composites of these carbon materials
with different additives. It has been found that the composite processing methods influence
the interfaces in a composite and hence the properties. There are many synthesis processes
depending on the type of reinforcing material. Some of those are mentioned below.
2.1. Carbon Fiber Reinforced Composites

Carbon fiber based composites are widely used in automobiles and aircrafts. In this regard,
carbon fiber and epoxy (CF/E) composites are most popular one in many different engi-
neering fields, owing to their excellent and specific mechanical and structural properties.
However, their poor delamination resistance has seriously limited many practical applica-
tions [11]. Over the past 2–3 decades, many techniques have been developed to improve the
fracture toughness of CF/E composites, which include notably Z-pinning [12], stitching [13]
and interleaving [14,15] at failure-prone regions of composite structures. Various electro-
spun polymer fibers, such as polysulfone, poly(ε-caprolactone) and polyacrylonitrile, were
employed as interleaves in CF/E composite interfaces [14,15], resulting in varying degrees
of success on increasing the toughness against delamination. Furthermore, incorporation of
these thermoplastic interleaves led to possible reductions of electrical and in-plane mechan-
ical properties of the laminates because of their high electrical resistance and mechanical
weakness. To overcome these issues, various conductive carbon nanomaterials as fillers (such
as carbon black [16], CNTs [17,18] and carbon nanofibers (CNFs) [19,20]) are investigated
as multifunctional reinforcements. In this regard, interleaving of carbon fiber epoxy layers
with graphene and/or CNTs have recently received enormous research focus to uplift the
fracture toughness of CF/E composites [21,22]. These nanostructures are very effective
toughening fillers in composites because of their 1D or 2D nanostructures, superior mechan-
ical properties, excellent electrical and thermal characteristics [23,24]. Figure 2 shows the
detailed steps of graphene based interleaving method in which graphene-epoxy composite
is used to fabricate a carbon fabric based prepreg. This prepreg is utilized for interleaving
into a carbon fiber reinforced polymer (CFRP) composite.
The curing process of epoxy in CF/E composites sometimes are found to be dictating
factor. Epoxy curing is done at various temperatures and different pressures for this purpose.
Figure 2. Schematic for fabrication of graphene interleaved carbon fiber/epoxy composites [11], Copyright
to Elsevier Inc. (2017).
There are different types of epoxies which possess different curing temperature, generally
divided into: low temperature curing (below room temperature), room temperature cur-
ing (room temperature to 50 °C), medium temperature curing (50 to 130 °C) and high
temperature curing (above 130 °C). Low temperature curing has always been pro-gaze,
mainly because it can greatly reduce the cost of output. Compared to low-temperature
curing, high-temperature curing certainly puts stringent requirements of equipments, but
can deliver excellent heat resistant products [25]. Therefore, it is necessary to select the
appropriate curing agent as per the curing temperature of the epoxy resin to fully reflect
the effect of the curing agent, while giving the best performance of the composite. Hand
lay-up, vacuum infiltration and hot press methods are involved in the fabrication process for
CF/E composites [11]. Hot press curing and vacuum bag processes at various temperatures
are widely used with different curing durations. Hot press curing is generally performed at
130–200 °C under pressure ranging from sub MPa up to several MPa [1,26].
For improving the interfacial adhesion properties and hence the mechanical properties of
carbon fibers reinforcements in CF/E composites, laser sintering, functional group attach-
ment on surfaces, polymer coating through chemical techniques and growth of nanostruc-
tures using chemical vapor deposition methods are used [27–30]. Such efforts are found to
be fruitful for improving CF/E composite performance for various applications.
2.2. Carbon nanotube based composite materials

Owing to their extraordinary thermal conductivity, mechanical, and electrical properties
together with high specific surface area, CNTs (both, single and multiwalled) find appli-
cations as additives to various structural materials. For instance, nanotubes form a tiny
portion of the material in some (primarily carbon fiber) baseball bats, golf clubs, car parts
or damascus steel etc. [31]. Since the last decade, research activities in the area of CNT
based polymer nanocomposites have been increased dramatically. Extensive efforts have
been dedicated for deep understanding of CNT/polymer composites [32–38]. As mentioned
earlier CNT based composites are generally called nanocomposites because of the size
of reinforcing CNTs. The interface chemistry and hence the synthesis procedure is very
important for CNT based nanocomposite materials.
Similar to CF/E composites, CNT based nanocomposites are also made through hot
pressing technique. Depending on the type of polymer, the synthesis process varies. For
example, CNT fibers/polypropylene composite thin film was fabricated by placing CNT
fibers between two polypropylene thin films and hot pressing at 200 °C to form a sandwich
composite [39]. The specimens were maintained at 200 °C for 5 min to erase thermal history
of the sample and then cooled at a rate of 20 °C/min to the desired isothermal crystalliza-
tion temperature. Interestingly, it is observed that CNTs act like heterogeneous nucleating
agents for polypropylene transcrystallization. Nucleation of polypropylene occurs first at
the surface of the carbon nanotube fiber and grows into transcrystals perpendicular to the
nanotube fiber axis. By analyzing kinetics of the transcrystallization process using the theory
of heterogeneous nucleation, the fold surface free energy of the transcrystals is deduced to
be about 6.8 × 10−2 J/m2. This technique can be easily scaled up to fabricate other polymer
based CNT nanocomposite materials, such as polyacrylonitrile (PAN), polyethylene (PE),
poly(vinyl alcohol) (PVA), polyamide (PA), polyurethane (PU), poly(methyl methacrylate)
(PMMA), polyethylene terephthalate (PET), poly(p-phenylene benzobisoxazole) (PBO),
polyaniline (PAni), polypropylene (PP), poly(ether ketone) (PEK), polyethyleneimine (PEI),

polyimide (PI), polycarbonate (PC), poly(vinyl acetate) (PVAc), polyethylene oxide (PEO),
poly(ethylenimine) catechol (PEI-C), poly(butylene tere-phthalate) (PBT), polyvinylidene
fluoride (PVDF), polyvinylpyrrolidone (PVP), vectra, random aramid copolymer of phy-
droxyben-zoic acid and 2-hydroxy-6-naphthoic acid etc. [40]. Sometimes, CNT/polymer
nanocomposite fibers are fabricated using various spinning methods, such as melt-spinning,
electro-spinning, coaxial electro-spinning, dry-jet wet electro-spinning, gel-spinning, coag-
ulation spinning, wet-spinning, dry-jet wet-spinning etc. [40]. Details of these techniques
can be found in another review paper [40].
The length of reinforcing CNTs has great influence on the properties of CNT/polymer
nanocomposites. The longer CNTs are desirable for improved mechanical and transport
properties in nanocomposites. In this context, Zhou et al. has recently reported synthesis of
three dimensional (3D) CNT sponge (CNTS) of 0.8 to 1 cm thickness [41]. The CNTS were
synthesized by CVD process using ferrocene and 1,2-dichlorobenzene as the catalyst precur-
sor and carbon source, respectively. Ferrocene powders were dissolved in dichlorobenzene
to make a solution at a concentration of ~60 mg/ml, which was then continuously injected
into a 2-inch quartz tube housed in a resistive furnace by a syringe pump at a feeding rate
of ~0.13 ml/min. The reaction temperature was set as ~860 °C. The carrier gas (a mixture
of Ar and H2) was flowing at a rate of ~2000 ml/min and ~300 ml/min, respectively. A 2
inch × 1 inch quartz sheet was placed in the reaction zone as the growth substrate. The
sponge-like products were collected from the quartz substrate after CVD, which typically
reach a thickness of 0.8 to 1 cm for a growth period of ~4 h. The bulk density of Carbon
nanotubes sponge was about 5–10 mg/cm3 with a specific surface area of 300 to 400 m2/g
and an average pore size of about 80 nm (porosity of > 99%). Very recently, Paul et al. has
also reported 3D CNT foam using microwave plasma assisted chemical vapor deposition
method which has even lower density of 4 mg/cm3 and 99.8% porosity [42]. Such ultra-low
dense and highly porous CNT structures are very promising for fabricating CNT/polymer
based composites for advanced applications.
CNT/epoxy composites are synthesized extensively for various applications. In a typi-
cal synthesis method, about 10 grams of epoxy resin is mixed with ~3.2 grams of D230 in
vacuum oven with stirring at ~50 °C to lower its viscosity without accelerating the curing
process significantly [41]. The pre-formed CNTS is then immersed into the mixed liquid,
which is then transferred to a vacuum oven at ~50 °C for ~1 h to facilitate the polymer
infiltration process. Then the nanocomposite was cured at ~75 °C for ~4 h in a vacuum
environment. Figure 3 illustrates the detailed steps for synthesizing CNT/epoxy composite
having dispersed CNT reinforcements [41].
The surface functionalization of CNTs is an effective method to improve the dispersion
of CNTs, and tailor the nanotube/polymer interface at a molecular level which is required
for strong interfacial interactions [43]. Covalent and noncovalent bond formation at the
interfaces have also been widely used for outer-wall modification of CNTs. In this context,
covalent functionalization is efficient in stabilizing dispersions, but the formation of new
covalent bonds generally disrupts the long-range π conjugation among CNTs. This fact inev-
itably leads to the disruption of the electronic conjugation in CNTs [44,45]. Furthermore, the
covalent functionalization normally involves complicated synthetic procedure and tedious
chemical treatments, which is not cost-effective or scalable. On the other hand, noncovalent
functionalization maintains the conjugated structure of CNTs and preserves the electric and
Figure 3. Fabrication of CNT sponge polymer composites (a) SEM images of CNTS (b, c) and CNTS/SMPs
nanocomposite (d, e) [41], Copyright to Macmillan Publishers (2016).
mechanical properties of CNTs, and is hence considered more suitable [46–49]. Moreover,
the noncovalent technique is advantageous for high efficiency, easy operation and low related
cost. Marginally, a balance between covalent and noncovalent interfacial bonding can be
beneficial in respect to cost, efficiency and mechanical properties.
For example, a new compatibilizer [P(GMA-co-VCz) copolymer] containing car-
bazole moiety and reactive epoxide group, which can functionalize multiwalled car-
bon nanotubes (MWNTs) for making superior epoxy composites, has been prepared
by a simple one-pot free radical polymerization [50]. The designed compatibilizer
could noncovalently functionalize MWNTs via π–π interaction and efficiently disperse
MWNTs in organic solvents. A good wrapping of P(GMA-co-VCz) on MWNTs surface
is observed by transmission electron microscope (TEM). P(GMA-co-VCz) function-

alized MWNT are more homogeneously dispersed in epoxy matrix than in the case
without compatibilizer, indicating that the compatibilizer improves the compatibility
between MWNTs and epoxy resin. In addition, the presence of epoxide groups in
compatibilizer could generate covalent bonds with the epoxy matrix and improve the
interface interaction between MWNTs and epoxy matrix. The resulting mechanical and
electrical properties of the epoxy composites with compatibilizer are largely improved
as compared with those of composites without compatibilizer. The addition of as little
as 0.15 wt. % of MWNTs to epoxy matrix affords a great increase of 40% in storage
modulus and 52.5% in elongation at break. Furthermore, a sharp decrease of almost
9 orders of magnitude in volume resistivity of epoxy composite is observed. Plasma
based surface functionalization of CNTs, using atmospheric pressure helium/oxygen
plasma, are also found to be very effective in improving epoxy-CNT interfaces [51].
2.3. Graphene based composite materials

Graphene, a monolayer of sp2-hybridized carbon atoms arranged in a two-dimensional
lattice, has attracted tremendous attention in recent years owing to its exceptional thermal,
mechanical, and electrical properties, large specific surface area and controlled modification.
Graphene based composite films (GCFs), prepared by combining graphene with differ-
ent functional nanomaterials (noble metals, metal compounds, carbon materials, polymer
materials, etc.), show unique optical, mechanical, electrical, chemical, sensing and catalytic
properties [52]. Large quantity of graphene or reduced graphene oxide flakes can be pro-
duced through micromechanical, liquid-phase, electrochemical, intercalation and chemical
(oxidation and reduction) exfoliation as well as sonication of graphite [53–57], whereas
graphene film can be synthesized by chemical vapor deposition method [58].
Owing to fabrication ease and cheapness, graphene based polymer composites have been
tremendously researched in recent years. A variety of processing routes have been reported
for dispersing both graphite nanoplatelet (GNP) and graphene oxide (GO)-derived fillers
into polymer matrices. Although contemporary, many of these procedures have been applied
uniquely to graphene-based composites [59]. Among other factors, the nature of the bond-
ing interaction at the interface between the filler and matrix has significant implications
for the final composite properties, and most dispersion methods produce composites that
are non-covalent assemblies where the polymer matrix and the filler interact through rela-
tively weak dispersive forces and π–π interactions. However, there is a growing attention on
introducing covalent linkages between graphene-based filler and the supporting polymer
to promote stronger interfacial bonding [60].
As an example, the synthesis procedure of reduced graphene oxide (rGO)-PAni com-
posite film has been illustrated in Figure 4(a) [61]. The aniline molecules forms ions in
hydrochloric acid solution and the residual oxygen functional groups in rGO helped
to form rGO-PAni composite through electrostatic interaction, hydrogen bonding and
π–π stacking interaction (Figure 4(a)) [61]. Furthermore, addition of ammonium per-
oxydisulfate helped the aniline monomers to polymerize. The PAni nanoparticles were
found to anchor onto rGO surfaces, which increased the specific surface area of the
composite. Moreover, the rGO sheets provided high carrier mobility, which resulted
Figure 4. (a) Schematic diagram for preparation process of the RGO-PANI hybrid film [61], Copyright to
Royal Society of Chemistry (2015). (b) Schematic illustration of the formation of RGO Phenol Formaldehyde
(PF) composite film [62], Copyright to American Chemical Society (2014).
in the rapid response time towards NH3 gas sensing. Except a fast response at room
temperature, the sensor exhibited high sensitivity and good selectivity to aromatic
organic vapors.
In another report, Zhao et al. synthesized phenol formaldehyde (PF)-rGO compos-

ites with an interactive oxidation-reduction reaction by in situ intercalate polymeriza-
tion (Figure 4(b)). Owing to non-covalent interaction through π–π stacking and covalent
bonding between GO and phenol homologs, GO sheets have achieved excellent dispersion
and strong interfacial interactions with the PF matrix, resulting in enhanced mechanical
strength, electrical conductivity and thermal conductivity. These non-covalent polymeri-
zation techniques can be easily extended for producing graphene based different polymer
nano-composites and micro-composites (with agglomerated graphene particles) [63].
There have been extensive studies on graphene and various functionalized graphene
nanocomposites with polymers, such as, epoxy, PS, polyaniline (PAni), polyurethane (PU),
poly(vinylidene fluoride) (PVDF), Nafion, polycarbonate (PC), PET, etc. More research
on high-performance graphene based polymer nanocomposites is needed. In this context,
tetracyanoquinodimethane (TCNQ) is very effective in functionalization of graphene and
modifying its career mobility and concentration which may be beneficial for various appli-
cations, such as opto-electronics [64]. TCNQ can be easily fabricated through thermal
evaporation method as presented in Figure 5 where a solar cell anode is fabricated using
layered structure of graphene and TCNQ. There are many reports on polymer based func-
tionalization for modifying the interfaces in graphene composites. More detailed works on
graphene based polymer nanocomposites can be found in other review reports [65–70].
Graphene based epoxy composites are also attractive due to abundant interfacial and
edge interactions between the basal plane and edges of graphene flakes and epoxy which
trigger various functionality in graphene/epoxy nanocomposite materials [71]. In many
cases, dispersed graphene sheets are utilized as an agent to modify the interfaces between
reinforcing fibers and epoxy. Such attempt is found to improve the dielectric permittivity
and good processability of composite and strong interfacial bonding, which provides high
strength and modulus and moderate dielectric property [72]. Graphene composite is also
very promising ink in 3D printing processes for nanocomposite fabrication [73].
2.4. CNT and/or Graphene Based Hybrid Carbon Composite Materials

Combination of CNTs and graphene together with fiber based carbon matrix has great
promise in making multifunctional and mechanically advanced composite materials with
polymers. Graphene and/or CNTs serves as filler nano-additives particularly at interfaces
between polymer and fibers which imposes multifunctional activities with great efficiency. In
this context, modified carbon fiber reinforced plastic (CFRP) laminates have received great
Figure 5. Schematic of a solar cell anode consisting of layer by layer structure of graphene and thermally
evaporated tetracyanoquinodimethane (TCNQ) [64], Copyright to American Chemical Society (2012).
enthusiasm in aerospace and automotive engineering owing to their excellent mechanical

properties. The main components of CFRP laminates are carbon fabric layers combined
by various epoxies [74]. In such layered laminate structure, delamination and crack prop-
agation at the interfacial regions are two major drawbacks against fabricating mechanically
stable composite materials. To minimize these problems, there have been various efforts to
modify the fiber epoxy interfacial regions with different mixtures of polymer and carbon
nano-structures. Such as, coating polydopamine (PDA) and graphene oxide (GO) on the
surface of carbon fabric [74], coating GO on CF surfaces [75], electrochemical oxidation
coupled with the electrophoretic deposition of GO on fiber [76], coating CNTs or CVD
growth of CNTs at CF/epoxy interfaces [77–82] hybrid coating of GO and CNTs both on
fiber surfaces [83] are worth mentioning. Use of functionalized rGO and CNTs are also
well known as effective filler in fiber/epoxy composites [74,81,84].
Figure 6 shows detailed structural and micro-morphologies of the failure at fiber/epoxy
interface with GO and polydopamine (PDA) [74]. At first the functional groups, such as
catechol and amino groups are introduced on the surface of carbon fabric by coating an
ultrathin layer of PDA on CF surface. For synthesizing GO, graphite powders are oxidized
through acid oxidants consisting of concentrated sulfuric acid, potassium permanganate
and sodium nitrate via the modified Hummers method [85] and graphite oxide is thus
obtained. The oxidated product is purified by rinsing and centrifuging with a 10% HCl
Figure 6. Schematic diagrams and micro-morphologies of the failure of fiber/epoxy interface of (a) pure
CFRP; (b) GO sized CFRP and (c) PDA&GO sized CFRP [74], Copyright to Elsevier Inc. (2017).
solution, repeatedly washing with copious amounts of deionized water. The resulted sus-
pension is treated by ultrasonic technique (1000 W) for 2 to 3 h to exfoliate the graphite
oxide in layered GO and to form a homogeneous GO in a solution, as per experimental
requirements. Afterwards GO/ethanol solution (0.2 mg/ml), is sprayed onto PDA coated
carbon fabric for 10 times from left to right at a relatively constant speed. The interval
between each spraying is kept at 5 min to evaporate the ethanol.
Well-adhered GO coating on CF surface can also be performed by simple solution casting
of carbon fibers and GO in aqueous solution followed by stirring, drying and then cooling
naturally to room temperature [75]. Figure 7 illustrates the procedure in details. In order
to evaluate the coating efficiency of GO on short CFs (SCFs) in such physical adsorption
process, dried GO coated SCFs are re-dispersed and intensively stirred in deionized water
and then observed by SEM. The result shows that GO is still firmly adsorbed on the surfaces
of SCFs. Moreover, the weights of SCFs before and after 0.5 wt% GO-coating are measured
and it is found that approximately 96% of the prescribed GO is adsorbed on the surfaces of
SCFs. The obtained GO-coated SCFs are then compounded with polyethersulfone (PES)
to prepare the PES composite extrudates using a TSE-20/600-4-48 co-rotating twin-screw
extruder at a screw speed of 30 rpm and a feed rate of 6 rpm. All the materials are dried in
an oven at 130 °C for 6 h prior to melting process. The extrudates are continuously cooled
Figure 7. Schematic method of GO coating on SCFs: (a) SEM image of bare SCF; (b) at the beginning of
drying, stress analysis on the emersed GO and SCF surface and demonstration of surface tension (F); (c)
in a further drying process, stress analysis on the emersed GO and SCF surface and demonstration of
surface tension (F) and additional tension (Ps) and (d) SEM image of one GO-coated SCF [75], Copyright
to Elsevier Inc. (2017).
by water and then pelletized. Afterwards, the as-prepared pellets are dried in an oven at
130 °C for 6 h before injection molding. The test bars are obtained by injection molding at
the mold temperature of 180 C using HTF80X/1 plastic-injection molding machine.
The surface modification of carbon fiber (CF) by electrochemical oxidation is also an
effective way to increase adhesion properties [76]. After such oxidation, GO adhesion on
CF surfaces is achieved easily through the electrophoretic deposition technique to improve
the mechanical performance of carbon fiber reinforced epoxy composites. The surface
roughness and wettability increased after the electrochemical oxidation treatment of CF by
the electrophoretic deposition technique, which can be an attractive and feasible method.
A uniform distribution of GO coating is easily constructed and the GO sheets are firmly
coated on the CF surface through covalent attachments. This continuous fabrication process,
does not involve long processing times or complex chemical reactions and offers a potential
industry compatible method for preparing multiscale GO/CF reinforcements.
The Vacuum infiltration and hot-pressing techniques can also be combined to make
CNT/CF/epoxy composites [78]. Short carbon fibers (SCFs) were prepared by cutting plain
woven carbon fiber fabrics (Inter-Turbine Advanced Logistics Pty Ltd, 203GR/SM) [86]. The
diameter and average length of SCFs were about 7 mm and 750 (±200) mm, respectively.
Then, carbon nanotubes (CNTs) grew on the SCF surface by the ethanol flame synthesis
method for 3 min. Functional organic groups could be found on the CNTs after the flame
growth process [87]. The size of CNTs was ~20 nm diameter and 1–2 μm length. The weight
fraction of CNTs on the carbon fibers was ~18%. The detailed synthesis process is shown
in Figure 8(a) [78]. The resin and curing agent are mixed in weight ratio of 100:5. Areal
densities of short carbon fibers (SCF)/epoxy or CNT-SCF/epoxy interleaves in the middle
Figure 8. (a) Schematic for the fabrication of SCF or CNT-SCF interleaved CF/EP laminates and SCF modified
epoxy bulk composites [78], Copyright to Elsevier Inc. (2017), (b) scheme of MWNT growth on carbon
fiber (CF) using chemical vapor deposition (CVD) method; FESEM images of bare CF (c) after desize by
Soxhlet extraction and (d) hairy MWNT-graft-CF grown by CVD method [77], Copyright to American
Chemical Society (2017).
layer are set at 0.5 mg/cm2, 1.0 mg/cm2 and 2.0 mg/cm2. This process seems scalable for
fabricating different nanomaterial interleaved CF/polymer composites.
To improve the interlaminar shear strength (ILSS) of carbon fiber reinforced epoxy
composite, networks of multiwalled carbon nanotubes (MWNTs) can be grown on micron-
sized carbon fibers and single-walled carbon nanotubes (SWNTs) can be dispersed into the
epoxy matrix so that these two types of carbon nanotubes entangle at the carbon fiber (CF)/
epoxy matrix interface [77]. For this purpose, the MWNTs on the CF fiber (CFMWNTs)
are grown by chemical vapor deposition (CVD), while the single-walled carbon nanotubes
(SWNTs) are finely dispersed in the epoxy matrix precursor with the aid of a dispersing
agent polyimide-graft-bisphenol A diglyceryl acrylate (PI-BDA) copolymer (Figure 8(b)).
Using vacuum assisted resin transfer molding, the SWNT-laden epoxy matrix precursor is
forced into intimate contact with the ‘hairy’ surface of the CF-MWNT fiber [77]. The tube
density and the average tube length of the MWNT layer on CF can be well controlled by
the CVD growth time. Figure 8(c)–(d) show the surface morphologies of MWNT grown
carbon fibers. The CVD grown nanostructures are both physically and chemically attached
to the CF lattice and this could be beneficial for maintaining good conducting properties
between carbon fiber and nanostructures which are used as fillers at the interfacial region
in epoxy or other polymer composites.
Combination of GO and CNTs as a filler material at CF/polymer composites may be very
effective for interfacial property modulation. However, there are few reports on this attempt.
Recently Kwon et al. has reported a graphene/carbon nanotube hybrid material stabilized in
an aqueous medium, and coated on carbon fibers by anodic electrophoretic deposition [83].
Chemically oxidized graphene, graphene oxide, is used as a stabilizing agent for dispersion
of carbon nanotubes and as a transport medium for the graphene oxide/carbon nanotube
hybrid during electrophoretic deposition. This hybrid coating increases the wettability and
surface roughness of carbon fibers, which led to improved affinity between the carbon fibers
and epoxy matrix. The resulting hybrid-coated carbon fiber-reinforced composites show
an enhancement of over 10% in the short beam strength compared to un-coated carbon
fiber composites and demonstrate significantly improved through-thickness electrical con-
ductivity (increase of over 1400%) [83]. In another report, Gao et al. has prepared effective
carbon fiber/graphene oxide/carbon nanotubes (CF-GO-CNTs) multiscale reinforcement
by co-grafting carbon nanotubes (CNTs) and graphene oxide (GO) onto the carbon fiber
surface [88]. The multiscale carbon fibers grafted with GO and CNTs are used as the base
material to synthesize the CNTs/GO/CF/epoxy resin hybrid composites by compression
molding method with epoxy resin and hardener H-256 (weight ratio: 100:32). The resulting
composite shows improved mechanical properties [88]. Obviously, more research attention
is needed in combining graphene and CNTs together in CF/polymer composite systems.
2.5. Carbon composites with organic, inorganic and metallic materials

To provide multifunctional properties in a composite material, carbon materials are often
composited with polymers together with different organic, inorganic compounds as well
as metal and metal oxides. Such composites are generally fabricated to increase a particu-
lar functionality in addition to other properties with cheaper production cost than carbon
composites. As for example, basalt fiber is a silicate based material made from extremely
fine fibers of basalt, which is composed of the minerals plagioclase (Na–Al–silicate or
Ca–Al–silicate), pyroxene (silicon-aluminum oxides with Ca, Na, Fe, Mg, Zn, Mn, Li),
and olivine (Mg–Fe–silicate). It is similar to fiberglass, having better physicomechan-
ical properties than fiberglass, but is significantly cheaper than carbon fiber. Recently,
a multifunctional composite with combined dielectric and mechanical properties was
prepared using conductive nanofiller to modify continuous basalt fiber (BF)-reinforced
polymer composite with graphene and epoxy [89]. At first graphene nanoplates (GNPs)
were added into N,N-dimethylformamide (DMF) solvent and then treated by four cycles
of ultrasonication using an ultrasonic cell disruption system before E-51 epoxy resin
was dissolved in DMF. The GNPs/BF/E-51 composite was fabricated by means of hand
lay-up and hot press molding. The prepared uncured GNPs/E-51/BC126 was coated
on basalt fiber fabrics, then the fabrics were unidirectionally laid up layer by layer and
cured at 120 °C for 2 h under 0.8 MPa in a hot press machine. The three-phase graphene
nanoplates/basalt fiber/E-51 epoxy resin (GNPs/BF/E-51) composite was designed as
structural/dielectric composite that could perform energy storage process and sustain
mechanical loading simultaneously, possessing potential application as dielectric layer in
structural capacitors. The effects of GNPs content on morphology, mechanical, dielectric
and electrical properties of E-51 epoxy resin and BF/E-51 composite were investigated.
Dielectric mechanism was proposed based on interfacial polarization and electron con-
duction process.
Either CNT or GO modification on glass fiber surfaces can also help in achieving
improved interfaces in composites by physical-chemical method. It was demonstrated
that 2D GO can be entangled by 1D CNTs in the hybrid coating and this can significantly
enhance the interfacial bond strength of glass-fiber (GF) reinforced composites. Namely,
CNTs was implanted into surfaces of fibers like an ‘anchor’ and meanwhile, GO wrapped
the CNTs and fibers. When GO/CNT hybrid coating was applied to fiber surfaces, the
chemical reaction of grafting on fibers can be supplemented with a silane coupling agent
[90]. Prior to grafting, glass fiber surfaces were treated with silane coupling agent and
thus GO and CNTs were covalently grafted onto GFs by amidation reaction between the
carboxy groups of GO, CNTs and the amino groups of amino-terminated GFs [91,92].
The detailed fabrication steps are shown in Figure 9 [90]. Contact angle measurement
on fiber surfaces indicates that the fiber modification by GO/CNT hybrid coating can
dramatically increase the wetting ability of the fiber surfaces. The detailed experimental
investigation for the interfacial normal bond property clearly showed that the hybrid
GO/CNT coating has a great positive synergistic effect on the fiber matrix interfacial
bond property.
In the context of metal and metal oxide based carbon composites, there have been tre-
mendous research studies to understand the interfacial characteristics, such as, metal matrix
composites with graphene and CNTs [93–95], dielectric and electron emission properties in
Ag or Au and amorphous carbon core-shell structures [96–99], UV responsive properties in
ZnO and rGO composite due to interstitial vacancies and charges at the interfacial regions
[100,101], electrochemical properties in carbon nanostructure (graphene, CNT etc.) and
metal based nanocomposites [102,103] etc. Such composites are synthesized through differ-
ent physical, chemical or physicochemical methods and the interfaces play a crucial role in
dictating the related functionality and applicability. These composites are being explored for
energy storage, transportation, safety, environmental and biomedical applications [95,104].
Figure 9. (a) Schematic illustration of simultaneously grafting CNTs and GO onto one glass fiber, in which
OH or HO represents hydroxyl group, H2N denotes amino group and COOH represents carboxyl group.
Silane coupling agent for GF surface modification acts as a sort of intermediary which bonds organic
materials to inorganic materials, (b) Schematic showing of grafting, coating and washing processes for
coating glass fibers [90], Copyright to Elsevier Inc. (2017).
3. Adhesion and interface modification

Adhesion is the tendency of dissimilar particles or surfaces to cling to one another. The adhesion
properties of different polymer matrices with carbon based reinforcements, particularly with
carbon fibers, for composites used especially in aircraft and space structures are very important
to understand [105–107]. However, owing to the small active specific surface area, low energy
and lipophobic surface, non-polar characteristics and chemical inertness, the surface of carbon
fibers possesses weak interfacial adhesion in polymer matrix [108,109]. Therefore, the stress is
not effectively transferred from the matrix to the carbon fibers, and good mechanical properties
of these composites such as toughness, longitudinal, and transverse strength remain uncer-
tain. Therefore, an appropriately engineered interface is essential to ensure the efficient load
transfer from matrix to reinforcements, which helps to relieve internal stress concentrations
effectively and enhance the mechanical behavior and environmental stability of composites
significantly. Various methods have been employed for surface modification of CF to improve
the compatibility between CF and polymer matrix, such as, sizing [110–114], coating [115,116],
oxidation [117,118], plasmas treatment [119,120], chemical grafting [121,122], electropho-
retic deposition [123,124] and high-energy irradiation [125,126]. Recently, secondary nano-
scale reinforcements (e.g. graphene, carbon nanotubes) into the interface between fiber and
matrix has become popular [127–130]. The mechanism lays behind the fact that, the surface
roughness, surface chemical activity and surface energy of CF are fundamentally improved
through all these techniques which result in remarkable improvement of interfacial properties.
Therefore, introducing micro/nano scale reinforcements onto CF surface can improve the
interfacial strength by improving adhesion properties, increasing fiber surface area, creating
mechanical interlocking and local stiffening at the fiber/matrix interface.
CF sizing is useful in improving interfacial adhesion in composites. Figure 10(a) describes
a schematic illustration of manufacturing sized CFs and the composites in which the CFs
tows were passed through sizing at 1 wt% concentration and dried immediately in a hot
oven for 30 min [131]. This procedure was aimed at evaporating the water completely. The
sizing agent was achieved by PEG-HBPAE sizing where an epoxy resin (HBPAE) is modi-
fied by polyethylene glycol (PEG) to synthesize a self-emulsifying waterborne epoxy resin
(WEP) emulsion called PEG-HBPAE [131]. The emulsion polymerization was conducted
in a 500 mL four-necked flask equipped with a mechanical stirrer, a thermometer, and a
reflux condenser. At first, HBPAE-E44 and PEG were added into the flask in certain pro-
portion and mixed uniformly. Next, the total primary emulsion and the solution of catalyst
Figure 10. (a) Schematic illustration of manufacturing sizing CF and the composites. Fracture of CF
composite laminates measured by SEM: (b) unsized CFRPs, (c) Takemoto S64-sized CFRPs and (d) PEG2000-
HBPAE sized CFRPs [131], Copyright to Wiley Periodicals, Inc. (2017).
were introduced into the flask. Afterwards, the mixture was heated to 85 °C while stirring
at 300 rpm in a thermostatically controlled water bath. This reaction was kept at constant
temperature for 2.5 h. Finally, a quantity of deionized water was slowly dripped in to the
system and the mixture was stirred in a high speed (4500 rpm) homogenizer to make the
emulsion disperse uniformly. The CF/epoxy composite fabrication process is described
in Figure 10(a). The fracture surface and interlaminar shear strength (ILSS) of the CF/EP
composites were examined (Figure 10(b-d). The results indicated that PEG2000 modified
HBPAE sizing had the optimum emulsion stability and film forming ability. The results also
demonstrated that a continuous and uniform sizing layer was formed on the surface of CFs
and the surface sizing was excellent in improving the chemical activity of CFs. Compared
with unsized CFs, the O1s/C1s composition ratio was observed to increase from 11.51 to
33.17% and the ILSS of CF/EP composites increased from 81.2 to 89.7 MPa, exhibiting better
mechanical property than that of commercial Takemoto S64 sized CFs [131].
For nanoscale reinforcement into the interface between carbon fiber (CF) and resin for
improving the interfacial adhesion of CF composites of interface, Figure 11 shows a one-pot
chemical-polymerization process which provides a rapid and efficient method for preparing
polyphosphazene microspheres/CF hybrid reinforcement using hexachlorocyclotriphos-
phazene (HCCP) and bis(4-hydroxyphenyl) sulfone (BPS) as monomers [132]. The fibers
were oxidized by concentrated acid (HNO3) treating (named as CFO) and was also mod-
ified by a uniform poly(cyclotriphosphazene-co-4,4′-sulfonyldiphonel) (PZS) coating and
numerous PZS microspheres (PZSMS) well-dispersed on the fiber surfaces. By the in-situ
polymerization modification, HCCP and BPS were demonstrated to cross-link and deposit
on the CF surface. Figure 11 presents the surface morphology of bare and polymerized CF
through SEM images. This technique establishes that the surface modification can signifi-
cantly increase the fiber roughness, polarity, wettability and surface energy, thus improving
Figure 11. Schematic illustration of the preparation of CF-PZSMS and SEM morphologies of the surface
of (a) untreated CF, (b) CFO and (c, d, e and f) CF-PZSMS [132], Copyright to Elsevier Inc. (2017).
the interfacial shear strength of CF/epoxy composites. The detailed schematics of the inter-
phase region of CF-PZSMS/EP composites before and after debonding and the interfacial
shear strength (IFSS) of the CF/EP composites were evaluated by the microbond test and
is presented in Figure 12(a), (b) and (c) respectively [132]. The IFSS of modified CF/EP
increases obviously. The IFSS of untreated CF, CFO and CF-PZSMS reinforced composites
are 68.91, 70.18 and 84.75 MPa, respectively (Figure 12(c)). The CF-PZSMS/EP composites
have the highest value of IFSS, which show an improvement of 23.0% compared to that of
untreated CF composites. Single fiber physical property tester was employed to study the
effect of the surface modification on the tensile strength of fibers. After the oxidation, the
fiber tensile strength (TS) decreases. It might be because of some flaws or defects which were
introduced onto fiber surface during the oxidation process. While after further modification,
the TS of CF-PZSMS increased from 4.17 to 4.82 GPa with an increase of 15.59%. And
compared with untreated CF, TS of CF-PZSMS increased by 5.93%. This polyphosphazene
coating and PZSMS distributed on the fiber surfaces might have heal the surface defects of
CFO to some extent and assist in holding back or absorbing excessive stress or changing
the propagation paths, resulting in the improvement of tensile strength. Therefore, only
importing surface defects is not sufficient to increase the interfacial properties and hence
the adhesion of CF surfaces in composite structures.
In this context, covalent and non-covalent grafting of polymer chains on the carbon fiber
surface have attracted considerable attention because this method can modulate the surface
properties of carbon fibers and increase the reactivity between the fiber and polymer matrix
Figure 12. Schematic representation of the interphase region of CF-PZSMS/EP composites: (a) before
debonding, (b) after debonding, and (c) Single fiber microbond test of untreated CF, CFO and CF-PZSMS
[132], Copyright to Elsevier Inc. (2017).
resulting in significant improvement of the interfacial adhesion between carbon fiber and
matrix [132]. Until now, various polymers have been successfully grafted onto the carbon
fiber surface through a series of reaction strategies [133,134]. For example, the interfacial
adhesion can be improved by coating a sizing agent composed of polyimide and epoxy on
the surface of CF [135]. Compared with other grafting methods, reversible addition-frag-
mentation chain transfer (RAFT) is an important and effective method to modify inorganic
materials surface with polymer chains due to advantages including the control of molecular
weight and structure of grafting polymer and therefore, a large number of monomers can
be polymerized [136,137].
Introduction of various chemical/functional groups on CF surfaces is also performed
for enhancing interfacial adhesion between CF and matrix resin [138,139]. A strong cor-
relation between surface chemistry and adhesion properties is found. For a carbon fiber
surface without functional groups, a low residual interfacial shear strength probably due
to mechanical interlocking was observed [140]. On the contrary, the chemical modifica-
tion of CF for efficient functionalization, is normally related to complex processes and
high manufacturing cost. Therefore, it is crucial for the improvement of the interfacial
adhesion between CF and epoxy resin to develop a simple functionalization process.
Microwave (MW) assisted heating process is recently considered as the rapid resin-curing
technique of composites composed of CF and epoxy resin of thermosetting type [141].
In the case of MW process, the CF/EP composite is heated from inside by heating CF
in the composite [142–144]. Therefore, the curing of composite is progressed effectively
within a short time and it is found that the curing rate of CF/EP composite cured by
MW process was nine times faster than the one cured by conventional oven owing to
the selective heating of CF [145]. Furthermore, the MW process resulted in significantly
improved mechanical property of CF/EP composite by local heating as compared to the
one heated in conventional oven [146]. Later on, it is examined that the effect of MW
irradiation influences especially on the interfacial adhesion between CF and epoxy resin.
However, excessively high output power can led to decrease in the interfacial adhesion
of composites [147]. The optimal MW input power was found to be 114 W for the best
adhesion between CF and epoxy resin. Additionally, the interfacial adhesion was found
to improve by decreasing the irradiation time. The interfacial shear strength (IFSS) of
the MW-irradiated composite was increased by 21% by controlling the MW conditions
as compared curing in conventional oven [147].
High interfacial wettability is the ultimate prerequisite for guaranteed interfacial adhesion
in carbon fiber/epoxy composites and all the above-mentioned techniques are efforts in
this direction [148,149]. Conceptually, an axially symmetric profile of deposited polymer,
so-called barrel, on the single fiber, are typically shaped when there is a good wettability
between polymer and fiber [150,151]. For example, after clay based modification of CF
surface, compatibility between the epoxy droplets and the fiber was found to increase sig-
nificantly leading to decrease in relevant contact angle from 42° to 25° [152].
3. Mechanical properties

The mechanical properties of a composite material are generally examined by tensile, com-
pressive, bending and shearing conditions among which tensile and bending tests are very
commonly used in exploring the composite materials. To assess the mechanical properties of
a composite material several physical parameters are uses, such as, Young’s modulus, tensile
strength, flexural modulus, flexural strength, toughness, stiffness, etc. Young’s modulus and
tensile strength are generally calculated from the tensile tests while other parameters are
obtained through bending tests. Young’s modulus (Y) defines the relationship between the
applied stress (force per unit area) and generated strain (proportional deformation) in a
composite material. Tensile strength (TS) or ultimate strength is the capacity of a material
or structure to withstand loads tending to elongate. It is sometimes named as longitudi-
nal tensile strength of the material. The flexural modulus or simply bending modulus is
an intensive material property that is computed from the slope of a stress-strain curve
produced by a flexural test (such as the ASTM D790). It is the ratio of stress to strain
in flexural deformation, or the tendency for a material to bend [153]. Flexural strength,
known as modulus of rupture or bend strength, or transverse rupture strength, is a material
property which is defined as the stress in a material just before it yields in a bending test
[154]. Toughness is the energy absorbing ability of a material while undergoing plastic
deformation without fracturing. Simply, it is the amount of energy per unit volume that a
material can absorb before rupturing [155]. Lastly, the stiffness is the rigidity of an object
and is measured as to which extent it can resist deformation in response to an applied force
[156]. Flexibility is complimentary to stiffness as the more flexible an object is, the less
stiff it becomes [157]. The shear stress arises when the force vector component becomes
parallel to the cross section of the specimen. Furthermore, the mechanism of mechanical
failure in a composite material enlightens its mechanical reliability and applicability [158].
Delamination, debonding, crack formation, crack deflection and its propagation within
a composite under mechanical loading are important to study in this context [159,160].
Moreover, the prevention of mechanical failure has been studied extensively through inter-
leaving, interface improvement, various physical and chemical modifications as mentioned
in the synthesis section [161–163].
Naturally available but mechanically reliable materials, such as, wood, foam, corals etc.,
have influenced the urge to synthetically produce fiber-reinforced composites for realizing
mechanically advanced composites. However, there are several factors, such as the elastic
moduli of fibers, properties of matrix, physical states of fibers within a matrix (distribu-
tion, concentration, relative orientation, size and shape), their relative compatibility and
crystallinity, and most importantly their interfacial properties [164,165]. Figure 13 shows
Figure 13. Schematic representation of the deformation pattern in the matrix surrounding a fiber that is
subjected to an applied tensile load (F).
a representative schematic of a fiber/matrix composite undergoing a tensile deformation.

The mechanical properties of composites are sometimes estimated from the rule of mix-
ture of fiber and matrix with a knowledge of volume fraction of each [166]. In the classical
view of fiber reinforced composites, the strong fiber-matrix interfaces lead to high com-
posite strength, but to low composite toughness because of the brittleness of the fiber and
the absence of crack deflection at the interface [161]. Vice versa, composites with weak
interfaces usually have relatively low strength, but higher toughness [167]. With carbon
nanomaterial, such as, nanotube, graphene-based composites, the conjectural notion may
be possible whereby strong interfaces would lead to high composite strength, but at the
same time to tougher composites because of the nanomaterial’s ability to deform prior to
breaking [149,157]. As such, if weak interfaces are present, tough composites would still
be obtained via the rationale used in traditional composites, such as, nano-cracking and
crack deflection within the deformation zone [168]. Thus, inherently tough composites
may be possible in such cases. Only strength and toughness are influenced by interfacial
adhesion but not stiffness. Additionally, the elastic modulus of the composite may be mod-
ified sometimes upon surface treatments, in particular for particulate filled composite,
due to the change in particle distribution and orientation. But, this secondary influence of
the interfacial modification should not be mistaken as the direct influence of the interface
modification on the modulus.
Therefore, the improvement in the mechanical properties of a composite material
consequently means the propagation of externally applied stress from the matrix to the
reinforcing fibers through the interface between them. The amount of stress propagated
depends on the mechanical and adhesive properties of the interfaces between fiber and
matrix. Hence, interfacial modification is crucial for producing mechanically advanced
composite materials. In this context, various methods have been examined, such as,
increasing wetting properties of the fiber surface [152], functionalization of fiber surface
[164], incorporating carbon nanomaterials (CNTs, graphene, CNT-graphene hybrids etc.)
at the interface [71–170], use of interlocking derivatives [171], grafting polymers on the
fiber surface [169,172] etc.
Figure 14(a) presents the stress-strain curves of functionalized SWCNT and reactive
ethylene terpolymer (RET) composites with varying SWCNT vol%. Single-walled and
multi-walled carbon nanotubes were functionalized with carboxyl groups and dispersed
in a polymer containing epoxide group [169]. There was chemical reaction between the
functional groups on the CNTs with the polymer epoxide group which enhanced, both
the tensile strength (Figure 14(b)) and elastic modulus, E, of single walled CNT/polymer
composites (Figure 14(c)). The theoretical model was also developed to understand the
variation of E with CNT volume fraction, considering its agglomeration effects. An increase
in the work of fracture, obtained from the experimental stress-strain curves, was seen at low
nanotube filling fractions and is presumably due to crack bridging of the polymer matrix
by CNTs [169].
CNTs can also be used as efficient interlocking agent at interfaces [171]. The mechanically
interlocked derivatives of SWNTs (MINTs) can improve both Young’s modulus and tensile
strength up to 200% for the polystyrene-MINT composites with an optimized loading
of just 0.01 wt % (Figure 15), while the supramolecular models with identical chemical
composition and loading showed negligible or even detrimental influence. This behav-
ior is found for three different types of SWNTs and two types of macrocycles. Molecular
Figure 14. (a) Stress-strain curves of functionalized SWCNT-RET composites with varying SWCNT vol%,
(b) The ultimate tensile strength (UTS) of functionalized and unfunctionalized (pristine) SWCNT/RET
composites with varying SWCNT vol%, (c) Elastic modulus, E, of functionalized SWCNTs and MWCNT-
RET composites and pristine SWCNT-RET composites with varying CNT vol%. The data were fit (dotted
lines) through a modified Halpin-Tsai equation. The inset shows a schematic to indicate the defined
agglomeration factor p related to the bundle length (b) and diameter (a) [169], Copyright to Elsevier
Inc. (2010).
Figure 15. (a) Young’s modulus of polystyrene (white), SWNTs (black), supramolecular complexes
(blue), and MINTs (red) with (6,5)-SWNTs (left), pp-SWNTs (center), and o-SWNTs (right), (b) Tensile
strength of polystyrene (white), SWNTs (black), supramolecular complexes (blue), and MINTs (red) with
(6,5)-SWNTs (left), pp-SWNTs (center), and o-SWNTs (right), (c) Strain of polystyrene (white), SWNTs
(black), supramolecular complexes (blue), and MINTs (red) with (6,5)-SWNTs (left), pp-SWNTs (center),
and o-SWNTs (right) [171], Copyright to Americal Chemical Society (2016).
dynamics simulations shows that the polymer adopts an elongated conformation parallel
to the SWNT when interacting with MINT fillers, irrespective of the macrocycle chemical
nature, whereas a more globular structure is taken upon facing with either pristine SWNTs
or supramolecular models. Figure 16 describes this mechanism in details. The MINT com-
posite architecture demonstrates that the mechanical bond imparts distinctive advantageous
properties at the interfaces of composites.
Growth of dendrimers, such as generation 1–3 melamine, onto carbon fiber surface
showed that melamine-based dendrimers grafting enhanced surface roughness, and this
effect was more pronounced with increasing generation [168]. The results of dynamic con-
tact angle (DCA) indicated that the surface energy and the wettability of the grafted CFs
were increased with generation. After generation 3 dendrimers grafting, the interfacial shear
strength (IFSS) and impact strength of CF/epoxy composites were enhanced by 61.8% (from
~50 to ~78 MPa) and 39.9% (from 60 to 84 kJ/m2), respectively [168].
In case of nanocomposites, a compatibilizer containing carbazole moiety and reactive
epoxide group can also effectively functionalize multiwalled carbon nanotubes (MWNTs or
MWCNTs) for making superior epoxy composites interfaces via noncovalent π–π interac-
tion for excellent mechanical properties [50]. The designed compatibilizer increased tensile
strength of MWNT/epoxy nanocomposite from 42.61 to 59.61 MPa.
On the other hand, in a composite material, delamination between different fabric layers
is an important issue in determining their mechanical stability and reliability [173,174], and
such delamination is always accompanied with the unstable crack propagation process due
to a prominent stick-slip behavior of viscoelastic epoxies [175,176]. Once the critical load
of crack initiation is reached, the crack rapidly propagates because a part of work applied to
Figure 16. MD snapshots of (a) polystyrene and its composites with (b) SWNTs, (c) SWNT-1, (d) SWNT-2,
(e) MINT-1, and (f) MINT-2 after MD simulations. Carbon atoms are shown in red for the SWNTs, green
for the macrocycles, and cyan for polystyrene. Hydrogens are shown in white, oxygen in red, and sulfur
in yellow, (g) Average dihedral angles of the polystyrene backbone for the last nanosecond of the MD
simulation. Color code: polystyrene (gray triangle) and its composites with SWNTs (black square), SWNT-
1 (blue circle), SWNT-2 (blue triangle), MINT-1 (red circle), and MINT-2 (red triangle) [171], Copyright to
American Chemical Society (2016).
carbon fiber reinforced plastics (CFRPs) is converted into kinetic energy. When the crack
velocity decreases and stops, an arrest load is attained. This process can be repeated several
times as the crack passes through the sample from the pre-crack position, and thus a saw-
tooth shaped load-extension [177,178] profile is formed. Apparently, this unstable fracture
behavior is very dangerous for practical application of composites. The generation and inter-
action of shock wave during the transient load drop process may cause acoustic emission,
and induce the large structure vibration as well as catastrophic failure. It is highly desired
to find a method to modify the stick-slip behavior and minimize the instability for a better
safety protection. There have been enormous efforts to improve the stick-slip properties in
composites through strengthening the interlaminar regions or interfaces adopting various
techniques similar to as mentioned earlier, such as, functionalization, grafting nanomaterials
and polymers etc. [74,179,180–183].
Utilization of functionalized carbon nanomaterials for improving mechanical properties
in composites is very effective. For example, Bortz et al. used 1.0 wt% of oxygenated GNSs
nanofiller in an epoxy matrix to enhance the flexural stiffness and strength by up to 12%
and 23%, respectively, as compared to the unmodified epoxy resin [184]. An increase in the
tensile modulus and strength by ~10 and ~48%, respectively, resulting from the addition of
0.25 wt% silane-functionalized graphene oxide (GO) nanofiller in the epoxy matrix, was
observed by Wan et al. [185]. The incorporation of 0.5 wt% of ammonia-modified GNSs
into an epoxy polymer matrix resulted in improvements of 27.84 and 7.75% in the tensile
strength and flexural modulus of the nanocomposite, respectively, as reported by Zang et al.
[186]. Furthermore, Pan et al. increased the impact and tensile strength of an epoxy com-
posite by 50.8% and 62.3%, respectively, with addition of 0.7 wt% reduced graphene oxide
(rGO) functionalized with perylene bisimide hyperbranched polyglycerol [187]. Ashori
et al. also achieved a maximum increase in tensile strength of 22.5% by using 0.3 wt% of
diamine-functionalized GO sheet in carbon fiber/epoxy nanocomposite structures [188].
These examples establish the importance of functionalization in the carbon nanomaterials
used as nanofillers with respect to establishing stronger interfacial bonding in the epoxies
[84]. As comparison to graphene based nanocomposites, there have been more studies on
CNT based nanocomposites for mechanical property improvement [189].
The influence of defects of CNT walls on the mechanical properties in composites
has recently been studied [190]. CNT walls possess defects through structural vacancy
or functionalization means. Molecular dynamic (MD) simulation on the effect of most
common defects in CNTs (as described in Figure 17) are examined upon the interfacial
shear strength (ISS) of nano-reinforced thermoset epoxy before and after cross-linking.
ISS is estimated using both the total potential energy and interfacial interaction energy. It
Figure 17. Geometries of CNTs containing different defects and functionalization: (a) monovacancy, (b)
bivacancy, (c) trivacancy, (d) single carbon adatom defect, (e) Stone-Wales (SW) defect, and (f) phenyl
group functionalization [190], Copyright to Elsevier Inc, (2017).
is concluded that the deformation energy of defective CNT reinforced polymers needs to
be considered to obtain accurate ISS of uncured epoxy polymers. As such, the defective
and functionalized CNTs in cured epoxy or other polymer matrices can lead to increased
ISS and improved load transferability. However, the presence of defects in the CNTs and
epoxy matrices would ultimately result in a decrease in the effective elastic properties of
the nanocomposites [190–192]. Table 1 enlists the mechanical properties of polymer com-
posites containing functionalized CNTs [191]. A trade-off between the degradation in the
mechanical properties of nanocomposites and the improvement in the ISS of the result-
ing multifunctional nanocomposite systems should be carefully considered and addressed
[190–193]. Therefore, the mechanical properties of composites depend on multiple factors
relying both on reinforcement and matrix. The interface properties considerably influence
the mechanical properties in composite materials. Great efforts have been and yet more
to be given for interface modification to improve mechanical properties of composites for
various applications. For nanocomposites, different carbon nanomaterials individually or
in combination (hybrid carbon) can play important role in improving mechanical proper-
ties with an aim to improve the interfacial regions. Table 2 summarizes the effectiveness of
using carbon nanomaterials in improving mechanical properties in nanocomposites with
different polymers [194].
4. Thermal properties

Because the modern electronic industry moves forward rapidly with high power consump-
tion, integrated functions and miniaturisation, the power densities of modern electronic
devices have been increasing dramatically. Therefore, the dissipation of large amounts of heat
has become a critical issue in the electronics industry and this problem has generated great
research interests [195]. Carbon based materials are well known for their superior thermal
conductivities other than metals. However, to replace costly metal based materials as heat
conductor, carbon based composite materials have gained tremendous research attention
because of related low cost, fabrication ease and light weight [196,197]. For example, ver-
tically aligned CNT films can have volume-averaged axial thermal conductivities as high
as those of metals, with reported values reaching ~265 W/m/K [198]. But, only the carbon
materials themselves do not always offer the mechanical properties required by structural,
aerospace, and other applications [199].
Materials with high thermal conductivity are generally rigid. Therefore, it is difficult for
a non-composite material to possess both softness and high thermal conductivity. For this
reason, the coexistence of softness and high thermal conductivity has been attempted by
adding carbon based fillers with high thermal conductivity (e.g. pitch-derived carbon fiber
(p-CF), CNTs, graphene and their hybrids) to a soft elastomeric material as the matrix to
create a composite for thermal interfacing material (TIM) [196,200,201]. Especially, soft
and high thermal conductive materials are widely required for thermal energy transfer from
heat source to heat sink. Therefore, carbon based composite materials have become very
popular for thermal application, such as, thermal conduction, heat dissipation, Thermal
protection and thermoelectric applications [199,202–204].
The interfacial thermal conductivity in a carbon-based nanocomposite is a dictating
factor in determining the overall thermal properties. Haddon et al. added CNT to graphite/
Epoxy composite to decrease the thermal resistivity between graphite nanoplates and the
Table 1. Mechanical properties of polymer composites containing functionalized CNTs [191].
CNT/polymer composite CNT content (wt%) CNT functionality YComp (GPa) YMax (GPa) dY/dVf (GPa)
CVD-MWCNT/methyl and ethyl methacrylate P(MMA-co-EMA) 10 Octadecylamine 1.64 2.62 15
SWCNT/epoxy 4.0 Large-organic group 2.02 3.4 95
SWCNT/polyamide 6(PA6) 1.5 PA6 0.44 1.2 120
SWCNT/PVA 0.8 Hydroxyl 2.4 4.3 305
CVD-MWCNT/PVA 1.5 Ferritin protein 3.4 7.2 380
MWCNT/PC 5.0 Epoxide 2.0 3.8 95.5
MWCNT/PMMA 3.0 PMMA 2.7 2.9 18.2
CVD-MWCNT/PVC 1.0 CPP 0.56 0.9 115
CVD-MWCNT/PS 1.0 CPP 1.48 2.63 304
SWCNT/copolymers of styrene and vinyl phenol (PSVPh) 5.0 Carboxylic acid 1.5 2.1 24.25
CVD-MWCNT/PU 20 Carboxylic acid 0.05 0.42 4.5
SWCNT/bisteel (synthetic spider silk) 0.125 Octadecylamine 1.6 1.9 381
SWCNT/PAMAM 1.0 Epoxy 2.76 3.49 153
CVD-MWCNT/kevlar 2.0 PVC 1.5 2.5 300
CVD-MWCNT/epoxy 0.6 TETA 1.56 2.4 355
CVD-MWCNT/PS 0.25 Butyl 1.29 1.63 433
COMPOSITE INTERFACES
565
Table 2. Mechanical properties of polymer composites with different carbon nanomaterials [194].
Increase in
Filler loading Fabrication tensile or yield Increase in
Filler type (Wt. %) Matrix method strength (%) modulus (%)
SWCNT/PVA 5 PVA Wet-casting 54 55
GO/PVA 1 PVA Solution mixing 88 150
GO/PVA 0.24 PVA Solution mixing 55 80
MWCNT 0.5 PVA Solution mixing 6 3
GO 1 29 13
MWCNT/GO 1.5 46 31
MWCNT 0.6 PVA Solution mixing 27 23
Reduced GO (rGO) 47 38
MWCNT/GO 77 65
MWCNT 5 PES Solution mixing 32 31
Graphene −44 70
Graphene/MWCNT 11 98
MWCNT 5 HydroMedTM Solution mixing 42
D640 62
Graphene 70 82
MWCNT 3 HDPE Melt mixing 58 57
Graphene 77 87
MWCNT 1 Epoxy Solution mixing 13 2.5
Graphene 11 23
MWCNT 2 PEN Solution mixing 8 5
Graphene 11 9
conductivity of the composite is 1.6 W/m/K with 8wt% fillers [205]. In this system, CNTs
were associated as long range thermal carrier. However, Ata et al. demonstrated that the
CNTs can effectively be utilized as short ranged thermal carrier [196]. In this study, the effi-
ciency of heat transfer between p-CFs was increased by adding CNTs, which have relatively
high thermal conductivity and a specific surface area of about 1000 m2/g, to a composite
made of p-CF and rubber. By keeping the amount of filler upto 25% or less, thermally con-
ductive and flexible sheets were fabricated with a thermal conductivity of 80 W/m/K, which
is higher than that of iron. Figure 18 demonstrates its detailed fabrication procedure and
thermal properties [196]. The flexible materials made of CNT/p-CF/FKM and CB/FKM
composite showed excellent temperature diffusivity on aluminum plate during heating with
hand, and 15, 30, and 45 s after removing hand form sample. The important aspect of this
study is that the combination of p-CF and CNTs within a matrix could effectively increase
the conductivity with an assumption that CNTs acted as short ranged phonon transport
medium particularly at the interfaces of the p-CF and fluorinated rubber (FKM).
Functionalized graphene is also a potential candidate for inproving thermal interface
conductance in nanocomposites. In this effort, the interfacial thermal resistance for pol-
ymer composites reinforced by various covalently functionalized graphene are examined
by using MD simulations [195]. The results indicate that the covalent functionalization in
graphene plays a significant role in reducing the graphene-paraffin interfacial thermal resist-
ance. This reduction is dependent on the coverage and type of functional groups. Among
the various functional groups as presented in Figure 19(A), butyl is found to be the most
effective one in reducing the interfacial thermal resistance, followed by methyl, phenyl,
and formyl, respectively (Figure 19(B)). The other functional groups under consideration
such as carboxyl, hydroxyl, and amines are found to produce negligible reduction in the
Figure 18. (a) Typical sample preparation process of CNT/p-CF/FKM composite, (b) Photograph of SG-
SWNT/p-CF/FKM composite. Weight fraction of SG-SWNTand p-CF are 4.8 and 19.6 wt%, respectively,
(c) SEM image of fracture surface of SG-SWNT/p-CF/FKM composite, (d) Thermal conductivity versus
density of metals (circle), inorganic materials (triangle), organic materials (diamond) and CNT/p-CF/FKM,
(e) Specific thermal conductivity of CNT/p-CF/FKM, other materials and prior works, (f) Temperature
diffusivity demonstration of CNT/p-CF/FKM and CB/FKM composite on aluminum plate. From left to
right, during heating with hand, 15, 30, and 45 s after removing hand form sample, respectively [196],
Copyright to WILEY-VCH Verlag GmbH & Co (2016).
interfacial thermal resistance. For multilayer graphene with a layer number up to four, the
interfacial thermal resistance is insensitive to the layer number (Figure 19(C)). The effects
of the different functional groups and the layer number on the interfacial thermal resistance
are also elaborated using the vibrational density of states of the graphene and the paraffin
Figure 19. (A) Simulation models of (a) pristine graphene and graphene functionalized with (b) butyl,
(c) methyl, (d) phenyl, (e) formyl, (f) carboxyl, (g) amines, and (h) hydroxyl; (B) Variation of the relative
interfacial thermal resistance with respect to the coverage of various types of functionalization and (C)
Variation of the relative interfacial thermal resistance with respect to the number of graphene layers
[195], Copyright to American Chemical Society (2015), (D) Thermal interface resistance for bare fiber and
graphene-petal decorated fiber samples. Uncertainty bars correspond to uncertainty obtained from 95%
confidence bound on the fitted values, inset shows scanning electron microscope (SEM) image of vertical
graphene petals grown on a CF surface [208], Copyright to American Chemical Society (2016).
matrix which can provide useful guidelines in the application of functionalized graphene
for practical thermal management [206,207]. Beside functionalization, the crystalline conti-
nuity of the reinforcing fiber and filler nanomaterial is very important in improving TIM in
epoxy composites. In this context, vertically alinged graphene grown by microwave plasma
chemical vapor deposition is worth mentioning [208,209]. Such nano-petal like vertical
graphene decoration onto CF surface effectively reduced TIM from 8 mm2 K/W for bare
fibers to 3 mm2 K/W for fibers with petal growth with epoxy as shown in Figure 19(D). In
fact, the graphene-petals modified the intarface and increased the phonon transport across
the interface [208].
Carbon based thermal conductive material does have electrical conductivity and applica-
tion should not be restricted for such areas where both thermal and electrical conductivities
are desirable. One example could be the thermoelectric (TE) application of carbon based
composites where a low thermal conductivity but high electrical conductivity is required.
This can be performed by choosing suitable matrix. However, despite remarkable achieve-
ments, the field of carbon-composite based TE still needs considerable attention. The TE
mechanism at the molecular level is far from clear, although some concepts in nanocompos-
ite structures (such as phonon scattering, carrier-energy-filtering and quantum confinement
effect) have been employed to preliminarily explain the molecular mechanism in conduct-
ing polymer/carbon particle TE composites [204]. In addition, the intrinsic advantages of
each constituent, such as the flexibility and solution-processability of conducting polymer,
need further exploration [204,210,211] (Table 3 enlists thermal properties of carbon-based
nanocomposites).
By selecting proper matrix, such as nanoclays, carbon composites can also be used as
effective heat and fire resistant [212]. As for example, carbon based composites made of
carbon/phenolic prepregs with nanoclays was utilized as effective fire resistant material
[212]. The addition of clay improved the peak of the heat release rate and the residual mass
of the burned samples. Additionally, this composite presented low modulus and flexural
stiffness but presented a higher degradation in the properties after fire, which could be
related with the different fiber content in both composites [212].
5. Electrical properties

The increasing demand for efficient machines has driven a trend towards the miniatu-
ration of devices and instruments with smaller volume, lesser power consumption but
greater performance, light weight and mechanically reliable. For this purpose, conductive
polymer composites (CPCs) have received intensive academic and industrial attentions
due to their good processability, low cost, light weight, tunable properties, and wide
ranges of applications [213–215]. In fact, for achieving insulator/conductor transition,
very high loading of conductive fillers are generally incorporated into an insulating
Table 3. The thermal conductivity and thermal stability of the polymer composites based on graphene
and CNTs [194].
Increase in thermal
Filler type Filler loading (Wt. %) Matrix Fabrication method conductivity (%)
MWCNT 1 Epoxy Shear mixer 62.0
Graphene 23.8
MWCNT/graphene 93.0
MWCNT-COOH 1 Epoxy Rolling 14.6
Graphene 17.4
MWCNT-COOH/graphene 21.3
MWCNT 20 PPS Melt mixing 295
Graphene 30 768
MWCNT 0.5 PEI Solution mixing 9
Graphene 22
Graphene-MWCNT 45
MWCNT 0.5 HDPE Melt mixing –
Graphene
MWCNT-CN 8 PEN Solution mixing –
Graphene-CN-MWCNT-CN
polymer matrix. However, this leads to complex processing, poor mechanical properties,
and high cost of the materials [216,217]. Therefore, superior CPCs with ultralow perco-
lation threshold (i.e. the critical concentration for the insulator/conductor transition)
are desired.
For this purpose, double percolation structure has been introduced, where the con-
ductive fillers are selectively located in one phase of a co-continuous polymer blend.
This implies that less conductive fillers are required to establish a percolated network
throughout the composite structure. In fact, double percolation structure has been applied
to a larger number of polymer blend systems with various conductive fillers, such as car-
bon black (CB) [218,219], carbon fibers [220,221], CNTs [222,223], graphite [220], and
graphene [224,225].
For CF based composite, epoxide (butyl glycidyl ether) functionalized MWCNT
(MWCNT-BGE) reacted with epoxy resin to form a new type of pre-dispersion mixture
has been conceived [81]. Subsequently, the MWCNT-BGE/epoxy pre-dispersion mixture
was transferred to the interlayer of carbon fiber/epoxy composite laminates by well-designed
spraying technique. The composite indicated about formation of three-dimensional (3D)
continuous conductive pathways and consequently an 283% increase (up to 2.87 S/m)
was realized in the through-thickness electrical conductivity after spraying pre-dispersion
mixture with a concentration of 0.5 wt% (Figure 20). Further, the incorporation of pre-dis-
persion mixture can efficiently enhance the interlaminar shear strength of carbon fiber
composite laminates simultaneously [81].
Graphene/CNT hybrid carbon material can also serve very effectively as a mul-
ti-functional interfacial nano-reinforcement to enhance the mechanical and electrical
properties of CF/epoxy composites [83]. At first, CNT and GO was electrophoretically
coated onto CF surface followed by epoxy composite fabrication using vacuum molding
process. In-plane electrical conductivity of the un-coated CF composite (108 S/cm)
was much higher than that in the through-thickness direction (0.05 S/cm) because
the conductive carbon fibers were aligned along the in-plane direction. The resulting
hybrid-coated carbon fiber-reinforced composites showed an enhancement of over 10%
in the short beam strength compared to un-coated carbon fiber composites and demon-
strated significantly improved through-thickness electrical conductivity (increase of
over 1400%) [83].
In case of nanocomposites, formation of percolation path of CNTs can lead to greatly
improved electrical conductivity of polymer. Figure 21 expresses the double percolation
schematically in CB and CNT reinforced fibers composites [40,226]. If the CNTs in pol-
ymeric fibers are aligned along fiber axis matrix, it leads to an anisotropic electrical con-
ductivity [227–230]. For example, in an oriented PP/MWNT (5.3 wt %) tape, the ratio of
electrical conductivity in longitudinal direction over transverse direction increased from
1 for the isotropic film without stretching (electrical conductivity ∼5 S/m) to 100 for the
oriented film after tape was stretched in solid state to a draw ratio of 6 (longitudinal direc-
tion electrical conductivity ∼0.07 S/m) [228]. For CNT reinforced composite fibers, the
conductivity is measured along the fiber axis, if not mentioned specifically. Although neat
PEK is non-electrically conductive, PEK/FWNT (20 wt %) composite fiber, with a tensile
strength of 0.12 GPa and tensile modulus of 17.3 GPa, has an axial electrical conductivity
of 240 S/m [230].
Figure 20. (a) Schematic diagram of three directions in the carbon fiber/epoxy composite laminates.
Electrical conductivity of the MWCNT/epoxy pre-dispersion mixture modified carbon fiber/epoxy
composite laminates: (b) z-direction; (c) x-direction; (d) y-direction [81], Copyright to Elsevier Inc. (2017).
Following the double percolation structure, a strategic technique is that all the con-
ductive fillers are precisely controlled at the interface of a co-continuous polymer blend
to design CPCs. If the conductive fillers only need to form the conductive pathways at the
continuous interface, then the required conductive fillers will be very small in amount.
To ascertain the interfacial distribution of conductive fillers, there may be two strategic
methods. The first one is by kinetically controlling the migration of fillers between the
two immiscible polymer phases [231–233]. For example, MWCNTs can be concentrated
mainly at the interface of a co-continuous immiscible poly(lactic acid)/poly(ε-caprolac-
tone) (PLA/PCL) blend through controlling the migration process of MWCNTs from
the unfavorable PLA to the favorable PCL phase [233]. In this energy-based strategy, the
fabricated PLA/MWCNTs/PCL composites displayed an ultralow percolation threshold,
0.025 wt.% [233]. The second strategy would be a thermodynamic strategy where the
block copolymer or random copolymer is grafted onto the fillers to make them affinitive
to the two immiscible phases simultaneously [216,234]. According to thermodynamics,
the interfacial free energy must be the minimized to gather fillers preferentially at the
interface of two liquid phases [235]. The location of fillers can be predicted through
wetting coefficient [236],
𝛾f −B − 𝛾f −A
𝜔𝛼 = (1)
𝛾A−B
Figure 21. Schematic presentation of double percolation phenomena for (a) carbon black-containing
polymer composites [226], Copyright to Hindawi Ltd. (2012) and (b) fiber-polymer composites without
and with CNT reinforcement [40], Copyright to American Chemical Society (2014).
where γf−A is the interfacial tension between filler and phase A, γf−B is the interfacial tension
between filler and phase B, and γA−B is the interfacial tension between phases A and B. The
fillers tend to distribute at the interface when −1 ≤ ωα ≤ 1 [236]. If both the fillers are affinitive
to each phase, ωα is close to 0, and γf−A ≈ γA−B. Fillers locate in A or B phase for ωα > 1 or
ωα < −1 respectively [236]. Consequently, a smart technique is to graft amphiphilic molecules
onto fillers, which makes them affinitive to each individual phase. Utilizing this technique,
graphene was modified using PS-PMMA random copolymer, which strategically migrated
the graphene nanosheets at the interface of a co-continuous PS/PMMA interface [234].
With some success, the kinetic technique sometimes yields a structure in nonequilib-
rium state and fragile in subsequent material processing. On the other hand, the classi-
cal thermodynamic strategy is challenging to make amphiphilic fillers through grafting
block copolymer or random copolymer. In this context, incorporation of non-covalent
π–π or dipole-dipole interactions between filler and phase molecules may be an alternative
approach [237,238]. However, the best strategy would be to find a balance between π–π and
dipole-dipole interactions to have an ideal system [239]. Using this technique, it has recently
been possible to precisely control MWCNTs at the interface of a co-continuous PS/PMMA
blend by tuning the content of the carboxylic group on MWCNTs. When the content of
the carboxylic group is 0.73 wt.%, it is observed that most MWCNTs are distributed at the
interface of a co-continuous PS/PMMA blend owing to the balance between π–π interac-
tions and dipole-dipole interactions [239]. Figure 22(a) and (b) show the AC conductivity
Figure 22. (a) AC conductivity (at 1 Hz) vs PMMA content in PS/PMMA blends. All the measurements were
performed at room temperature. The weight concentration of MWCNTs-2 in all the PS/PMMA blends is
fixed at 0.5 wt%; (b) AC conductivity (at 1 Hz) of MWCNTs-2/PMMA, MWCNTs-2/PS and PS/MWCNTs-2/
PMMA composites as a function of MWCNTs-2 content. The weight ratio of PS/PMMA was fixed at 40w/60w
for all the PS/MWCNTs-2/PMMA composites. All the measurements were performed at room temperature
[239], Copyright to Elsevier Inc. (2017).
of PS/MWCNTs-2/PMMA composites with varied PMMA and MWCNT contents respec-

tively [239]. Furthermore, for such composites, it is important to estimate the exact value of
conductive percolation threshold that can be determined by the following equation [240],
𝜎 ∝ (𝜑 − 𝜑c )t for 𝜑 > 𝜑c (2)
where σ is the electrical conductivity of the CPCs, φ is the mass fraction of filler, φc is the con-
ductive percolation threshold and t is a critical exponent related to dimension of conductive
network in CPCs. φc is generally obtained through linear fitting to experimental electrical
conductivity (σ) data. For above example, an ultralow percolation threshold of 0.017 wt.%
was achieved since all the MWCNTs were enriched at the continuous phase boundary [239].
Furthermore, CNT/epoxy nanocomposite based on aligned CVD-grown MWCNTs with
weight fractions ranging from as low as 0.001 up to 1 wt.% were found to result in electrical
conductivity ranging from 1x 10−9 to 2 S/m respectively with a mean percolation threshold
to form conductive network of approximately 0.0025 wt% and an exponent, t, of 1.2 (from
equation 2) [241]. Similar to one dimensional (1D) CNTs, 2D graphene is also useful as
potential filler for CPCs [69,242–249]. Supramolecular polymer-functionalized graphene
(SPFG), a combination of exfoliated graphite nanoplatelets and a low-molecular-weight
supramolecular polymer, can be incorporated into poly(L-lactic acid) (PLLA) matrices
for efficient production of SPFG/PLLA composites (Figure 23) which possesses superior
electrical conductivity of up to 9.58 × 10−3 S/cm at a SPFG loading of 10.0 wt.%, which is
nearly four orders of magnitude higher than control graphite/PLLA composites at the same
nanofiller content [248].
Polystyrene and reduced graphene oxide (PS/r-GO) composite films (with 5 wt.% GO)
were prepared by the hot press molding method, possessing a conductivity of as high as
22.68 S/m [249]. The superior conductivity arises from the high reduction degree of GO
and its high dispersion and the formation of a network structure in the PS matrix. In fact,
attaining an equilibrium chemical or physical state in CPCs should be the primary focus
Figure 23. Graphical representation for preparation of PLLA composites by solvent blending with graphite/
UrCy-PPG [248], Copyright to Elsevier Inc. (2017).
for fabricating carbon based nanocomposites. Moreover, the percolation thresholds of con-
ductive fillers play an important role in determining the electrical properties of polymer
composites. According to percolation theory, there is a critical concentration of conductive
fillers above which they form pathways where the composites containing these fillers become
electrically conductive themselves. The percolation threshold of carbon nanomaterials in
nanocomposites depends on the dispersion, alignment, aspect ratio, degree of surface mod-
ification of nanomaterials, filler types, polymer types, and composite processing methods
[250]. Furthermore, combination of CNT and graphene as fillers within a nanocomposite
can perform interestingly [194]. The electrical conductivities and percolation thresholds
of carbon nanomaterial/polymer composites are shown in Table 4. It is observed that the
percolation threshold of CNTs was only 0.0021 wt.% as compared to 0.1 wt.% for graphene
in polymer nanocomposites [241,242,251]. These differences may arise from the filler’s
aspect ratio and the population density, which affect the formation of the three-dimensional
interconnected filler network in the matrix [252].
6. Effect of interface on electrochemical properties of carbon based

composites
Carbon based composites have also gained intense attention for various electrochemical
applications without or with having an added advantage of mechanical robustness [253–
257]. Such electrochemical applications include supercapacitors (double layer and pseudo),
different types of batteries (Li/Na/K/Zn/S-ion, air and polymer-based), fuel cells (oxygen
reduction reaction (ORR), hydrogen oxidation reactions (HOR)) and electrodes for other
chemical oxidation/reduction reactions, such as hydrogen evolution reaction (HER), oxygen
evolution reaction (OER), chemical conversion reactions (CCR) etc. [255–257]. Lithium-ion
batteries (LIBs) have been widely studied having good energy density and performance.
With the commercial success of lithiated graphite, other graphite intercalation compounds
(GICs) have recently been intensively reported, with metals other than Li, such as, Na, K,
Al-ion batteries [258,259]. Detailed understanding of the graphitic-carbon intercalation
by Li, K, Na, Al elements and related chemical as well as physical property modulation
Table 4. The electrical conductivity and percolation threshold of carbon nanomaterials/polymer com-
posites [194].
Highest electrical
Filler loading Fabrication Percolation conductivity
Filler type (Wt. %) Matrix method threshold (S/m)
MWCNT/graphene – PPS Melt mixing 5 wt.%
10 wt.% –
MWCNT 2 Epoxy Milling 0.2 wt.% 1.76 × 10−1
Graphene 0.3 wt.% 4.0 × 10−3
MWCNT 5 PES Solution mixing – 1.43 × 10−4
Graphene 0.22 wt.% 5.82 × 10−4
Graphene/MWCNT 1.28 × 10−3
MWCNT 4 PDMS Solution mixing – 2.53 × 10−5
Graphene 7.89 × 10−5
Graphene/MWCNT 1.24 × 10−3
MWCNT – HDPE Alcohol-assisted 0.25 wt.%
dispersion and
hot-pressing –
Graphene 1 vol.%
MWCNT 4 PS/PPO Solution blending 0.2 wt.% 57
Graphene 1 wt.% 0.9
CNT 69.2 PANI In-situ polymeri- –
zation 680
Graphene 150
CNT/Graphene 410
MWCNT 5 PS Melt mixing 0.05 wt.% 7.98 × 10−1
Reduced GO (rGO) 4 PS Solution mixing – 22.68
CTAB-wrapped GO 6.47 PVC Solution mixing 0.6 vol.% 5.8
MWCNT 20 PVC Solution mixing – 175
MWCNT 4 LCP Melt Mixing – 1.33 × 10−1
Graphene 5 LCP Solution casting 3 wt.% 4.5 × 10−3
and compres-
sion molding
would be a proper step towards commercial success to develop diverse high-energy bat-
teries for stationary energy storage in the future [260–262]. The interface chemistry play
a crucial role in all electrochemical reactions. To increase the electrochemical activities
of carbon-based nanocomposite electrodes, the interfaces are generally modified either
through heteroatom doping onto the carbon lattice or through grafting of polymer, metal,
metal oxides etc. [263–265].
There have been and yet being extensive studies on advancement of carbon based com-
posite materials for efficient electrochemical performance and device applications. Besides
considering the activity of interfaces (namely conversion efficiency/number of electrons
transferred etc.), the overall electrode conductivity of such composites is very important. As
such, there have been serious efforts to replace costly precious and non-precious metal elec-
trodes with equally or better efficient carbon composite electrodes [255–257,263,265,266].
Figure 24 shows the timeline for developing carbon based metal-free catalysts (modified
from Ref. [256]). Google contains many thousands of research articles based on electro-
chemistry of carbon based composites or catalysts. It has been observed that, abundance
of active sites such as, edges, interfaces and defects on carbon materials play incremental
influence on the material-level electrochemical conversion efficiency, but degrade the con-
ducting property resulting in poor device-level efficiency. Therefore, it is crucial to find a
balance between density of active sites and electrode conductivity or there must be strategic
electrode designing taken into account. More research is indeed essential to practically have
Figure 24. Timeline showing the important developments of carbon-based metal-free catalysts (modified
from Ref. [256]).
these carbon catalysts commercially replace the metal based electrochemical catalysts for
developing cheaper energy storing devices. The cost, conductivity and mechanical compact-
ness (CCC-issue) are three key factors of carbon based electrodes for electrochemical energy
storage advancements. In this respect, carbon fiber or carbon textile based carbon-carbon
or carbon-polymer electrodes have already demonstrated and hold great promise [267,268].
7. Photo or radiation interactive properties of carbon composites

The interface chemistry of carbon nanostructures has continued their exciting venture into
photo-interactive applications, such as, photo-voltaic cells, photo-degradation, photo-de-
tection and optoelectronics etc. CNT, fullerene and graphene based composite materials
are mostly utilized for these applications [269–279]. Interface engineering of these carbon
nanostructures is crucial for achieving efficient dye sensitized or perovskite solar cells, yet
a comprehensive understanding of the interface between a metal electrode and electron
transport layer (ETL) is lacking [270–279]. In this context, the major challenge in using
CNT for optical-electronic applications is related to the dependence of its band structure
on the structural chirality which makes CNTs either metallic or semiconducting. Graphene
is intrinsically a zero-gap semiconductor, or a semimetal. To overcome such electronic
heterogeneity of CNTs and graphene, their band structure is generally modulated through
doping with heteroatoms or grafting with organic or inorganic materials or polymers, such
as dyes, perovskites etc. Sometimes, CNTs are simply used as the electron collectors in pho-
tovoltaic devices. However, such devices typically yield inexplicably low power-conversion
efficiencies but extraordinarily large open-circuit voltages of up to 1.8 V [270]. This obser-
vation is attributed to the electronic band bending at the CNT and polymer junction. The
alignment of Fermi levels occurs in such a way, that they energetically favor hole transfer
from the polymer to the nanotubes [271,272]. Therefore, CNTs act like a hole transport
material (HTM) as demonstrated by Dabera et al., where polymer-wrapped SWNTs were
composited in an organic polymer solar cell as hole-extraction layer and thereby improving
the overall performance of the device [273].
Even if being the newest type of photovoltaic solar cell system, perovskite solar cell which
is continuously chasing for even higher efficiencies, has to date produced a certified effi-
ciency of 22.1% [274]. The early stage solid-state architecture of perovskite cells was based
on layered structure of a transparent anode at the bottom, the perovskite as absorber in the
middle, and the hole-collecting metal cathode at the top [275,276]. The hole-transporter has
two primary functionalities, firstly, it impedes the electron transfer and supports the hole
transfer, which can then be injected into the external circuit. The application of CNTs as
HTMs in perovskite cells offers two benefits, cheaper and more stable than the commonly
used organic molecular or polymeric materials. The mechanical resilience of CNTs may
further be beneficial for developing flexible perovskite solar cells [277]. Figure 25 illustrates
the utilization of CNTs in perovskite solar cells [97].
Graphene being transparent it can be utilized to demonstrate highly efficient and reliable
super flexible perovskite solar cells. For graphene based cells, the performance reached to
16.8% with no hysteresis comparable to that of the counterpart fabricated on a flexible indi-
um-tin-oxide electrode with a maximum efficiency of 17.3% [279]. The flexible devices also
demonstrate superb stability against bending deformation, maintaining 90% of its original
efficiency after 1000 bending cycles and 85% even after 5000 bending cycles with a bending
radius of 2 mm. Although the resistance of the graphene electrode is much higher than
that of the indium doped tin-oxide (ITO) anode, the graphene based devices show higher
transmittance, better energy level alignment with the HOMO level of the hole transport
layer, larger grains yielding higher short circuit current density (JSC) and open circuit voltage
(VOC), and a comparable efficiency compared to the ITO-based devices. Therefore, high
bending stability highlights that perovskite photovoltaics with graphene electrodes can
Figure 25. In panels (a) and (b) the schematics of two of the first publications in which carbon nanotubes
are employed in perovskite solar cells. The device in (a) uses a laminated CNT film as an electrode without
dedicated hole-transport material and is shown to perform even better than a control device with a gold
electrode (panel c). In the architecture in (b) a composite structure of functionalized SWNT and an inert
polymer matrix constitutes the hole-selective charge transport layer, which yields a performance of up
to 15.3% (panel d) [278], Copyright to WILEY-VCH Verlag GmbH & Co (2016).
replace ITO based anodes and pave the way for rollable and foldable photovoltaic applica-
tions [279]. However, in order to compete with other types of solar cells, graphene or CNT
based perovskites solar cells needs to be modified to a great extent as expressed in Figure
26. The details understanding of the interfacial electronic diagram and charge transport
must be attained for this purpose [280].
The interfaces chemistry of CNTs and rGO flakes within a polymer or metal oxide or
doped hybrid carbon composite can be beneficial for other optoelectronic or photochem-
ical applications, such as photodegradation of methylene blue [281], photoactive com-
posite [282–284], photocatalytic activity and anti-photocorrosion [278], and efficient UV
detection [279]. Figure 27 shows the photo responsive activities of graphene incorporated
ZnO composites [283,284]. The band modulation at the interfacial region of graphene and
ZnO together with the modification in the overall composite conductivity enhances the
Figure 26. Comparison of perovskite solar cells with other types of solar cells: energy-conversion efficiency
versus external radiative efficiency (ERE) for various experimental cells [280], Copyright to Macmillan
Publishers Limited (2017).
excitonic transition and the recombination of excitons is reduced which imply the enhanced
photoactivity of graphene-ZnO composites as compared to only ZnO [284]. Furthermore,
it is observed that the core-shell structured noble metal (Ag, Au) nanoparticle incorpo-
rated amorphous carbon composite can demonstrate stable surface plasmon resonance
[285–287]. There are two advantages of metal core and amorphous carbon shell structured
composites: first, the carbon shell prevents individual metal particles from agglomeration
with each other as well as it saves the nanoparticles from atmospheric contaminations and
second, the photo-excitation characteristics of electrons at the interfaces can be easily tuned
by changing RF-CVD process parameters. It is also observed that the modification in the
interfacial dielectric constant at metal/carbon junction can be utilized in effective electron
field emission, optical switching, stress reduction within carbon-based hard coatings, besides
opto-electronic and biomedical applications [285–287].
Now-a-days, our addictive dependency on electronic gadgets and equipment generate
pollutant radiation, namely, unwanted electromagnetic energy. Our electronic and/or elec-
trical devices produce electrical and magnetic fields that interrupt the operation of other
devices, nearby. This phenomenon is called electromagnetic interference (EMI) [288–290].
High-performance EMI shielding (or screening) materials are necessary to resolve the issues
of electromagnetic wave attenuation in both civil and military applications [291]. Owing
to their controllable aspect ratio, lightweight, excellent electrical conductivity, and flexibil-
ity, CNTs and graphene are used as effective conductive fillers to fabricate EMI shielding
composite structures [291,292]. Their EMI shielding effectiveness (SE) has the capacity to
dissipate electromagnetic energy which is expressed in decibels (dB). For high-efficiency
shielding materials, the specific SE (dB.cm2/g) is also a crucial criterion. Among various
polymers, such as, poly(methyl methacrylate) (PMMA), poly(vinylidene fluoride) (PVDF),
epoxy, waterborne polyurethane (WPU), polypropylene(PP), polyaniline (PAni), polyure-
thane (PU or PUR), polymer clay (PUG), polyethylene (PE), Acrylonitrile butadiene styrene
Figure 27. (a) Illustration of the proposed reaction mechanism for photocatalytic reduction of Cr(VI) in an
aqueous solution over graphene-ZnO (G-ZnO) nanocomposites upon visible light irradiation (λ > 400 nm)
and (b) photocatalytic performance of bare graphene, blank ZnO, G-ZnO with different weight addition
ratios of G, and 10% G-blank-ZnO in the reduction of Cr(VI) aqueous solution under visible light irradiation
((λ > 400 nm) in an aqueous solution [278], Copyright to Royal Society of Chemistry (2016), (c) modulation
of crystallite size with carbon content in GO-ZnO composite films (inset shows GO flakes in 25% GO–ZnO
film) and (d) UV photoresponsivity of ZnO and GO-ZnO films [284], Copyright to Royal Society of Chemistry
(2016).
(ABS), polyethylenimine (PEI), polyimide (PI), polystyrene (PS) etc., have demonstrated
excellent EMI SE while composited with CNT and graphene [291]. Table 5 summarizes
the EMI SE for these polymers in nanocomposites with CNTs, graphene, CNT/graphene
and graphene foam [291].
Among all the nanocomposites, PVDF has shown consistent EMI SE with graphene
and/or CNTs with minimum filler loading amount (Table 5). EMI SE in between 19 to
28 dB is achieved with 10 to 15 wt. % CNT and graphene loading in PVDF. Figure 28
shows the schematic of EMI shielding mechanisms for PVDF/CNT, PVDF/graphene, and
PVDF/CNT/graphene nanocomposite films. The specific EMI SE values of PVDF/CNT,
PVDF/graphene, and PVDF/CNT/graphene nanocomposite films at 0.1 mm thickness
are also presented for different frequency and filler loading (Figure 28 (d) and (e) respec-
tively). In the PVDF composite films, due to presence of interfaces between the carbon
materials and PVDF, the interfacial polarization loss induced by the EM waves is con-
tributed to the absorption. Generally, electrical transport in polymer composites can take
place either through direct-contacts between the conductive fillers or by the hopping of
Table 5. EMI shielding performance of carbon-based polymer composites [291].

Specific SE (dB.
Filler type Filler loading (Wt. %) Matrix Thickness (mm) EMI SE (dB) cm2/g)
Graphene 4.23 PMMA 3.4 30 74
Graphene 10 PS 2.8 18 62
Graphene 5 WPU 2.0 32 112
Graphene 10 PEI 2.3 20 68
CNT 33 Cellulose 0.64 30 312.7
CNT 16 PP 1.0 34.8 356.9
CNT 20 PMMA 4.5 30 49.0
CNT 76.2 WPU 2.3 35 2143.0
CNT 0.66 Epoxy 2.0 33 169.2
CNT 10 PE 3.0 35 117.0
CNT 10 ABS 1.1 40 317.9
CNT 10 PAni 2.0 35 194.4
Graphene foam 16 PI 0.8 21 937
Graphene foam 30 PS 2.5 29.3 260
Graphene foam 10 PUG 60 57.7 332
CNT 60.6 Phenolic 0.14 32.4 1257.6
CNT 61.5 WPU 0.32 35 778.5
CNT 5 PVDF 0.1 22.41 1310
CNT 8 PVDF 0.1 25.02 1430
Graphene 10 PVDF 0.1 18.70 1067
Graphene 15 PVDF 0.1 22.58 1265
CNT/Graphene 5/10 PVDF 0.1 27.58 1557
Figure 28. EMI shielding mechanisms for (a) PVDF/CNT, (b) PVDF/graphene, and (c) PVDF/CNT/
graphene composite films, (d) specific EMI SE values of PVDF/CNT, PVDF/graphene, and PVDF/CNT/
graphene composite films at a 0.1 mm thickness and (e) average specific EMI SE values of PVDF/CNT,
PVDF/graphene, and PVDF/CNT/graphene films with a thickness of 0.1 mm [291], Copyright to American
Chemical Society (2017).
electrons between sufficiently close conductive particles [291]. In the PVDF/CNT/graphene

the multiple reflections and greater interfacial polarizations contributed to the enhanced
microwave absorption properties. Furthermore, the greater number of charges coupled
with their uniform state of dispersion generated a conductive network, which consequently
dissipated more electrical energy and thus resulted in a higher ohmic loss. These PVDF/
carbon composite films can be utilized as flexible, ultrathin, and high-efficiency electro-
magnetic screening devices.
9. Sensing and biomedical properties of carbon composites

Sensor is such a device that detects or measures a physical property and records, indicates,
or otherwise responds to it. There are mainly two types of sensors, chemical gas sensors and
biosensors. Sensors can also be used for environmental, security, agriculture or food safety
applications, and to healthcare including clinical diagnosis and treatment of diseases. The
important parameters for a sensor are sensitivity, selectivity, and rapid and cost-effective
detection of target molecules [60,292,293]. Carbon based nanomaterials, like, CNTs and
graphene are two of the most widely used nanomaterials with unique electronic, optical,
mechanical, chemical and electrochemical properties. On the other hand, polymers are
one of the most widely exploited classes of materials due to their availability in incredible
varieties, subsequent compendium of properties, relatively low cost, easy processing, and
potential for easy recycling and application as sustainable materials. The polymeric com-
posites based on CNTs and graphene possess structural and functional properties superior
to those of the pure components and enhanced performance in a broad range of techno-
logical fields such as telecommunications, electronics, energy, biomedicine and transport
industries [63,66,294]. As such, these carbon-based polymer nanocomposites (CPNs) play
different roles in chemical sensors and biosensors besides providing mechanical stability
and improving the nanofiller dispersion leading to enhanced sensitivity and selectivity
[295,296]. Figure 29 summarizes different kinds of CPN films for sensing applications.
There are different gas sensors depending on how the gaseous adsorbates with different
compositions and molecular structures interact with the CPNs. Examples include field-ef-
fect transistor (FET) gas sensor, chemiresistor gas sensor, surface acoustic wave (SAW) gas
sensor, resistance gas sensor, Radio-frequency identification (RFID)-based gas sensor and
other toxic gas sensors. Table 6 summarizes different CPN gas sensors in details. There have
been extensive studies on CPNs for efficient and accurate sensing of various gases, however
several problems need to be addressed. Firstly, selective detection of a particular gas in a
gas mixture has seldom been investigated, which is required to be improved. Secondly, in
order to fabricate high-performance CPN gas sensors, the influences of contaminations
and the interruption of environment (moisture, water etc.) should be efficiently nullified.
Most importantly the conductivity and the interfaces should be strategically designed for
an advancement in carbon based nanocomposite gas sensors, because the interfaces most
actively take part in gas selection and detection.
Beside chemical gas sensor, CPNs have been intensively used for the detection of diverse
biologically-relevant substances including DNA, H2O2, glucose etc. For example, AuNP
can covalently associate with multiple thiolated probes, single-stranded DNA molecules,
antibodies and other biomaterials, contributing to construct biosensors. Similar to gas sen-
sors, there are different types of biosensors, such as, Field-effect transistor (FET) biosensor,
Figure 29. Different kinds of carbon-based polymer nanocomposites (CPN) and sensing applications of
CPN-based detection devices [60], Copyright to Elsevier Inc. (2017).
Table 6. Chemical gas sensors based on carbon nanocomposites (modified from Ref. [60]).
Materials Sensing mechanism Target gas Linear range Response time
GO-Pt NPs FET H2 1–200 ppm 500 s
G-SnO2 NPs FET H2 1–100 ppm 1s
G-Pd NPs Resistive H2 100–50000 ppm 30 s
rGO-Al NPs Resistive NH3 5–100 ppm
NO2 1.2–5 ppm –
rGO-porous PEDOT Resistive NO2 50 ppb-20 ppm 170–180 s (40 nm)
rGO-Na-Ag Resistive NO2 1–10 ppm 10 min
G-TiO2 Resistive O2 134 ppm-100% 193 s
G-SnO2 Resistive Ethanol 1–100 ppm 78–97 s
rGO-PPr Chemiresistor Toluene/chloroform/ 24–500 ppm
hexane 10 s
G-alanine-Ni SAW CO2 0–38500 ppm –
rGO-Pt NPs RFIS H2 1–50 ppm 15 s
G-SrCO3 Cataluminescence n-propanol 0.2–32 mg/L 2s
SWCNT-DAP-Dextran, NIR fluorescence NO 10−6–10−7 mol/L
Ref. [297] –
PEDOT–MWCNT/CPE, Differential pulse Dopamine 10−7-2 × 10−5 mol/L –
Ref. [298] voltammetry
photoelectrochemical (PEC) biosensor, fluorescent biosensor, electrochemical enzyme-

based biosensor, electrochemical non-enzymatic biosensor etc. [60,299]. Figure 30 illustrates
fluorescent-based glucose using phenoxy-derivatized dextran-wrapped SWNT and PVA
coated SWNTs [299]. Figure 31 describes the protein (chitosan) detection through NIR
fluorescence biosensing method using SWNTs [300]. This was the first chemical approach
for selective protein recognition using fluorescent SWNTs enabling label-free microarrays
capable of single protein detection. Hexahistidine-tagged capture proteins directly expressed
by cell-free synthesis on SWNT/chitosan microarray were bound to a Ni2+ chelated by
Figure 30. Schematic representation of polymer-wrapped SWCNT systems used for glucose detection:
(a) introduction of concanavalin A (ConA) to phenoxy-derivatized dextran-wrapped SWCNT initiates
nanotube agglomeration, resulting in a decrease in nanotube fluorescence. The addition of glucose,
which binds to ConA, separates the nanotube bundles with the recovery of fluorescence, (b) PVA-wrapped
SWCNT is covalently tethered to GBP. Upon addition of glucose, the GBP undergoes a conformational
change, resulting in a change in the SWCNT fluorescence intensity [299], Copyright to Royal Society of
Chemistry (2014).
Figure 31. (a) Sensor array fabricated using SWCNT-chitosan (CS). A SWCNT-CS suspension is spotted on
glass and functionalized with Ni-NTA to bind His-tag proteins, (b) Optical and NIR fluorescence image of
the SWCNT-CS array, (c) Signal transduction mechanism for detection of protein-protein interactions: a
NIR fluorescence change from the SWCNT occurs when the distance between the Ni2+ quencher and the
SWCNT is altered upon analyte protein binding [300], Copyright to American Chemical Society (2011).
Nα,Nα-bis(carboxymethyl)-l-lysine grafted to chitosan surrounding the SWNT. The Ni2+

acts as a proximity quencher at the interface of SWNT. This ability to discern single pro-
tein binding events decreases the apparent detection limit from 100 nM, for the ensemble
average, to 10 pM for an observation time of 600 s [300].
Table 7 enlists different important biosensors based on graphene and CNT polymer
nanocomposites. There have been many studies for advancing conventional biosensors.
Detailed study indicated that more and more molecular structural changes or chemical-re-
actions are used as the bridging media of the biosensors. The selectivity and sensitivity of
Table 7. Biosensors based on graphene/CNT-nanocomposites (modified from Ref. [60]).

Materials Analyte Sensitivity Detection limit Linear range
rGO-CuNPs Glucose – 3.4 μΜ 0.01–1.2 mM
rGO-PLL-MnO2 Glucose oxidase 28.8 μA/μM/cm2 0.02 μΜ 0.04–10 mM
H2O2 45.4 mA/mM/cm2 0.01 μΜ 0.05 μM–7 mM
rGO-AuNPs-engyme H2O2 124.6 μA/μM/cm2 25 nM 0.01–14 mM
Cholesterol 3.14 μA/μM/cm2 0.05 μΜ 0.05–0.35 mM
G-NiO Cholesterol 240.6 μA/μM/cm2 0.13 μΜ 2–40 μM
rGO-AuNPs Acrylamide (pheochrom – 0.04 mM
ocytoma) 0.1–5 mM
rGO-AuNPs-antibody Transferrin – 0.038 μg/mL 0.038–40 μg/mL
G-AuNPs-PAni BCR/ABL fusion gene of – 2.11 pM
chronic myelogenous
leukemia 10–1000 pM
G-mesoporous silica-AuNP Adenosine triphosphate – 0.023 nM 0.05–56.5nM
rGO-AuNPs L-lactate tumor biomarker 154 μA/μM/cm2 0.13 μΜ 10 μM–5 mM
G-CdS-DNA Catechol – 4.9 × 10−9 mol/L 10−8–10−6 mol/L
G-4-amino-3-hy- Melatonin – 60 × 10−9 mol/L
droxy-1-napthalenesul-
fonic acid-melamine 0.05–100 μM/L
rGO-ZnO DNA – 2.4 × 10−15 M 10−14–10−7 M
TNT – 5.3 × 10−8 M 10−7–5 × 10−6 M
Vertical G-PEDOT-PtNPs, Glucose – 0.3 μM
Ref. [301] 0.01–50 mM
SWCNT-PtNP, Ref. [301] Glucose – 0.5 μM 0.005–5 mM
the biosensor can further be improved by using the large surface-to-volume ratio of carbon
nanomaterials and the special recognition ability of the biological molecules. However,
there are still some problems of CPNs-based biosensors, for example, high salt concentra-
tion causes the aggregation and precipitation of carbon nanomaterials which influence the
surface charge arrangement of CPNs. Therefore, biosensors with abundance in interfaces
between carbon nanomaterials, robustness in their relative structure and chemical states
within composites, and the matrix with some mechanical stability would be crucial for
advancement of biosensors.
Carbon based composite and nanocomposite materials have drawn immense research
attention for medical and biomedical applications. In fact, there has been continuously grow-
ing demand for real-time personal health monitoring devices for daily life, and considerable
attention has recently been devoted to the development of highly flexible and stretchable
pressure sensors for skin-mountable human motion detectors [302–305]. Among a variety
of transduction mechanisms of the pressure sensors, particularly, resistive sensing function-
alities have been the most widely applied mainly due to the easy signal collection capability,
simple sensor architecture, and facile fabrication process [306]. Resistive pressure sensors
typically react to an applied pressure by a decrease in the contact resistance (or increase in
the electrical conductivity) between the top and bottom sensing electrodes.
Carbon based nanocomposites being mechanically robust are very much desirable for
such actuation based application. However, the interface fabrication must be carefully taken
care because interface is the most sensitive portion for pressure sensors. A simple-archi-
tectured wearable resistive pressure sensor based on highly compliant yet robust carbon
composite conductors are fabricated using a vertically aligned carbon nanotube (VACNT)
forest embedded in a polydimethylsiloxane (PDMS) matrix with irregular surface mor-
phology. The fabrication process has been schematically presented in Figure 32 [307]. A
roughened surface of the VACNT/PDMS composite conductor is strategically formed using
Figure 32. Resistive pressure sensor based on flexible VACNT/PDMS composite conductors with irregular
surface morphology: (a) schematic illustration of the fabrication process of the flexible pressure sensor, (b)
digital image of the fabricated sensor (scale bar: 20 mm), (c) cross-sectional SEM image of the sensor (scale
bar: 10 μm), and (d) schematic illustration of the basic working principle of the sensor [307], Copyright
to American Chemical Society (2017).
a sandblasted silicon master in a low-cost and potentially scalable manner which plays an
important role in improving the sensitivity of resistive pressure sensor.
For real-time health monitoring, artificial electronic skins, and human-to-machine inter-
faces, wearable pressure sensors are the crucial building blocks. After assembling two of the
roughened composite conductors as shown in Figure 32, the pressure sensor was ready to
examine. The pressure sensitivity of the device is defined as S = (ΔR/R0)/ΔP, where ΔP is
the change in applied pressure [307]. With applied pressure in the range of 0–0.7 kPa, the
sensor had a high sensitivity of S = ∼0.3 kPa−1, which means that many new contact junctions
between the conductive protrusions on the upper and lower electrodes were developed in
addition to the gradual increase in contact area between the initially contacting protrusions
in this pressure regime. Moreover, the sensor showed stable steady-state responses under
various pressures, a wide detectable range of up to 5 kPa before saturation, a relatively fast
response time of ∼162 ms, and good reproducibility over 5000 cycles of pressure loading/
unloading. The fabricated pressure sensor can be used to detect a wide range of human
motions ranging from subtle blood pulses to dynamic joint movements. Figure 33 presents
the characteristics of the flexible pressure sensor as a skin-mountable human motion detec-
tor for wrist pulse, neck pulse and elbow pulse [307].
Furthermore, the sensor can be used to map spatial pressure distribution in a multipixel
platform (in a 4 × 4 pixel array) [307].
On the other hand, interactivity between humans and smart systems, including wearable,
body-attachable, or implantable platforms, can be enhanced by realization of multifunc-
tional human-machine interfaces, where a variety of sensors collect information about
the surrounding environment, intentions, or physiological conditions of the human to
which they are attached [308,309]. Recently a stretchable, transparent, ultrasensitive, and
patchable strain sensor is fabricated from a novel sandwich-like stacked piezoresisitive
nanohybrid film of single-wall carbon nanotubes (SWCNTs) and a conductive elastomeric
composite of polyurethane (PU)-poly(3,4-ethylenedioxythiophene) polystyrenesulfonate
(PEDOT:PSS) [310]. This sensor, capable to detect small strains on human skin, was created
using environmentally benign water-based solution processing technique. The tunability
of strain sensitivity (i.e. gauge factor), stability, and optical transparency were attributed to
enhanced formation of percolating networks between conductive SWCNTs and PEDOT
phases at interfaces in the stacked PU-PEDOT:PSS/SWCNT/PU-PEDOT:PSS structure.
The mechanical stability, high stretchability of up to 100%, optical transparency of 62%,
Figure 33. Flexible pressure sensor as a skin-mountable human motion detector: (a) measurement of
wrist pulse (inset: digital image of device attached on the wrist for measurements (scale bar: 20 mm)),
(b) magnified waveform extracted from (a) of a period of the wrist pulse, (c) measurement of neck pulse
(inset: digital image of device attached on the neck for measurements (scale bar: 20 mm)), (d) sensor
response to sequential flexion motions of the wrist, and sensor responses under repeated dynamic flexion
and straightening motions of (e) the wrist and (f) the elbow (inset: digital images of the sensor under the
tests (scale bars: 20 mm)) [307], Copyright to American Chemical Society (2017).
and gauge factor of 62 suggested that when attached to the skin of the face, this sensor
would be able to detect small strains induced by emotional expressions such as laughing
and crying, as well as eye movement, and was confirmed experimentally [310]. Therefore,
carbon nanocomposites can be applied for very advanced application if the structure and
interfacial chemistry are well understood and strategically designed. However, the cytotoxic
properties of carbon-based nanomaterials must be considered with great precautions for
in-vivo or in-vitro biomedical applications [311,312].
10. Application of carbon composites for aerospace, marine, construction

and automotive
Carbon fiber based epoxy composites are suitable for aerospace, marine, construction and
automotive industries. These applications require a material that is light weight, having
high mechanical strength, high flexural modulus, and high stiffness [313–317]. The com-
posite must be robust in temperature variations and harsh atmospheric conditions, such as,
salt water, high wind, high fracture toughness etc. Carbon fiber based epoxy composited
laminate structures are very easy and cost effective to fabricate as discussed elaborately in
the synthesis section. Such laminate composite structures with or without a lightweight
core material is generally utilized as building blocks in marine, aviation, automotive and
construction industries. In order to improve the mechanical properties or to strengthen
Figure 34. Schematic of morphing composite propeller (MCP) (a) conventional propeller (b) simplification
of MCP (c) cavities of MCP (d) ultimate design. [324], Copyright to Elsevier Inc. (2017).
particular mechanical property in carbon fiber epoxy composites, nanocarbon fillers, such
as, CNTs, graphene, GO, rGO and their hybrids are used with or without functionalization
[318,319]. In this context, multifunctional composites would be very interesting. More elab-
orately, a combination of existing excellent mechanical properties of CF/epoxy composites
together with other embedded functionalities, such as thermal management, energy storage
and sensing properties would bring a technological breakthrough in applicability of carbon
based composites. Recently, there has been very few attempt in this direction [320–322] and
certainly more research attention is required. For example, Tawfic et al. has demonstrated
weight reduction a marine vessel by 44.32% through replacing the steel hatch covers with
composites including added benefits, such as, fuel saving, deadweight Increment, lower
center of gravity and most importantly strengthening the hatch cover by 150% [323]. In
an another study, morphing composite propeller (MCP) has been predicted to improve
the performance (increase in 1.1% efficiency and structural durability) for marine vehicles
considerably [324]. Figure 34 presents the structural details. These examples indicate that
strategic and rational designing of these vehicles (in air, water and ground) using carbon
composites could bring enormous prosperity.
11. Conclusions and prospects

Carbon based materials, such as, carbon fiber (CF) generally composited with epoxy to have
superior mechanical properties. However, the interfacial regions between carbon fiber and
epoxy often undergo delamination resulting in inferior applicability for advanced technolo-
gies. In this respect, carbon nanomaterials, such as, graphene, CNTs and their hybrids can
be incorporated as a filler to improve the mechanical properties. The interfacial wettability
can also be improved through chemical methods, like functionalization with heteroatoms
or chemical groups or grafting various polymers. CF/epoxy based composites are gener-
ally mechanically robust and therefore they are suitable for aviation, automotive, marine
and construction applications. Carbon nanomaterials themselves can be composited with
different polymers to form carbon nanocomposites. Such nanocomposites have different
functionalities ranging from adsorption, thermal, electrical, electrochemical, sensing, and
biomedical applications. The important factor in all carbon-based composites is the func-
tionality of the interfaces. Various functionalities can be imparted to carbon composites, if
the interfaces are controlled or manipulated as desired. The overall thermal and electrical
conductivities of these composites are crucial for their applicability in electrochemistry,
optoelectronics, photovoltaic as well as chemical and bio-sensing applications. Wearable,
flexible and stretchable advanced biomedical devices (like, pressure and strain sensors) can
also be made from carbon nanocomposites.
The prospects of carbon composites are very promising. However, the interface chemistry
should be well understood and controlled with strategic planning for a particular func-
tionality. In this respect, composites using three-dimensional ordered carbon architectures
would be very interesting to impose mechanical reliability for different applications. Besides
using carbon composites for a particular application, enormous efforts must be undertaken
to produce multi-functional carbon composites to make them more practical and cheaper
for a technological breakthrough.
Acknowledgements
Authors would like to thank NSF, NASA, and the Department of Defense—Multidisciplinary
University Research Initiative for financial assistance. Thanks are also due to our colleagues, collab-
orators and peers for their work cited in this article.
Disclosure statement
There is no potential conflict of interest.
Funding
This work was supported by the NSF [grant number CMMI-1400274]; NASA [grant number
NNC16CA42C], [grant number NNX16AD48A]; Department of Defense-Multidisciplinary University
Research Initiative, Air Force Research Laboratory [grant number DoD-MURI-FA9550-12-1-0037].
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Interfacial aspects of carbon composites

Article in Composite Interfaces · March 2018

Carbon Materials View project

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ISSN: 0927-6440 (Print) 1568-5543 (Online) Journal homepage: http://www.tandfonline.com/loi/tcoi20

Interfacial aspects of carbon composites

Rajib Paul & Liming Dai

To link to this article: https://doi.org/10.1080/09276440.2018.1439632

Published online: 26 Mar 2018.

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Interfacial aspects of carbon composites

ABSTRACT ARTICLE HISTORY

CONTACT Liming Dai liming.dai@case.edu

Figure 1. Schematic presentation of classification for composite materials.

and transparent energy storage systems, extensively mountable sensors, opto-electronics

2. Synthesis of carbon composites

2.1. Carbon Fiber Reinforced Composites

2.2. Carbon nanotube based composite materials

polyaniline (PAni), polypropylene (PP), poly(ether ketone) (PEK), polyethyleneimine (PEI),

is observed by transmission electron microscope (TEM). P(GMA-co-VCz) function-

2.3. Graphene based composite materials

In another report, Zhao et al. synthesized phenol formaldehyde (PF)-rGO compos-

2.4. CNT and/or Graphene Based Hybrid Carbon Composite Materials

enthusiasm in aerospace and automotive engineering owing to their excellent mechanical

2.5. Carbon composites with organic, inorganic and metallic materials

3. Adhesion and interface modification

3. Mechanical properties

a representative schematic of a fiber/matrix composite undergoing a tensile deformation.

4. Thermal properties

5. Electrical properties

of PS/MWCNTs-2/PMMA composites with varied PMMA and MWCNT contents respec-

6. Effect of interface on electrochemical properties of carbon based

7. Photo or radiation interactive properties of carbon composites

Table 5. EMI shielding performance of carbon-based polymer composites [291].

electrons between sufficiently close conductive particles [291]. In the PVDF/CNT/graphene

9. Sensing and biomedical properties of carbon composites

photoelectrochemical (PEC) biosensor, fluorescent biosensor, electrochemical enzyme-

Nα,Nα-bis(carboxymethyl)-l-lysine grafted to chitosan surrounding the SWNT. The Ni2+

Table 7. Biosensors based on graphene/CNT-nanocomposites (modified from Ref. [60]).

10. Application of carbon composites for aerospace, marine, construction

11. Conclusions and prospects

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