Polymer Reviews

ISSN: 1558-3724 (Print) 1558-3716 (Online) Journal homepage: http://www.tandfonline.com/loi/lmsc20

Recent Developments in Carbon Fibers and

Carbon Nanotube-Based Fibers: A Review

Nitilaksha Hiremath, Jimmy Mays & Gajanan Bhat

To cite this article: Nitilaksha Hiremath, Jimmy Mays & Gajanan Bhat (2016): Recent
Developments in Carbon Fibers and Carbon Nanotube-Based Fibers: A Review, Polymer
Reviews, DOI: 10.1080/15583724.2016.1169546

To link to this article: http://dx.doi.org/10.1080/15583724.2016.1169546

Accepted author version posted online: 20

Apr 2016.
Published online: 20 Apr 2016.

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POLYMER REVIEWS
http://dx.doi.org/10.1080/15583724.2016.1169546

REVIEW

Recent Developments in Carbon Fibers and Carbon

Nanotube-Based Fibers: A Review
Nitilaksha Hirematha, Jimmy Maysb,c, and Gajanan Bhata
a
Department of Materials Science and Engineering, The University of Tennessee, Knoxville, TN; bDepartment of
Chemistry, The University of Tennessee, Knoxville, TN; cChemical Sciences Division, Oak Ridge National
Laboratory, Oak Ridge, TN

ABSTRACT ARTICLE HISTORY

Carbon fibers are a very vast topic to discuss in a limited space such as Received 19 February 2015
this review paper. Nevertheless, we herein attempt to provide a Accepted 20 March 2016
succinct summary of current research in carbon fibers (CF), especially KEYWORDS
carbon nanotube (CNT) based CFs. A brief introduction to CFs with Carbon Fibers;
respect to precursors, characterization techniques, and applications is polyacrylonitrile (PAN); pitch;
presented. Following discussion on different commercially used CF graphene oxide; lignin;
precursors, is a description of the latest new precursors being stabilization; carbon
researched. While finding new low-cost precursors has been a focus of nanotubes; new precursors;
recent research, large scale production of CFs from these new CNT applications; composite
materials is not being realized at the present time. CNTs have received fibers; current trends and
a great deal of attention due to their unique structure and properties. future prospects of carbon
fibers
So CNTs and CNT-based CFs or carbon yarns (CYs) are discussed. In
addition to providing a brief overview of different methods of
providing CNTs, physical and electronic properties of CNTs are
discussed. The major focus of this review is CNT based composite
fibers. Efforts by several researchers have shown that incorporation of
CNTs in carbon fibers is a challenging task, and only a small percent
could be introduced successfully. Applications of CFs in various sectors
such as the airline industry, sporting industries, and automotive
industries are discussed. Applications of CNTs, focusing on composite
materials, coatings and films, microelectronics, energy applications,
and biotechnology are briefly reviewed. Some statistics of world
market of CFs as well as future prospects are discussed.

1. Introduction
The carbon fibers (CFs) were first used in the famous light bulb experiments conducted by
Sir Thomas Edison in the 1870s. Edison used cellulose (cotton or bamboo) as the precursor
material and carbonized it for conducting electricity. Though the fibers did not have tensile
strength, they sustained high temperature treatment. Eventually, in the 1950s, regenerated
cellulose, i.e., rayon was used as the precursor for CFs and hence high tensile strengths were
achieved. Other precursor materials (such as PAN, mesophase pitch) were researched to

CONTACT Gajanan Bhat gbhat@utk.edu Department of Materials Science and Engineering, The University of
Tennessee, Knoxville, TN 37996.
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/lmsc.
© 2016 Taylor & Francis Group, LLC
2 N. HIREMATH ET AL.

increase the carbon yield as rayon fibers lost most of the weight during carbonization. CFs
have become so important in the present time because of the exceptional and indispensable
properties they contain. They are deployed in automotive, aerospace, biomedical, sports,
industrial, light weight construction materials, electronics, and various other industries.
Carbon’s exceptional capacity to form bonds, both to a wide range of other atoms and to
other carbon atoms, make it the most studied element for advanced scientific research.
Ordered arrangements of covalently bonded carbon atoms produce various (nano) struc-
tures such as graphene, nanotubes, fullerenes, and diamond. Bonded arrangements of car-
bon atoms in one dimension, produces ultra-high strength fibers, commonly known as
carbon fibers (CF). Commercially, CFs are produced from various precursors, polyacryloni-
trile (PAN), pitch, and rayon; however, other precursors such as carbon nanotubes (CNTs),
graphene, lignin, cellulose, polyethylene, etc., are also being studied. PAN-based fibers are
produced by spinning a filament, and processing it through stabilization, carbonization, and
graphitization processes, all under tension. Industrially accepted spinning techniques include
wet spinning, dry spinning, dry-jet wet spinning, and melt spinning.1 Pitch fibers are made
from molten aromatic plastics or natural sources such as petroleum products. Pitch fibers
also undergo stabilization, carbonization, and graphitization. Rayon is one of the first com-
mercially used precursors for CF. Rayon is a regenerated cellulose fiber and is mixed with a
suitable solvent to make it spinnable. Following the spinning process, the rayon fibers
undergo stabilization and carbonization to form CFs. Lately, there has been increasing inter-
est in using CNTs. CNTs exist in different forms, multi-walled carbon nanotubes
(MWCNTs), and single-walled carbon nanotubes (SWCNTs) (chiral, armchair, and zigzag).2
CNT-based CFs or carbon yarns (CYs) are reported to have higher strength than CFs
derived from other precursors. Recently production of graphene-based CFs with good prop-
erties has been demonstrated. Theoretically, the highest tensile modulus (> 1TPa) can be
achieved by graphene-based CFs.3 To increase the strength of the CFs, intra-fiber interac-
tions must be improved by surface modification. Commonly practiced surface treatments
are oxidation (gas-phase, liquid phase, and catalytic), plasma treatment, washing, and siz-
ing.1 However, high strength, low cost fabrication, and large scale production of CFs cannot
be achieved at the present time due to limitations, such as lack of inexpensive precursors,
optimized synthesis techniques, marketability, etc.
Diameter of the CFs are mostly in the range of 5 to 10 mm. Thousands of such strands of
CFs are assembled to form a tow or yarn, and such yarns are used for various applications.
CF, being a thin long filament, contains more than 90 wt.% of carbon and exhibits outstand-
ing properties. High tensile strength (2»7 GPa), high compressive strength (up to 3 GPa),
high elastic modulus (200»900 GPa), low thermal expansion, and high electrical and ther-
mal conductivity are some of the prominent properties of CFs. Because of these outstanding
properties, CFs are used in composite materials in the airline and automotive industries,
sporting goods, wind turbine blades, etc.1 In addition, as the CF density is lower than that of
steel and it has higher specific strength than steel, virtually products of any shape that exhibit
excellent structural properties can be fabricated. In order to use CFs in commercial applica-
tions, it is critical to characterize them thoroughly so that the desired working standards
(such as, for electrical or mechanical applications, etc.) are ensured with the use of CFs alone
or in the composite structure.
In this brief review, variants of CFs from different precursors, other new precursors that
are being researched, CNTs (brief overview on structure and electronic properties) and
 POLYMER REVIEWS 3

carbon yarns (CYs), CNTs based composite polymer fibers, applications of CFs and CNTs,
current trends, and future prospects are discussed.

2. Variants of CFs
Commercially available carbon fibers vary in processing, structure, and properties based on
the precursors such as PAN, pitch, and rayon. Finding new precursors has been of continu-
ing interest to the community and recent materials, such as graphene, lignin, poly (p-phenyl-
ene vinylene), etc., and low cost CF are important. A brief overview on processing techniques
and characterization of CFs from various precursors is presented in the following sections.

2.1 PAN based CFs

PAN is the most important precursor in the CF industry, and it contains about »68 wt.%
carbon. The high melting temperature of PAN is due to the presence of the polar nitrile
groups which promote strong intermolecular interactions. Because PAN degrades below its
melting temperature, it is mostly processed by solution spinning techniques. Acidic co-
monomers are added to reduce the stabilization temperature and glass transition tempera-
ture, resulting in heat release and advancing stabilization reactions.4–6 Manufacturing CFs
involves several steps including polymer synthesis, fiber spinning followed by stabilization,
carbonization, and graphitization. The stabilization reaction constitutes cyclization during
which the nitrile groups of PAN transform to a ladder like structure that is high temperature
resistant and increases the carbon yield in carbonization step, oxidation which further
increases the thermal stability during high temperature treatment, and dehydration reactions
where the CHC double bonds are formed releasing H2O molecules. The carbonization reac-
tion involves removing any oxygen or other elemental content and increasing the crystallin-
ity (by increasing CHC bonding) of the carbon fiber. The graphitization reaction rearranges
the carbon atoms into hexagonal structure and hence makes the final fiber highly crystalline
forming high modulus fibers. The tensile properties of the resultant CFs may be enhanced
by careful optimization of the processing conditions. The cross section of a PAN-based CF
is as shown in Fig. 1, which displays a microstructure with a very high level of order and ori-
entation.7 Currently the gel-spinning technique is most widely employed for the production
of precursor fibers as it provides a high draw ratio of up to 51 for PAN fibers.8–12 In gel spin-
ning high molecular weight PAN is dissolved in a solvent making a viscous solution. This
solution is either wet or dry-spun to form polymer fibers containing partial solvent. As fibers
are stretched in hot water the solvent diffuses out and solvent free, elastic PAN fibers are
formed. The stabilization process is carried out under exothermic conditions and released
heat should be carefully dissipated out of the forming fibers. Various physical and chemical
changes such as shrinkage of the fiber in the axial direction, cyclization, aromatization, and
structure evolutions are observed.13–21 Differential scanning calorimetry (DSC) is used to
monitor the kinetics of the exothermic reactions during the stabilization process. A single
broad exothermic peak is often observed, even though various reactions occur such as cycli-
zation, oxidation, dehydrogenation, and cross linking during the stabilization process.22–25
As PAN stabilization is a slow process, it is common to pretreat the PAN fibers by expo-
sure to high energy radiations such as UV, electron beam, and g-rays to trigger partial cycli-
zation before stabilization in air. This can lead to a reduction in stabilization reaction
4 N. HIREMATH ET AL.

Figure 1. A typical SEM image of commercial oxidized PAN fiber.7 © Jordan Marcuzzo. Reproduced by per-
mission of Jordan Marcuzzo. Permission to reuse must be obtained from the rightsholder.

activation energy and the reaction time. In oxidative stabilization, oxygen diffusion controls
the reaction. A skin-core morphology is observed in oxidative stabilization, as the skin con-
tains higher oxygen content than the core, resulting in weaker surface influencing crack for-
mation and propagation.26–28 To prevent the skin-core morphology a stabilization reaction
inhibitor is coated on the PAN fibers to reduce the surface oxidation rate. Boric acid coated
PAN fibers are found to retard the rate of oxidative stabilization reaction on the surface, bal-
ancing the stabilization reaction throughout the fiber cross section. 29,30
Chemical and physical structural changes during stabilization are studied using various
characterization techniques such, as XRD (X-Ray Diffraction), (for crystallinity and orienta-
tion information), DSC (for stabilization reaction peak information), FTIR (for information
on carbon content in the stabilized fiber and defect ratio (ID/IG)), etc.1 The other ways of
improving the performance of CFs is by reinforcing PAN fiber with CNTs. The CNTs
improve the orientation of PAN fibers and hence the strength of the PAN based CFs.1 For
example, inclusion of 5 wt.% SWNT in dry-jet wet spun fibers increased tensile strength
from 0.24 to 0.34 GPa, tensile modulus from 7.8 to 13.6 GPa, PAN crystal size from 3.7 to
5 nm and Herman’s orientation factor from 0.52 to 0.62.31–33 Average orientation of polymer
chain to the fiber axis is calculated by Herman’s equation. Cosine square (cos2u) of the angle
between the chain and fiber axis is calculated and used in the Herman’s orientation equation
to estimate the orientation of the fiber.
After heat treating PAN- and mesophase pitch- (MPP) based CFs in the range of 1300
–2700
C mechanical properties such as Young’s modulus increase for both. However, the
tensile strength of PAN-based CFs decreases after reaching a maximum, while that of MPP-
based CFs continues to increase with heat treatment temperature. At 2700
C the tensile
strength of MPP-based CFs exceeds that of PAN-based CFs. Evolution of structure of CFs at
 POLYMER REVIEWS 5

various temperatures leads to rearrangement of layers of graphene resulting in differences in

the mechanical properties. Physical entanglements and covalent crosslinking of graphene
ribbons contribute to a higher shear stress. However, it also generates voids and cracks due
to extensive transformation from a turbostratic to ordered structure along with removal of
nitrogen. For MPP-based CFs radial texturing with ordered and parallel arrangement of gra-
phene layers in the cross-section helps to bond to adjacent layers leading to fewer voids and
cracks.34
PAN fibers form a rigid ladder structure by intramolecular cyclization when heated and
stretched in a steam bath in the presence of nitrogen. Due to this preferred orientation and
crystallite dimensions the resultant mechanical properties are enhanced as compared with
those of untreated CFs.
Mechanical properties of CFs are also enhanced by boron doping and heating the CF at
2500
C. Increase in boron content in the fiber increases the tensile strength and modulus by
16% and 26%, respectively, as compared to untreated CFs. Boron diffuses substitutionally
and interstitially, which helps remove structural defects and relaxes the distortions in the CF
structure to enhance its mechanical properties.34,35

2.2 Pitch based CFs

Pitch is produced either from natural sources such as petroleum or coal or by pyrolyzing
synthetic polymers. The molecular weight of pitch is in the range of 600»1000 g/mol, and it
contains aromatic groups. The major cost of pitch-based CFs is due to the purification steps
involved. The diameter of pitch-based CF ranges between 10»12 mm. MPP contains an ani-
sotropic phase which corresponds to the high degree of molecular alignment along the fiber
axis. The MPP-based fibers have higher tensile modulus as compared to PAN-based CFs,
however the compressive strength is lower. The tensile strength and modulus of pitch based
CF are »3 GPa and 960 GPa, respectively. The cross sections of pitch-based CFs are shown
in Fig. 2.36 A highly developed sheet-like morphology (A-1, A-2, and B) and extended sheets
along the fiber axis make them highly oriented strong fibers. Pitch-based CFs also require
optimization of pitch type, fiber spinning, thermal treatment, surface, and structural modifi-
cations.37–43 Pitch has isotropic and anisotropic regions. These regions correspond to the
smaller and larger micro-domains in the resultant CFs, respectively. By controlling the

Figure 2. SEM images of pitch based carbon fibers, sheet like morphology can be observed in the cross
section.36 Reproduced by permission of Taylor & Francis, LLC. Permission to reuse must be obtained from
the rightsholder.
6 N. HIREMATH ET AL.

structure of isotropic and anisotropic phases, the mechanical properties of the resultant CFs
can be manipulated. Pitch-based CFs can also be reinforced with CNTs.44 Adding 5%
SWNT into isotropic pitch-based CF increased the tensile strength and modulus from 0.47
to 0.83 GPa and 34 to 77 GPa, respectively. However, the tensile strength and modulus of
CNT reinforced mesophase pitch-based CFs were moderately reduced in comparison to that
of isotropic pitch-based CFs.45,46

2.3 Rayon based CFs

Rayon is a regenerated cellulose fiber. Derived primarily from woodpulp, rayon is made
soluble chemically and filaments of cellulose fibers are produced by wet spinning. Cel-
lulose fibers, first used by Thomas Edison in his famous electric bulb design experi-
ment, by pyrolyzing it to a carbon filament that conducted electricity, are also proven
precursors for CF synthesis.47 The reactions involving the conversion of cellulose to CF
are as shown in Fig. 3. First, oxidative reactions take place in stages 1 and 2. Carboni-
zation of cellulose is the process of formation of graphitic layers from 300 to 900
C as
shown in Stages 3 and 4. Once the graphitic layers are formed, following graphitization
at a high enough temperature (900 to 3000
C), CF with more than 99% carbon content
can be achieved. The Young’s modulus also increases as the process is carried out in
tension. The reported tensile strength and modulus of rayon-based CFs are about
580 MPa and 59 GPa, respectively.47

2.4 Other precursors

2.4.1 Graphene based CFs
There has been a recent surge in research on synthesis of graphene-based fibers. The impetus
behind choosing graphene as the raw material for CF synthesis is that large mesogenic graphitic
structures that are solution spun at room temperature could be ideal building blocks for making
high-performance CFs in an economical process.48 Graphene layers form liquid crystals in super-
acid, and this finding has led to solution-spun mesogenic graphitic structure fibers.49,50 The gra-
phene is oxidized to prevent agglomeration, and the graphene oxide nanoribbons (GONR) are
usually obtained by oxidative unzipping of multiwalled CNTs.51 These GONRs can be directly
spun by choosing the right solvent for dispersion and selecting an appropriate coagulation bath.
The GONRs are chemically reduced and spun into fibers followed by annealing. Annealing helps
eliminate residual stresses that are generated during the spinning process. The spinning method
practiced is wet spinning where the GONRs are dispersed in a solvent such as chlorosulfonic acid,
generally found in manufacturing sulfonamide antibacterial and pesticides, to form anisotropic
liquid crystal phases. The dispersed GONRs are then passed through a spinneret under pressure
using a piston. The fibers are collected in a coagulation bath as shown in Fig. 4. The air gap in the
fiber drawing process controls the drawability and tensile properties. The most commonly used
coagulation bath solvent is diethyl ether. As the GONRs are constructed with preformed graphene
layers, the stabilization process may not be necessary. Both the GONR and chemically reduced
GONRs are soluble in chlorosulfonic acid making it a preferred solvent for CF manufacture. The
typical tensile strength and Young’s modulus values for graphene based fibers (8 wt.% with 12 cm
air gap) after thermally annealing at 1050
C were »378 MPa and »36 GPa, respectively.52
 POLYMER REVIEWS 7

Figure 3. Conversion of cellulose into carbon fibers at various stages.

8 N. HIREMATH ET AL.

Figure 4. Schematic of dry-jet-wet spinning setup. The air gap helps the fiber orientation and forms circu-
lar cross section.

2.4.2 Lignin-based carbon fibers

Lignin-based CFs were first produced in 1965 by melt-spinning and dry spinning lignin and
then converting to carbon fibers.53 The CFs were about 20 to 30 mm in diameter and exhib-
ited tensile strength of about 0.785 GPa. Since lignin is a very inexpensive precursor, low
cost CFs could be produced on a large scale meeting the demand of the market for low cost
CFs. The preferred method of manufacturing of CF from lignin is by preparing lignin to be
melt spinnable into a fiber in an inert atmosphere. The resulting fiber is then thermally stabi-
lized in an oxidative atmosphere, followed by carbonization. The glass transition tempera-
ture Tg of the lignin fiber should be above the processing temperature allowing for
crosslinking of lignin fibers to increase strength. To make lignin melt spinnable the process
should be designed such that the softening temperature should be low so the liquid flows
under low shear. So in a narrow range of temperatures CF precursors may be made from lig-
nin. The greatest advantages of lignin over pitch or PAN are that it is very inexpensive,
renewable, and can be thermally stabilized at much higher rates than PAN. Typical
manufacturing of lignin based CFs is as shown in Fig. 5. In a new technique for developing
low cost CFs, lignin is copolymerized with acrylonitrile in dimethyl-sulfoxide (DMSO) by
radical copolymerization.54 Following wet spinning, the resulting fibers are further thermally
stabilized at 105
C for an hour in air and at 280
C for an hour in nitrogen. Carbonization is
carried out under tension (7.86 Pa) at 800
C in a nitrogen atmosphere. The highest tensile
strength and modulus reported are 1.7 GPa and 176 GPa, respectively.55
Many scientists are trying to find new precursor materials for making low cost CFs.
According to Baker’s55 review, 51% of the cost of production of CFs is due to the precursor
 POLYMER REVIEWS 9

Figure 5. Schematic of lignin based carbon fiber production. Lignin is melted and extruded through spin-
nerets. Lignin fibers are carbonized and graphitized to form carbon fibers.

material. Hence, finding an inexpensive precursor which can yield high strength CFs could
lead to a billion dollar business.
Synthesis and carbonization of triethylammonium-based poly (p-phenylenevinylene)
(PPV) has led to a new precursor material. Unsubstituted PPV is hard to process so the syn-
thesis of a DMSO soluble ammonium-based PPV precursor solves that problem. 56 Also,
most of the polymers with carbon backbones contain a high concentration of carbon which
could be used as precursor materials for conversion to CFs. Aromatic polyimides have been
studied as precursors for carbon nanofiber preparation, and various other carbon materials
such as membranes, foams, nanofibers, etc.57 The advantages of using polyimides as precur-
sors are availability of a wide range of chemical structures, a high yield after carbonization,
and a simple procedure for carbonization and graphitization steps.
Polyacetylene fibers have also been investigated as precursors. Modified polyacetylene fibers
are melt spun, thermally stabilized, and carbonized at 1000
C, resulting in tensile strength and
modulus of 2.3 GPa and 386 GPa, respectively.58 Another example is polyethylene (PE), an
inexpensive synthetic polymer. PE fibers are oxidized and sulfonated using sulfuric acid, fol-
lowed by carbonization at 1200
C. The resulting CFs result in carbon yield of 75% and a tensile
strength of 2.5 GPa and a modulus of 139 GPa.59 Recently, partially biobased PAN-lignin blends
have been studied as potential CF precursors.60 Lignin alone has a tensile strength of 3–5 GPa;
therefore, when lignin is mixed with PAN it improves the overall strength of the blend.60

3. Carbon nanotubes (CNT)

3.1 Introduction to CNT
In this section, a brief overview on the discovery, structure, theory, and synthesis of CNTs is
presented. Though it is important to understand the precise structure of CNT, it is not easy
to conceive, as there are many theories related to its explanations.2 Readers are requested to
refer to the references for a deeper understanding on the physics of CNTs.
10 N. HIREMATH ET AL.

Smalley and Kroto, in 1985, started their work to identify the products of vaporization of
graphite, as their motive was to understand the processes that occur on stars. They used high
energy lasers to vaporize graphite in a helium atmosphere and found that the soot contained
C60, a carbon nano sphere or the famous “buckminsterfullerene.” In similar experiments,
Kr€atschmer and Huffman in 1990, were able to find 90% C60 and 10% C70. In 1991, Iijima, in
the NEC laboratories in Japan, discovered CNTs which are cylindrical in nature with closed
ends. CNTs “archetypal” zig-zag and armchair structures could be understood by bisecting
along the three-fold axes and five-fold axis, respectively. Chirality comes into picture depend-
ing on the angle of rotation along the axis of the nanotube. To understand the chirality of the
structure of the nanotube, we have to open up the nanotube to form a layer of carbon atoms, a
graphene sheet. CNTs are of interest to many researchers from various fields such as physics
(electronic, magnetic, and thermal properties, etc.), chemists (bonding, nano-test-tubes, etc.),
and materials scientists (mechanical properties such as strength, modulus, elasticity, etc.).2

3.2 Structure of CNTs

To understand the structure of nanotubes, it is hard to implement the rules of crystallogra-
phy even though the structure of CNT is crystalline in nature. Certain biological structures
come close to that of CNT; however, the factors governing these cylindrical biological struc-
tures are insufficient for CNT structure analysis. Many scientists have introduced different
methods to explain the nature of formation of the nanotubes. Theoretical structure analysis
has helped understand the electronic and vibrational properties of CNTs. Experimental stud-
ies, using high resolution electron microscopy, have helped further understand and affirm
the structure of CNTs.2,3

Figure 6. A graphene sheet explaining the formation of different types of carbon nanotubes. a1 and a2 are
the vectors. Red dots are carbon atoms which inherit metallic behavior (for all n D m and n-m D multiples
of 3) and the black dots inherit semiconductor behavior.2
 POLYMER REVIEWS 11

The two possible symmetric structures of nanotubes are armchair and zig-zag. In reality,
the hexagons on the CNTs arrange helically along the CNT axis. The degree of helical
arrangement or chirality is given by u. To understand the structure in terms of vector, C,
which joins two equivalent points on the graphene layer, vectors a1 and a2 as shown in
Fig. 6. A cylinder is formed when the graphene sheet is rolled such that the two end points
of the vector are superimposed. From Fig. 6, integer (n, m) represents a tubular structure.
Therefore, vector C could be expressed as

C D na1 C ma2

where a1 and a2 are of length 0.246 nm as the C–C bond length is 0.142 nm. Furthermore, it
is explicit that for n D m, armchair tubes (with u D 30
) could be formed and for m D 0,
zig-zag tubes (with u D 0
) could be formed. For these tubes the diameter d could be calcu-
lated by the expression,2,3
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
0:246 ðn2 C nm C m2 Þ
dD
p

and the angle of chirality could be expressed by u

pffiffiffiffiffiffiffi
3m
u D sin ¡ 1 pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
2 n C nm C m2
2

A unit CNT has the form translation of cylinder. In Figs. 7 and 8, unit cells of armchair
and zig-zag are shown. In the armchair type structure the width of the unit cell is same as
vector a, while for zig-zag it is x3a. The length of the unit cell depends on the diameter of
the CNT. Furthermore, for chiral structures lower symmetry results. The number of carbon
atoms in the unit cell can be calculated by the expression
 
N D 2 n2 C nm C m2 dH if n ¡ m 6¼ 3xd H
and
 
N D 2 n2 C nm C m2 3dH if n ¡ m D 3xd H

where dH is highest common factor of n and m and x is some integer.

Figure 7. A typical unit cell of armchair type of carbon nanotubes.2

12 N. HIREMATH ET AL.

Figure 8. A typical unit cell of zig-zag type of carbon nanotubes.2

3.3 Theory
Since CNTs have diameters smaller than 10 nm, these structures exhibit quantum mechani-
cal behavior. Many scientists have investigated the physics of CNTs structures and have
claimed that CNTs possess metal- and semiconductor-like natures. Certain structures with a
precise diameter (all armchair structures and n – m D multiples of 3) exhibit metal-like char-
acter and others behave as semiconductors. As the CNTs are highly anisotropic, electron
mobility along the basal planes is high while mobility perpendicular to the planes is low.2,3
Wallace, in 1947, calculated band structures for conduction only in planes, while ignoring
conduction between the planes. The expression is as follows:
vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
ffi
u( pffiffiffiffiffiffi !    )
  u ð 3 Þ k a k a
E2D kx ; ky D § g 0 t 1 C 4cos
y y
kx a cos C 4cos2
2 2 2

where g0, nearest-neighbor transfer integral and a D 0.246 nm, in-plane lattice constant. E is
the energy in two-dimensional k-space with kx and ky vectors.
The above expression is for 2D graphite structure with 2 atoms in the unit cell. This yields
four valence bands (three s bands and one p band). Figure 9 shows the E vs k data for the
2D graphite structure along K¡G¡M.61 Figure 10 shows the density of states for armchair
and zig-zag CNT structures.62

3.4 Synthesis
To achieve the amazing properties of ideal CNTs, it is critical that the CNTs should be fabri-
cated to 100% purity. In reality, however, this is extremely difficult. Various other carbon
materials such as amorphous carbon, other carbon nanoparticles, etc., act as impurities.
Some of the synthesis techniques used to fabricate high purity CNTs are briefly discussed
herein and Table 1 provides a summary of the synthesis techniques.

3.4.1 Arc discharge

A low voltage (12 to 25V), high current (50 to 120 amps) power supply on graphite electro-
des (5 to 20 mm in dia) placed 1 mm apart in the presence of He or Ar gas (100 to 1000
torr) produces CNTs with typical yields ranging from 30 to 90%, as shown in Fig. 11. In the
arc discharge method variations are made in the procedure to tune the properties of the
 POLYMER REVIEWS 13

Figure 9. Energy vs k-vector along K-G-M direction of 2D graphite structure.61 © Tsuneya Ando. Repro-
duced by permission of Tsuneya Ando. Permission to reuse must be obtained from the rightsholder.

CNTs. By mixing different gases, Ar and He, the properties can be varied; for example, a
higher Ar:He ratio produces a smaller diameter CNTs.3 This process is inexpensive and
yields high purity CNTs with varying lengths. It is a batch process, which means there will
be variation in the quality of the nanotubes between each batch.

3.4.2 Laser ablation technique

A cobalt/nickel with graphite composite target is evaporated by pulsed or continuous laser
by placing the electrode in a quartz tube, at 1200
C, in an inert atmosphere of He or Ar, The
laser used is usually a double beam of 532 nm and shot on the graphite target. The Ar or H2
gas is flown towards the colder end of the furnace where the vaporized carbon condenses on
the metal finger. The purity of the CNTs is about 90%. A schematic of a laser ablation tech-
nique is shown in Fig. 12.3 This is a batch process and yields a high purity CNTs with a
good diameter control. However, the process is very expensive.

3.4.3 Chemical vapor deposition (CVD)

Gaseous carbon feedstock, such as methane, is passed over metal nanoparticles at tempera-
tures ranging from 550 to 1200
C, where the feedstock reacts with the nanoparticles to pro-
duce SWCNTs. This method provides higher purity of CNTs (99%) in bulk quantities.
Other types of CVD include hot filament, water assisted, oxygen assisted, microwave plasma,
radio frequency, thermal, plasma enhanced, etc.3
Some of the recent advancements in CNTs synthesis involve finding new precursors, for
example coal, and new processing methods, such as the solar furnace. Coal is much less
expensive than graphite and high purity hydrocarbon gas sources. Even though CNTs can
be produced from both arc-discharge and thermal plasma jet with coal as precursor, large
scale production is not currently possible.63 However, CVD can be used to synthesize CNTs
in large quantities by optimizing the experimental conditions.
14 N. HIREMATH ET AL.

Figure 10. Density of states for a) armchair and b) zig-zag CNTs.62 © Mauricio Terrones. Reproduced by
permission of Mauricio Terrones. Permission to reuse must be obtained from the rightsholder.

3.4.4 Solar furnace

In the solar furnace method (Fig. 13) the graphite source with metal catalyst is placed in a
graphite crucible. A highly directed solar beam hits the source creating a temperature of
about 3000
K, triggering evaporation of carbon and resulting in soot settling on the walls of
the graphite tube in the form of soot. This soot on the walls of the graphite pipe contains
CNTs and other forms of carbon nanostructures such as fullerenes.
 POLYMER REVIEWS 15

Table 1. Advantages and disadvantages of the various CNT synthesis techniques.66

Methods Typical Yield Advantages Disadvantages

Arc Discharge 30 – 90% Simple process, inexpensive, high yield Shorter tubes with random length,
and high purity, dia D 1 to 20 nm batch process
Laser Ablation » 90% High purity, good diameter control Cost of the equipment is high, batch
process
Chemical » 95% High purity, long tubes, easy High defects present
vapor deposition processing, continuous process, dia
D 0.8 to 2 nm
Solar furnace » 60% dia D 1.2 to 1.6 nm Very slow process and random length
tubes.

The diameter of the CNTs produced by this method lies in the range of 1.2 to 1.5 nm,
with high purity comparable to those of CNTs produced by the laser ablation technique.64,65
However, the lengths of the tubes are random and it is a very slow process with a yield of
upto 60%.
In all these techniques, the important point is that when a carbonaceous material is
vaporized the C atoms are in their excited state. Graphite (sp2) forms in the nature at atmo-
spheric conditions. While diamond (sp3) forms at very high temperature and pressure.
CNTs and other carbon nanostructures are in their hybrid state with sp2 and sp3 combina-
tion. When the material is vaporized, graphene layers form and due to their dangling bonds
when they come close to the colder region of the furnace graphene layers roll up to form
CNTs. Multiple graphene sheets roll to form MWNTs while a single layer of graphene forms
SWNTs. Due to this there is reduction in energy and hence these structures are stable in the
atmospheric pressure and temperature.

4. Carbon nanotube-based fibers

4.1 CNT-based composite fibers
The high performance fiber industry has changed the face of the textile market, because of
the properties of the high performance fibers such as nylon, polyester, etc. To make compos-
ite fibers many researchers have studied new processes and materials that deliver higher

Figure 11. Schematic of arc-discharge tube with a small gap between electrodes.
16 N. HIREMATH ET AL.

Figure 12. Schematic of laser ablation technique.

strength and modulus. A polymer matrix with CNTs has proven to increase the strength and
modulus considerably, however the results have fallen far short of the theoretically expected
values. These lower values can be attributed to the lack of orientation and bonding of the
nanotubes in the polymer matrix, as these directly affects the final mechanical properties of
the composite filaments. Table 2 summarizes the strength and modulus of various composi-
tions of composite fibers derived using CNTs as fillers.67 From the table we can see that for
carbonized PAN with 1 wt.% SWNT, the tensile strength and modulus increased by 60%
and 49%, respectively. For Nylon 6, from addition of 1.5 wt.% of SWNT, the tensile strength
and modulus have increased by »66% and 172%, respectively. Similarly for PAN with
1 wt.% SWNT, the tensile strength and modulus have increased by »18% and »30%, respec-
tively. About a 4-fold increase in strength and about a 6-fold increase in modulus are
reported by Meng, Zhang et al. in the case of PVA C 10 wt%. SWNT. About 18% increase in
strength and 11% increase in modulus, in the case of UHMWPE C 5 wt%. MWNT, has
been reported by Ruan et al.68 Figures 14a and 14b are a pictorial representation of the dif-
ference between the tensile strength and elastic modulus of various composite fibers reported
in Table 2.

Figure 13. Schematic of CNTs produced by solar furnace technique.

 POLYMER REVIEWS 17

Table 2. CNT/polymer composites and their tensile strength, elastic modulus, and toughness.
Composite fiber Tensile Elastic
(CNT wt.% C polymer) Strength (GPa) modulus (GPa) Toughness References

Carbonized PAN 2.0 § 0.4 302 § 32 N/A 79, 80

Carbonized PAN C 1 wt% SWNT 3.2 § 0.4 450 § 49 N/A
Nylon 6 0.045 0.44 N/A 69
Nylon 6 C 0.1 wt% SWNT 0.086 0.54 N/A
Nylon 6 C 0.2 wt% SWNT 0.093 0.66 N/A
Nylon 6 C 0.5 wt% SWNT 0.083 0.84 N/A
Nylon 6 C 1.0 wt% SWNT 0.083 1.15 N/A
Nylon 6 C 1.5 wt% SWNT 0.075 1.2 N/A
Polyacrylonitrile (PAN) 0.9 § 0.18 22.1 § 1.2 35 § 9 MPa 8
PAN C 0.5 wt% SWNT 1.06 § 0.14 25.5 § 0.8 41 § 8 MPa
PAN C 1 wt% SWNT 1.07 § 0.14 28.7 § 2.7 39 § 8 MPa
Poly(p-phenylenebenzobisoxazole) 2.6 § 0.3 138 § 20 N/A 70
(PBO)
PBO C > 10wt% SWNT 4.2 § 0.5 167 § 15 N/A
Polypropylene (PP) 0.71 6.3 7.93 dN/tex 71
PP C 0.5 wt% SWNT 0.84 9.3 9.37 dN/tex
PP C 1 wt% SWNT 1.03 9.8 11.5 dN/tex
Poly(vinyl alcohol) 0.15 9 to 15 N/A 78, 81
(PVA) C >60 wt% SWNT
PVA C 60 wt% SWNT 1.8 80 570 J.g-1
PVA (commercial fiber) 1.6 40 N/A 74
PVA C >60 wt% SWNT 1.8 78 120 § 152 J.g-1
PVA C 60 wt% SWNT 0.3 40 600 J.g-1 72
PVA 1.2 § 0.3 21.8 § 3.0 55.8 § 12.3 J.g-1 73
PVA C 10 wt% SWNT 2.5 §0.1 36.3 § 1.3 101.4 § 11.4 Jg-1
PVA C 10 wt% SWNT 4.4 § 0.5 119.1 § 8.6 171.6 § 30.4
PVA »0.4 »13 N/A 75
PVA C 1 wt% SWNT »1.2 »17.5 N/A
PVA 1 § 0.1 45 § 7 22 § 4 J.g-1 76
PVA 1.6 § 0.1 48 § 3 40 § 6 J.g-1
PVA C 1 wt% SWNT 1.4 § 0.1 60 § 6 29 § 6 J.g-1
PVA C 1 wt% SWNT 2.6 § 0.2 71 § 6 59 § 7 J.g-1
PVA C 2–31 wt% SWNT »2.9 »244 N/A 77
UHMWPE 3.51 § 0.13 122.6 § 1.9 76.7 § 7.5 MPa 68
UHMWPE C 5 wt% MWNT 4.17 § 0.04 136.8 § 3.8 110.6 § 10.5 MPa

4.1.1 Nylon-CNT composite fiber

The CNT-caprolactam sonicated suspension was heated and mechanically stirred to 250
C
with 6-aminocaproic acid addition. Following the mixture formation, the product was
poured in water and the hard polymer was precipitated. The polymer was broken into small
pieces, was heated to 250
C, and extruded using a spinneret by pressurized nitrogen gas.
The fibers were then characterized with various mechanical tests. The incorporation of
1.5 wt% SWNTs into nylon 6 increased the tensile modulus and tensile strength about three
and two times respectively.69 These improvements in strength and modulus data are shown
in Figs. 14a and 14b.

4.1.2 PBO-CNTs
High pressure carbon monoxide nanotubes (SWNTs) were added to the PBO polymeriza-
tion solution in the ratio of 90 : 10 :: PBO : SWNT and 95:05. The fibers were spun using
dry-jet wet spinning process using a piston driven setup. The fibers were collected in the dis-
tilled water coagulation bath maintained at room temperature. The air gap was maintained
18 N. HIREMATH ET AL.

Figure 14. Tensile strength and elastic modulus data for Nylon 6-CNT based composite fibers.69 (A) Tensile
strength and (B) elastic modulus data for Nylon 6-CNT based composite fibers.

at 10 cm from the spinneret to coagulation bath. The fibers with 10% SWNT in PBO
increased the tensile strength to 50% of the PBO fibers and increased the creep resistance.70

4.1.3 PP-CNTs
The SWNTs were dispersed in decalin by sonication and the PP pellets were added to the
solvent mixture. The PP-SWNTs mixture, in the form of coarse powder was extruded with a
spinneret of 1.22 mm diameter and the fiber was further drawn. Though the PP-SWNT
composite fibers were of not enough strength compared to other composite fibers, with
1 wt% loading of nanotubes, the fiber tensile strength increased by 40% and the modulus
increased by 55%.
By incorporating CNTs dispersed in sodium dodecyl sulfate, a surfactant, by sonication,
the solution was injected in a co-flowing system of a polymer solution. The resulting CNT
ribbon was taken out and dried and characterized for mechanical properties. The strength of
the ribbon was 10 times higher than that of high quality bucky paper. Also, knotting the
fibers revealed that the fiber can be curved through 360
in few micrometers, which demon-
strates the flexibility and high torsion resistance of those fibers.71

4.1.4 PVA-CNTs
In Razal’s, Dalton’s, and Meng’s research, the PVA-CNTs composite fibers were extruded
using different spinning mechanisms. Razal’s group used coagulation-spinning method,
 POLYMER REVIEWS 19

which involved dispersion of SWNT injected into a PVA solution flowing in a glass tube. In
Dalton’s group, the aqueous dispersion of nanotubes was spun in a rotating coagulation
bath of aqueous PVA solution. In Meng’s group, shear-flow gel spinning method was used,
in which the methanol was stirred to provide shearing as the PVA-SWNT solution was
injected to form fibers. The spun fibers were subsequently drawn on hot plates at 90
C and
160
C. Hence there were variations in the tensile strengths of the PVA-CNTs composite
fibers.72–74
In Wang’s research group, the SWNTs were dispersed in DMSO, and PVA solution was
mixed to form the PVA-SWNT composite mixture. The mixture was spun by solid-state
spinning with a draw ratio of five. The tape drawn from the composite (PVA-SWNT) was
200% stronger than the PVA tape of same length. Hence, addition of one wt% SWNTs
increased the strength drastically.75 However, in Minus’s group, the PVA-SWNT composite
fiber was extruded by gel spinning method. The tensile properties of the composite fibers
were higher than that of the composite fibers from Wang’s group.76 This could be due to the
spinning method, the solution preparation techniques involved, and the fiber diameter,
purity of CNTs and interfacial binding between the polymer and the CNTs, etc. In Young’s
group, the PVA-CNT composite fiber was extruded using coagulation spinning. The diame-
ter of the fiber was in the range of 1»15 mm, the mean modulus was about 244 GPa and
strength about 2.9 GPa. This high strength was attributed to the distribution of the CNTs in
the polymer matrix and good bonding between the CNTs and the matrix.77 The higher the
concentration of the CNTs in the matrix, the higher is the load bearing interaction. The
increasing trend in strength and modulus observed with addition of CNT in PVA fibers are
showed in Figs. 15a and 15b, respectively. Some of the authors72,74,78 claim to have carbon
nanotubes as high as 60 wt% in the PVA based composite fibers; however, the percentage
calculated from the procedure in the respective paper does not exceed 8 wt% of CNTs. From

Figure 15. Tensile strength and elastic modulus data for PVA-CNT based composite fibers from various
researchers respectively.76,77 (A) Tensile strength and (B) elastic modulus data for PVA-CNT based compos-
ite fibers from various researchers respectively.
20 N. HIREMATH ET AL.

several studies it is well known that incorporating higher concentrations of CNT especially
above 5 wt% is extremely difficult.

4.1.5 UHMWPE-CNTs
In Ruan’s group, multiwalled CNTs were used as reinforcement in the polymer matrix.
5 wt% MWCNTs were reinforced in gel-spun ultra-high molecular weight polyethylene
(UHMWPE) resulting in a yield strength of 4.2 GPa and strain at break of 5%. By reinforce-
ment of CNTs in UHMWPE there was an increase of 18.8% in tensile strength and 15.4% in
ductility. In addition, a 44.2% increase in energy to fracture was observed.68

4.2 CNT based yarns and CFs

Carbon nanotube yarns (CYs) are produced by various approaches, such as aqueous disper-
sion, dispersion in strong acids, drawing from CNT forests, drawing from a CVD reactor in
the form of aerogel, etc. They are relatively ductile when compared to PAN- or pitch-based
CFs because the knot efficiency of CY is » 1 while PAN- or pitch-based CFs cannot be knot-
ted1. The tensile strength and modulus of CYs are higher for CNT fibers spun from CNTs
forests and from CVD reactors. However, stretching the CYs aligns the CNTs and improves
the mechanical properties by increasing the interaction between CNTs. Longer CNTs do
help to improve the performance; however, chemical modification, gamma-ray induced
crosslinking, and heat treatment, etc., on the CNTs surface, further enhance inter-nanotube
interaction, resulting in increase in strength. However, the compressive strength achieved is
low in case of CYs.1
When synthesizing CNTs by various processes discussed in section 3.4, if there is a possi-
bility to isolate the pure CNTs, the quality of the CYs produced using such nanotubes would
yield higher strength and modulus. However, during the preparation of CNTs there are vari-
ous other structures generated, such as fullerenes, amorphous carbon agglomerates, and
these structures are the weak points or defects in CYs.2 Furthermore, the CNTs that are pro-
duced with highest purity must also be dispersed well in the medium of interest. Generally
the CNTs are dispersed in suitable polymers and drawn to high draw ratios. Increasing the
draw ratio helps align the CNTs in the polymer matrix and hence increases the strength of
the CFs. CNTs can also be grafted into the CFs, such as PAN- or pitch-based, to increase the
alignment of the polymer matrix or to act as the load bearing structures in the CF matrix.82
Carbon nanofibers produced by the pyrolysis of cellulose contain no skin-core morphol-
ogy, resulting in high tensile modulus of 60 and 100 GPa, when carbonized at 1500 and
2200
C, respectively.83 By producing high purity and continuous nanotubes the inter-nano-
tube interaction can be increased resulting in high strength carbon fibers. In an attempt to
make the CNTs long, in 2009, a research group from Peking University, China, led by Qunq-
ing Li, grew ultra-long, single wall carbon nanotubes using an improved CVD technique.
Using ethanol or methane as the feed and Fe-Mo monodispersed catalyst, super aligned
ultra-long CNT was grown for a length of 18.5 cm.84 Homogeneous temperature during the
growth process is the key for constant electrical characteristics. However, improving the
mechanical properties of the CNTs along the length is also equally important for high
strength materials applications. In 2013, Zhang reported that 550 mm long CNTs were fabri-
cated using a floating CVD process and catalyst activation/deactivation probability.
 POLYMER REVIEWS 21

Following optimized processing parameters half-meter long CNTs fabricated exhibited a

tensile stress of up to 120 GPa.85

5. Applications of CFs and CNTs

In this section a brief overview on various applications of CFs and CNTs with a matrix or by
itself or other capabilities is presented. In the beginning of the section, CF-related applica-
tions in the airline industry, sporting industry, automotive industry, and other industrial
applications are discussed, followed by CNT-based applications.

5.1 Airline industry

CF-based composites are used in fairings, flight control surfaces, landing gear doors, floor
beams and floor boards, primary wing and fuselage structures on new generation aircrafts
(Boeing 787 and Airbus A 350 XWB), etc. About 50% or greater of the materials used in
new airplanes are composites compared to other materials, as shown in Fig. 16. For example,
a Boeing 787 Dreamliner contains nearly 50% of CF-based composite material and Airbus
A350 XWB contains nearly 53% of CF-based composite materials, and this increase in com-
posites usage raises the fuel efficiency by 25% as claimed by Airbus.

5.2 Sporting goods industry

The sporting goods industry accounts for 18–20% of the carbon fiber market as shown in
Figs. 17a and 17b. In terms of weight, nearly 46,000 tons of CFs are used globally in various
sporting equipment. CF composites are used in golf shafts, hockey sticks, rackets, fishing
rods, ski poles, snowboards, sailboards masts, marine hulls, backpack frames, tent poles,
bicycle frames, etc. The CFs tows are treated for surface reactivity with sodium hypochlorite,
nitric acid, etc. A sizing agent is applied to protect the fibers. These fibers are further impreg-
nated with resin or an epoxy and are partially cured at 121–176
C to form the desired shape

Figure 16. A statistical data of composition of B787- Dreamliner.86

22 N. HIREMATH ET AL.

Figure 17. (A) carbon fiber market share by companies and (B) Market share of Toray in various
industries.87,88

and are cured completely at 482
C. The CFs used in the various sports equipment not only
provide light weight but also improve the sporting performance.87

5.3 Automotive industry

The most recent example of CFs used in automotive industry is the BMW i3 electric vehicle.
The PAN-based carbon fibers are made into molds of various shapes and are fitted into the
car. Due to use of CFs in the BMW i3, nearly 550 lb. in weight reduction was achieved as
compared to the regular aluminum structures. BMW claims that due to this reduction in
weight the car will have an additional range of 80 to 100 miles per full charge. Furthermore,
due to use of CFs the production time of the car is drastically reduced from 40 hours for a
regular BMW 3 series cars to 20 hours for i3 E.V. Other commercially available CFs based
cars include Aston Martin, Ferrari, Lamborghini race cars, etc.

5.4 Composite materials

Electrical conductivity of CNTs was the initially exploited property. MWNTs impregnated
with polymers help in the automotive industry to dissipate electrostatic charge buildup in
mirror housing, fuel lines, and filters.89,90 Also, CNTs mixed with polymers are used for elec-
tromagnetic interference shielding in the microelectronics industry. CNT powder mixed
with various load-bearing polymers help to enhance the mechanical properties dramatically,
as the CNTs tensile strength and modulus are extremely high. However, the end use depends
on the length and diameter of the CNTs. Engineered CNTs mixed with polymer increase the
CNTs interactions and improves the energy damping especially in the sports industry, such
as in tennis racquets, baseball bats, bicycle frames, golf clubs, hockey sticks, fishing rods
etc.91,92 CNTs mixed in resins also enhance the performance of composites, such as the
wind turbine blades and hulls of speed boats. CYs have high tensile strength and are used
where both good electrical and mechanical properties of a material are required.93,94 Other
than carbon composites with polymers, CNTs added to metals are known to increase the
tensile strength and modulus.31,95 Such high performance CNT-metal composite materials
are normally used in the aircraft and automotive industry where weight and strength are
prime competing factors.96
 POLYMER REVIEWS 23

CFs are also used in boats, which make them much lighter, highly durable, and perfor-
mance oriented. CFs are impregnated with an epoxy resin and molded to the shape of the
hull and the desired shape of the boat is constructed. Many companies such as, mshipco.
com, M80 Stiletto, (US Navy based boats and ships), goetzboats.com, (speed boats), etc.,
make high performance CF based boats. For example, M80 Stiletto has a total of 6600 HP
power with dimensions of 88 ft. in length by 41 ft. in breadth and reaching a little higher
than 50 knots, about 93 kmph.
Other major commercial uses of CFs are in wind mill blades. The CF rib runs all through
the length of the blade and at the root of the blade. Over the rib, the fiber glass form the
blades. It is extremely important for the blade to be light weight so that maximum electricity
is produced. Furthermore, there are a number of applications of CNTs in the matrix and as
CFs, which are described in the following section.

5.5 Coatings and films

CNTs are nowadays used in conductive polymer technology. Coating steel with conducting
polymers prevents rusting by allowing electric pathway for cathodic protection. As CNTs
inherit high electrical conductivity, CNT based conductive polymer coatings prevent corro-
sion in metals.97 Another demanding application is that CNT coated films can replace
indium tin oxide coated (ITO) films for transparent conducting films, such as LCD screens.
ITO is very expensive because of the scarcity of indium, a rare earth metal.98 Furthermore,
CNTs transparent conductors are not brittle as ITO, which increases the advantages of
exploitation of CNT-based transparent conductive films.96 Other applications of thin film
CNTs are that they are used as thin-film heaters for defrosting windows.

5.6 Microelectronics
SWNTs were first used in field-effect transistor (FET) architectures. In 1998 the first CNT
FET was designed using SWNTs.99 A sub-threshold swing of < 60mV decade¡1 was
achieved in 2004, followed by CNT-based radio in 2007. By 2012, SWNT FETs with 10 nm
channel lengths, a current density of nearly 2.4 mA mm¡1 at 0.5V were observed, greater
than that of the silicon devices of same size.100–102 Another example of CNT-based applica-
tion in microelectronics is the thin film transistors (TFTs), organic light-emitting diode
(OLED) displays.103–105 The OLEDs show higher mobility than amorphous silicon and can
be fabricated at low temperatures with no-vacuum techniques required.106,107 The greatest
advantage of OLEDs is that the TFTs are flexible and hence the future screens could be
made to bend with the functionality restored without disturbing the structure. Low cost
radio frequency identification tags are made out of CNTs. Nonvolatile memory based CNT
crossbars electromechanical switches have been designed and commercialized. These ultra-
pure CNTs are made in industrial clean rooms and hence are compatible with CMOS proc-
essing standards.96

5.7 Energy storage applications

Lithium ion batteries in laptops and mobile phones contain the use of MWNTs.106,108 CNTs
in the batteries provide enhanced electrical connectivity and strength which increases the
24 N. HIREMATH ET AL.

battery cycle life. CNTs are also used in fuel cells as catalyst support reducing the use of plat-
inum by 60%.109 In solar cells the use of CNTs not only reduces the undesired carrier recom-
bination but also resists photo-oxidation.110,111 A new application of CNTs is in the
purification of water. Highly tangled CNT sheets provide mechanical and electrochemical
robustness to the network with nanoscale porosity. Portable CNT based filter meshes are
already commercialized to purify potable water. Also, due to the use of hollow CNTs, lowest
flow resistance is observed for both gases and liquids.96,112

5.8 Biotechnology
Continued research in CNTs as components of biosensors and medical devices is due to the
chemical and biological compatibility of CNTs with DNA and proteins.113,114 SWNTs based
biosensors show large changes in electrical resistance and optical properties in response to
the surface binding of target molecule on CNTs.115–117 The qualities of a biosensor are that
they should possess fast or near-immediate detection, low detection limit with high selectiv-
ity/specificity, and ease of use. CNTs to be used for biosensor applications require surface
functionalization. There are commercially available biosensors for estrogen and progester-
one detection with ink-jet printing technique. Such CNTs are made to disperse in a right
kind of solvent to be uniformly distributed.103,118 There are many publications on CNTs
based polymeric implants on rats, and it has been found that CNTs are biocompatible, per-
forming the required function of electrical signal mobility, improved strength of the prosthe-
sis, and flexibility.96
Readers are requested to refer to the references cited for more information on other types
of applications of CFs, CNTs based application.1,39,55,119

6. Current trends and future prospects

Carbon fibers are the major building blocks of futuristic high strength and high performance
composites. The high performance composites are important as they contain high strength
to weight ratio, increasing the energy efficiency and payload size/range in the field of applica-
tion. However, these composites, as they are in their early stage of usage, are extremely
expensive. Making these carbon fiber based composites inexpensive is the focus of many
researchers, companies, and end users in this field.
CF research is taking a new turn. There is presently intense focus on finding new precur-
sor materials, new processing techniques, making low cost CFs with recycled materials, etc.
Studying new precursor materials is very important since in the CF industry nearly 50% of
the cost of CFs is expended solely on the precursor, for PAN-based carbon fibers. Investiga-
tion of new precursors for CFs, such as lignin, cellulose, rayon, recycled PET, and other high
carbon content polymers, is presently being done by many research teams. The addition of
CNTs to enhance properties may help reduce the total cost of CFs as the precursor cost
decreases. Similarly, finding new processing techniques, such as CNT grafting onto PAN-
based fibers may reduce the precursor usage, thereby reducing the processing cost. Further-
more, not just the reduction in processing cost of the fibers is necessary but also structural
optimization is required for high end use.
If we look at the world market, it is growing with a positive economic impact on emerging
countries. However, the domestic market is not growing, or is growing very slowly.
 POLYMER REVIEWS 25

Figure 18. (A) Global production of carbon fibers by country by 2020 and (B) World usage of carbon fibers
in various fields.120

Countries such as China export most of the CFs, CF composites, etc., to various countries,
and the world requirement for CFs is also increasing due to their increased capture of the
market in various applications. For example Fig. 18a shows the expected share of CFs world
market by 2020 for different countries and Fig. 18b shows the world usage of CFs in prime
sectors. The automotive industry alone holds about 6% of total CF demand (carbon fiber
2013 conference highlights, compositesworld.com). Some of the findings about the CF usage
in carbon fiber reinforced plastics by 2015, according to Anthony Roberts, would be about
$28.2 billion and by 2020, $48.7 billion and CF alone will increase from $1.8 billion in 2013
to $3 billion by 2018. The CF demand globally would increase to 140 K tons in 2020. Fur-
thermore, the plant capacity, of producing CFs, would increase from 114 K tons in 2012 to
129 K tons by 2015 to about 185 K tons by 2020, according to Roberts’s survey.120
In the future, many new findings from various researches, such as coming up with
new precursors, new processing techniques, low cost CFs from recycled products such
as PET bottles, (Oak Ridge National Lab), etc., should be able to assist the world mar-
ket to reach the predicted values from market leaders. Increasing the use of CFs in var-
ious applications can help reduce the cost dramatically. As discussed earlier, the study
of newer precursor materials and optimizing new processing techniques could reduce
the cost of CFs and hence increase their applications. For demanding applications there
is need for stronger and stiffer carbon fibers and the hope is to have fibers with
strength and modulus values way higher than those of current commercial fibers by
innovative techniques.

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