Application of Carbon Nanotubes in the development of

Reinforced Composites: A Review

Mohd. Wamik.
Mechanical Engineering Department, National Institute of Technology Uttarakhand,
Srinagar, 246174, India.

Introduction

Nanotechnology is defined as the study and use of structures between 1 nanometre and 100
nanometres in size. To give you an idea of how small that is, it would take eight hundred 100
nanometre particles side by side to match the width of a human hair. The word Nano is a
scientific prefix that stands for 10-9 or one-billionth; the word itself comes from the Greek
word Nanos, meaning dwarf. Scientists have been studying and working with nanoparticles
for centuries, but the effectiveness of their work has been hampered by their inability to see
the structure of nanoparticles. In recent decades the development of microscopes capable of
displaying particles as small as atoms has allowed scientists to see what they are working
with.

Fig.1(a): carbon structure.[1] Fig.1(b): carbon nanotube sheets.[2]

A significant nanoparticle discovery that came to light in 1991 was carbon nanotubes where
buckyballs are round, nanotubes are cylinders that havent folded around to create a sphere.
Carbon nanotubes are composed of carbon atoms linked in hexagonal shapes, with each
carbon atom covalently bonded to three other carbon atoms. Carbon nanotubes have
diameters as small as 1 nm and lengths up to several centimeters. Although, like buckyballs,
carbon nanotubes are strong, they are not brittle. They can be bent, and when released, they
will spring back to their original shape.

What is Nanocomposites? A nanocomposite is a matrix formed by adding nanoparticles to

improve a particular property of the material. These Structural polymer composites are
engineered structures from strong load carrying reinforcements (e.g., carbon or glass fibres)
and matrix polymer materials having considerably lower strength and density than the
reinforcing phase and combination of these fibres and matrixes gives rise to high strength
materials with minimum weight. However because of the limited lengths that can be obtained
for nanotubes (several hundred micrometres, until recently), studies of continuous carbon
nanotube reinforced polymer composites is limited. That is why most of the extensive
research has focused on randomly oriented, discontinuous nanotube composites or short
fibre composites. Although these composites could be interesting for certain applications
(e.g., electrically conducting composites), but they are not the best for high strength structural
composites which require loads to be carried by continuous fibres across the dimensions of
the composite structures. Several important applications of these nanocomposites have been
developed such as structural materials for gas separation membrane [3]. Gas separation
polymeric membrane is a dynamic research area due to increasing interest in carbon dioxide
capture to alleviate global warming [4].

Carbon Nanotubes Reinforced Composite: Carbon nanotubes are very short fibres and
polymer composites. Carbon nanotube has remarkable physical and mechanical properties
[5, 6]. These are hexagonal network/sheet of carbon atoms, which are rolled up into a hollow
cylinder. Its ends are capped with half of fullerene molecule. Carbon nanotube is similar in
chemical composition to graphite. Nanotubes generally are of two types:- Single-walled
carbon nanotube (SWCNT) And Multi-walled nanotubes (MWCNT).

Multi-walled nanotubes consists a collection of several concentric graphene cylinders bound

together by weak forces to form a Russian doll-like structure. Carbon nanotube of polymeric
composites is generally used as nanofiller to form ultralight structural materials of enhanced
mechanical, electrical, optical and thermal, characteristics [7-9]. The initial nanotubes
production and employment in polymeric materials were not cost-effective due to expensive
production procedures. However advancing in CNT synthesis has improved quantity and
quality of nanotube at a very low cost. With the mass production of carbon nanotube,
advanced polymer/CNT nanocomposite with multifunctional features has attracted the
attention of both academia and industries [10, 11].

Applications of Nanocomposite materials:

Producing batteries with greater power output: Nanocomposites developed a method to make
anodes for lithium ion batteries from a composite formed with silicon nanospheres and
carbon nanoparticles. The anodes made of the silicon-carbon nanocomposite make closer
contact with the lithium electrolyte, which allows faster charging or discharging of power.
Speeding up the healing process for broken bones: Growth of replacement bone can be
speeded up when a nanotube-polymer nanocomposite is placed as a kind of scaffold which
guides growth of replacement bone. The researchers are conducting studies to better
understand how this nanocomposite increases bone growth.
Producing structural components with a high strength-to-weight ratio: An epoxy containing
carbon nanotubes can be used to produce nanotube-polymer composite windmill blades. This
results in a strong but lightweight blade, which makes longer windmill blades practical. These
longer blades increase the amount of electricity generated by each windmill.
Using graphene to make composites with even higher strength-to-weight ratios: Adding
graphene to epoxy composites may result in stronger/stiffer components than epoxy
composites using a similar weight of carbon nanotubes. Graphene appears to bond better to
the polymers in the epoxy, allowing a more effective coupling of the graphene into the
structure of the composite. This property could result in the manufacture of components with
higher strength-to-weight ratios for such uses as windmill blades or aircraft components.
Making tumors easier to see and remove: Joining magnetic nanoparticles and fluorescent
nanoparticles in a nanocomposite particle that is both magnetic and fluorescent. The magnetic
property of the nanocomposite particle makes the tumor more visible during an MRI
procedure done prior to surgery. The fluorescent property of the nanocomposite particle could
help the surgeon to better see the tumor while operating.
Nanocomposite formation:
Exfoliation: Nanocomposites can be formed from clays and organoclays in a number of ways
including various in situ polymerization [12-15], solution [16,17] and latex [18,19] methods.
one of the most important process involved melt processing [20,21] because this is generally
considered more economical, more flexible for formulation, and involves compounding and
fabrication facilities commonly used in commercial practice For most purposes, complete
exfoliation of the clay platelets, i.e., separation of platelets from one another and dispersed
individually in the polymer matrix, is the desired goal of the formation process. However, this
ideal morphology is frequently not achieved and varying degrees of dispersion are more
common and far from a completely accurate or descriptive nomenclature, the literature
commonly refers to three types of morphology: immiscible (conventional or
microcomposite), intercalated and miscible or exfoliated.

Fig.2.:IIustration of different states of organoclays in polymers.[22]

For the case called immiscible the organoclay platelets exist in particles comprised of
tactoids or aggregates of tactoids more or less as they were in the organoclay powder, i.e., no
separation of platelets. For completely exfoliated organoclay, no wide angle X-ray peak is
expected for the nanocomposite since there is no regular spacing of the platelets and the
distances between platelets would, in any case, be larger than what wide angle X-ray
scattering can detect. It has been found that a small amount of a polyolefin that has been
lightly grafted with maleic anhydride, w1% MA by weight is typical, can act as a very
effective compatibilizer for dispersing the organoclay in the parent polyolefin. This does not
lead to the high level of exfoliation that can be achieved in polyamides, but this approach has
allowed such nanocomposites to move forward in commercial applications, particularly in
automotive parts[15,19].

In the case of olefin copolymers with polar monomers like vinylacetate and methacrylic acid
(and corresponding ionomers), the degree of exfoliation that can be achieved progressively
improves as the polar monomer content increases [23]. In all cases, the best exfoliation is
achieved when the structure of the surfactant and the process parameters are optimized.

Exfoliation of graphite: The procedures currently used to produce graphene-like materials

have changed little. Techniques for the exfoliation of GICs have also been developed,
although most of these approaches do not yield single-layer sheets but rather platelets with
thicknesses typically above approximately 5 nm. Liquid-phase exfoliation of graphite and
chemical synthesis of graphene from polycyclic aromatic hydrocarbon precursors may also
eventually provide scalable alternative routes for production of graphene [12], as could the
further development of gas phase CVD methods [19]. Techniques for the exfoliation of GICs
have also been developed, although most of these approaches do not yield single-layer sheets
but rather platelets with thicknesses typically above approximately 5 nm. Liquid-phase
exfoliation of graphite and chemical synthesis of graphene from polycyclic aromatic
hydrocarbon precursors may also eventually provide scalable alternative routes for
production of graphene [12], as could the further development of gas phase CVD methods.
Due to variety of uses have been envisioned or demonstrated for GNPs and graphene-based
materials, and their use as a composite filler has attracted considerable interest recent work
has largely focused on use of graphene-based filler materials derived from GO(Graphene-
Oxide). GO-derived fillers can exhibit high electrical conductivities (on the order of
thousands of S/m) [8], high moduli (reported values ranging from 208 GPa [24] to over
650GPa [25]), and can be easily functionalized to tailor their compatibility with the host
polymer. The reported values of stiffness and electrical conductivity of GO derived filler
materials can be higher than those reported for nanoclays [26], but generally lower than those
reported for single-walled carbon nanotubes (SWNTs) [27].

Most exfoliated graphite fillers are derived from GICs, which are compounds of graphite with
atoms or molecules (such as alkali metals or mineral acids) intercalated between the carbon
layers [28]. The intercalation of graphite increases its interlayer spacing, weakening the
interlayer interactions and facilitating the exfoliation of the GIC by mechanical or thermal
methods. Varying structural arrangements of the intercalant are possible, such as alternating
layers of graphene and intercalant, as well as multiple (two to five) adjacent graphene layers
between intercalant layers (higher-stage GICs)[29]. It is the former arrangement, however,
which is preferred for the complete exfoliation of these materials into monolayer platelets
Intercalation of graphite by a mixture of sulfuric and nitric acid produces a higher-stage GIC
that can be exfoliated by rapid heating or microwave treatment of the dried down powder,
producing a material commonly referred to as expanded graphite (EG), spacing relative to
graphite, consisting of thin platelets which are loosely stacked [26]. Notably, an acid
treatment may also oxidize the platelets, albeit to a far lesser degree than GO [23]. EG itself
has been investigated as a composite filler, although its effectiveness in enhancing properties
compared with GO derived fillers is limited by its layered structure and relatively low
specific surface area. To produce a higher surface area material, EG can be further exfoliated
by various techniques to yield GNPs down to 5 nm thickness

Production and properties of GO (Graphene-Oxide): GO is generally produced by the

treatment of graphite using strong mineral acids and oxidizing agents, typically via treatment
with KMnO4 and H2SO4, as in the Hummers method or its modified derivatives, or KClO3
(or NaClO3) and HNO3 as in the Staudenmaier or Brodie methods . These reactions achieve
similar levels of oxidation (C:O ratios of approximately 2:1) which ultimately disrupts the
delocalized electronic structure of graphite and imparts a variety of oxygen-based chemical
functionalities to the surface. hydroxyl and epoxy groups are present in highest concentration
on the basal plane, with carboxylic acid groups around the periphery of the sheets as shown
in Fig. 1. GO has an expanded interlayer spacing relative to graphite which depends on
humidity (for instance, 0.6nm when subjected to high vacuum to roughly 0.8nmat 45%
relative humidity) due to intercalation of water molecules.
Fig.3: Schematic illustrating the chemical structure of graphite oxide (GO) and the structural
difference between layered GO and exfoliated graphene oxide (GeO) platelet.[30]

Production of graphene-based nanocomposite materials:

Graphene has a rich history which spans over forty years of experimental work [28].
Pristine graphene (a single, purely sp2-hybridized carbon layer free of heteroatomic defects)
has been produced by several routes [29] including growth by chemical vapour deposition
(both of discrete monolayers onto a substrate and agglomerated powders), micro-mechanical
exfoliation of graphite, and growth on crystalline silicon carbide. While these approaches can
yield a largely defect-free material with exceptional physical properties, current techniques of
making powdered samples of graphene do not yield large enough quantities for use as
composite [31]. Scalable approaches to GNPs and graphene-based materials (few-layer
platelets or monolayer carbon sheets with heteroatoms and topological defects) primarily
utilize GICs or GO as the precursor material, In the 1960s, Boehm and co-workers reported
the reduction of dispersions of GO using a variety of chemical reductants [15,16], as well as
thermal expansion and reduction [15], producing thin, lamellar carbon containing only small
amounts of hydrogen and oxygen. By using transmission electron microscopy (TEM), the
carbon material produced by chemical reduction was found to consist of single carbon
layers[32].

Chemical Vapour Deposition (CVD) Technique:

Commercial, high purity (>90%), double-walled and multi-walled CNT (DWNT and MWNT,
respectively) materials produced by the chemical vapour deposition (CVD) technique were
used in the fabrication of the sensor films. Short DWNTs, as well as carboxylic acid-
functionalized short DWNTs (DWNT-COOH) were purchased from Nanocyl S.A.
Transmission electron microscopy (TEM, JEOL JEM 2010F) characterization revealed that
these materials consist of CNTs having several hundreds of nanometres in length (Fig. 4a)
and5 nm in diameter, mainly containing two concentric graphene sheets (triple- and four-
walled CNTs can also be observed in high resolution TEM micrographs of these materials,
Fig. 4b). These DWNTs commonly appear self-organized in bundles, and exhibit open end-
caps and dangling bonds on the sidewalls as a result of CNT shortening and functionalization
(Fig. 4b). X-ray photoelectron spectroscopy (XPS) data indicated that less than 1% of the
CNT carbon atoms were modified during COOH functionalization [33]. CNT networks
were also fabricated from larger diameter (typically 1015 nm) and longer (10m) MWNTs
(Fig. 4c), purchased from Nanothinx S.A. High-resolution TEM micrographs revealed that
these CNTs typically consist of 715 concentric layers (Fig. 4d).
Fig.4: TEM micrographs of the employed MWNT (a and b) and DWNT (c and d).[34]
Properties of Carbon Nanotubes
The sp2 bonds in graphene is stronger than sp3 bonds in diamond that makes graphene the
strongest material, this atomic arrangement of carbon atoms are responsible for the unique
electrical, thermal, and mechanical properties of CNTs(Carbon Nanotubes).

Electrical Conductivity: A metallic CNT can be considered as highly conductive material.

Chirality, the degree of twist of graphene sheet, determines the conductivity of CNT
interconnects. Depending on the chiral indices, CNTs exhibit both metallic and
semiconducting properties. The electrical conductivity of MWNTs (Multi-walled Nanotubes)
is quite complex as their inter-wall interactions non-uniformly distribute the current over
individual tubes. However, a uniform distribution of current is observed across different parts
of metallic SWNT Electrodes are placed to measure the conductivity and resistivity of
different parts of SWNT rope. The measured resistivity of the SWNT ropes is in the order of
10-4 cm at 27 C, indicating SWNT ropes to be the most conductive carbon fibres.

Fig: Graph of Electrical conductivity vs wt.% of MWCNTs.

Strength and Elasticity: Each carbon atom in a single sheet of graphite is connected via
strong chemical bond to three neighbouring atoms. Thus, CNTs can exhibit the strongest
basal plane elastic modulus and hence are expected to be an ultimate high strength fibre. The
elastic modulus of SWNTs is much higher than steel that makes them highly resistant.
Although pressing on the tip of nanotube will cause it to bend, the nanotube returns to its
original state as soon as the force is removed. This property makes CNTs extremely useful as
probe tips for high resolution scanning probe microscopy. For different experimental
measurement techniques, the values of Youngs modulus vary in the range of
1.22 TPa1.26 TPa depending on the size and chirality of the SWNTs. The elastic modulus
of MWNTs is not strongly dependent on the diameter but correlated to the amount of disorder
in the nanotube walls.

Thermal Conductivity and Expansion: CNTs can exhibit superconductivity below 20 K

(approximately 253 C) due to the strong in-plane CC bonds of graphene. The strong C-C
bond provides the exceptional strength and stiffness against axial strains. Moreover, the larger
interplane and zero in-plane thermal expansion of SWNTs results in high flexibility against
non-axial strains. Due to their high thermal conductivity and large in-plane expansion, CNTs
exhibit exciting prospects in nanoscale molecular electronics, sensing and actuating devices,
reinforcing additive fibers in functional composite materials, etc. Recent experimental
measurements suggest that the CNT embedded matrices are stronger in comparison to bare
polymer matrices so they can significantly improve the thermo-mechanical and the thermal
properties of the composite materials.

Absorbent: Carbon nanotubes and CNT composites have been emerging as perspective
absorbing materials due to their light weight, larger flexibility, high mechanical strength and
superior electrical properties. Therefore, CNTs emerge out as ideal candidate for use in gas,
air and water filtration. A lot of research has already been carried out for replacing the
activated charcoal with CNTs for certain ultrahigh purity applications.
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