Carbon nanotube

Not to be confused with Carbon fiber. bridization best describes chemical bonding in nanotubes.
Carbon nanotubes (CNTs) are allotropes of car- The chemical bonding of nanotubes is composed en-
tirely of sp2 bonds, similar to those of graphite. These
bonds, which are stronger than the sp3 bonds found
in alkanes and diamond, provide nanotubes with their
unique strength.

1 Types of carbon nanotubes and

related structures

1.1 Terminology
There is no consensus on some terms describing car-
bon nanotubes in scientific literature: both "-wall” and
"-walled” are being used in combination with “single”,
“double”, “triple” or “multi”, and the letter C is often
omitted in the abbreviation; for example, multi-walled
carbon nanotube (MWNT).

Rotating single-walled zigzag carbon nanotube 1.2 Single-walled

bon with a cylindrical nanostructure. Nanotubes have • Armchair (n,n) i.e.: m=n
been constructed with length-to-diameter ratio of up to
132,000,000:1,[1] significantly larger than for any other • The translation vector is bent, while the chiral vector
material. These cylindrical carbon molecules have un- stays straight
usual properties, which are valuable for nanotechnology, • Graphene nanoribbon
electronics, optics and other fields of materials science
and technology. In particular, owing to their extraordi- • The chiral vector is bent, while the translation vector
nary thermal conductivity and mechanical and electrical stays straight
properties, carbon nanotubes find applications as addi-
tives to various structural materials. For instance, nan- • Zigzag (n,0)
otubes form a tiny portion of the material(s) in some (pri- • Chiral (n,m)
marily carbon fiber) baseball bats, golf clubs, car parts or
damascus steel.[2][3] • n and m can be counted at the end of the tube
Nanotubes are members of the fullerene structural fam- • Graphene nanoribbon
ily. Their name is derived from their long, hollow struc-
ture with the walls formed by one-atom-thick sheets of
Most single-walled nanotubes (SWNTs) have a diame-
carbon, called graphene. These sheets are rolled at spe-
ter of close to 1 nanometer, and can be many millions of
cific and discrete ("chiral") angles, and the combina-
times longer. The structure of a SWNT can be concep-
tion of the rolling angle and radius decides the nanotube
tualized by wrapping a one-atom-thick layer of graphite
properties; for example, whether the individual nanotube
called graphene into a seamless cylinder. The way the
shell is a metal or semiconductor. Nanotubes are cate-
graphene sheet is wrapped is represented by a pair of in-
gorized as single-walled nanotubes (SWNTs) and multi-
dices (n,m). The integers n and m denote the number of
walled nanotubes (MWNTs). Individual nanotubes nat- unit vectors along two directions in the honeycomb crystal
urally align themselves into “ropes” held together by van
lattice of graphene. If m = 0, the nanotubes are called
der Waals forces, more specifically, pi-stacking. zigzag nanotubes, and if n = m, the nanotubes are called
Applied quantum chemistry, specifically, orbital hy- armchair nanotubes. Otherwise, they are called chiral.

1
2 1 TYPES OF CARBON NANOTUBES AND RELATED STRUCTURES

SWNTs are an important variety of carbon nanotube be-

The (n,m) nanotube naming scheme can be thought of as a vector
(Ch) in an infinite graphene sheet that describes how to “roll up”
the graphene sheet to make the nanotube. T denotes the tube axis,
and a1 and a2 are the unit vectors of graphene in real space.
A scanning tunneling microscopy image of single-walled carbon
nanotube
cause most of their properties change significantly with
the (n,m) values, and this dependence is non-monotonic
(see Kataura plot). In particular, their band gap can vary
from zero to about 2 eV and their electrical conductivity
can show metallic or semiconducting behavior. Single-
walled nanotubes are likely candidates for miniaturizing
electronics. The most basic building block of these sys-
tems is the electric wire, and SWNTs with diameters of
an order of a nanometer can be excellent conductors.[4][5]
One useful application of SWNTs is in the development
of the first intermolecular field-effect transistors (FET).
The first intermolecular logic gate using SWCNT FETs
was made in 2001.[6] A logic gate requires both a p-FET
and an n-FET. Because SWNTs are p-FETs when ex-
posed to oxygen and n-FETs otherwise, it is possible to
protect half of an SWNT from oxygen exposure, while
exposing the other half to oxygen. This results in a single
SWNT that acts as a not logic gate with both p and n-type
FETs within the same molecule.
Single-walled nanotubes are dropping precipitously in
price, from around $1500 per gram as of 2000 to retail
prices of around $50 per gram of as-produced 40–60%
by weight SWNTs as of March 2010. As of 2016 the re-
tail price of as-produced 75% by weight SWNTs drops to
$2 per gram, cheap enough for widespread application .
SWNTs are forecast to make a large impact in electronics
applications by 2020 according to The Global Market for
Carbon Nanotubes report.

1.3 Multi-walled

A transmission electron microscopy image of a single-walled car-

bon nanotube

A scanning electron microscopy image of carbon nanotubes bun-

The diameter of an ideal nanotube can be calculated from dles
its (n,m) indices as follows
Multi-walled nanotubes (MWNTs) consist of multiple
rolled layers (concentric tubes) of graphene. There are
a√ 2 √ two models that can be used to describe the structures
d= (n + nm + m2 ) = 78.3 ((n + m)2 − nm)pm,
of multi-walled nanotubes. In the Russian Doll model,
π
sheets of graphite are arranged in concentric cylinders,
where a = 0.246 nm. e.g., a (0,8) single-walled nanotube (SWNT) within a
1.5 Nanobud 3

radii.[11] Properties such as magnetic moment, thermal

stability, etc. vary widely depending on radius of the torus
and radius of the tube.[11][12]

1.5 Nanobud

Triple-walled armchair carbon nanotube

larger (0,17) single-walled nanotube. In the Parchment

model, a single sheet of graphite is rolled in around it-
self, resembling a scroll of parchment or a rolled newspa-
per. The interlayer distance in multi-walled nanotubes is
close to the distance between graphene layers in graphite,
approximately 3.4 Å. The Russian Doll structure is ob-
served more commonly. Its individual shells can be de-
scribed as SWNTs, which can be metallic or semicon-
A stable nanobud structure
ducting. Because of statistical probability and restrictions
on the relative diameters of the individual tubes, one of
Carbon nanobuds are a newly created material combining
the shells, and thus the whole MWNT, is usually a zero-
two previously discovered allotropes of carbon: carbon
gap metal.
nanotubes and fullerenes. In this new material, fullerene-
Double-walled carbon nanotubes (DWNTs) form a spe- like “buds” are covalently bonded to the outer sidewalls of
cial class of nanotubes because their morphology and the underlying carbon nanotube. This hybrid material has
properties are similar to those of SWNTs but their re- useful properties of both fullerenes and carbon nanotubes.
sistance to chemicals is significantly improved. This is In particular, they have been found to be exceptionally
especially important when functionalization is required good field emitters. In composite materials, the attached
(this means grafting of chemical functions at the surface fullerene molecules may function as molecular anchors
of the nanotubes) to add new properties to the CNT. In preventing slipping of the nanotubes, thus improving the
the case of SWNTs, covalent functionalization will break composite’s mechanical properties.
some C=C double bonds, leaving “holes” in the structure
on the nanotube and, thus, modifying both its mechani-
cal and electrical properties. In the case of DWNTs, only 1.6 Three-dimensional carbon nanotube
the outer wall is modified. DWNT synthesis on the gram- architectures
scale was first proposed in 2003[7] by the CCVD tech-
nique, from the selective reduction of oxide solutions in
methane and hydrogen.
The telescopic motion ability of inner shells[8] and their
unique mechanical properties[9] will permit the use of
multi-walled nanotubes as main movable arms in coming
nanomechanical devices. Retraction force that occurs to
telescopic motion caused by the Lennard-Jones interac-
tion between shells and its value is about 1.5 nN.[10]

1.4 Torus
In theory, a nanotorus is a carbon nanotube bent into a
torus (doughnut shape). Nanotori are predicted to have
many unique properties, such as magnetic moments 1000
times larger than previously expected for certain specific
3D carbon scaffolds
Recently, several studies have highlighted the prospect
of using carbon nanotubes as building blocks to fabri-
cate three-dimensional macroscopic (>100 nm in all three
dimensions) all-carbon devices. Lalwani et al. have
reported a novel radical initiated thermal crosslinking
4 1 TYPES OF CARBON NANOTUBES AND RELATED STRUCTURES

method to fabricate macroscopic, free-standing, porous, 1.8 Nitrogen-doped carbon nanotubes

all-carbon scaffolds using single- and multi-walled car-
bon nanotubes as building blocks.[13] These scaffolds pos- Nitrogen doped carbon nanotubes (N-CNTs) can be pro-
sess macro-, micro-, and nano- structured pores and the duced through five main methods, chemical vapor de-
porosity can be tailored for specific applications. These position,[23][24] high-temperature and high-pressure reac-
3D all-carbon scaffolds/architectures may be used for tions, gas-solid reaction of amorphous carbon with NH3
the fabrication of the next generation of energy stor- at high temperature,[25] solid reaction,[26] and solvother-
age, supercapacitors, field emission transistors, high- mal synthesis.[27]
performance catalysis, photovoltaics, and biomedical de-
N-CNTs can also be prepared by a CVD method of py-
vices and implants.[14]
rolyzing melamine under Ar at elevated temperatures of
800–980 °C. However synthesis by CVD of melamine
1.7 Graphenated carbon nanotubes (g- results in the formation of bamboo-structured CNTs.
XPS spectra of grown N-CNTs reveal nitrogen in five
CNTs)
main components, pyridinic nitrogen, pyrrolic nitro-
gen, quaternary nitrogen, and nitrogen oxides. Further-
more, synthesis temperature affects the type of nitrogen
configuration.[24]
Nitrogen doping plays a pivotal role in lithium storage,
as it creates defects in the CNT walls allowing for Li
ions to diffuse into interwall space. It also increases
capacity by providing more favorable bind of N-doped
sites. N-CNTs are also much more reactive to metal ox-
SEM series of graphenated CNTs with varying foliate density
ide nanoparticle deposition which can further enhance
Graphenated CNTs are a relatively new hybrid that com- storage capacity, especially in anode materials for Li-ion
[28]
bines graphitic foliates grown along the sidewalls of mul- batteries. However boron-doped nanotubes have been
[29]
tiwalled or bamboo style CNTs. Yu et al.[15] reported on shown to make batteries with triple capacity.
“chemically bonded graphene leaves” growing along the
sidewalls of CNTs. Stoner et al.[16] described these struc-
tures as “graphenated CNTs” and reported in their use for 1.9 Peapod
enhanced supercapacitor performance. Hsu et al. further
[30][31]
reported on similar structures formed on carbon fiber pa- A carbon peapod is a novel hybrid carbon material
[17]
per, also for use in supercapacitor applications. Pham which traps fullerene inside a carbon nanotube. It can
et al. [18][19]
also reported a similar structure, namely possess interesting magnetic properties with heating and
“graphene-carbon nanotube hybrids”, grown directly onto irradiation. It can also be applied as an oscillator during
[32][33]
carbon fiber paper to form an integrated, binder free, high theoretical investigations and predictions.
surface area conductive catalyst support for Proton Ex-
change Membrane Fuel Cells electrode applications with
enhanced performance and durability. The foliate den- 1.10 Cup-stacked carbon nanotubes
sity can vary as a function of deposition conditions (e.g.
temperature and time) with their structure ranging from Cup-stacked carbon nanotubes (CSCNTs) differ from
few layers of graphene (< 10) to thicker, more graphite- other quasi-1D carbon structures, which normally behave
like.[20] as quasi-metallic conductors of electrons. CSCNTs ex-
hibit semiconducting behaviors due to the stacking mi-
The fundamental advantage of an integrated graphene-
crostructure of graphene layers.[34]
CNT structure is the high surface area three-dimensional
framework of the CNTs coupled with the high edge den-
sity of graphene. Graphene edges provide significantly
higher charge density and reactivity than the basal plane,
1.11 Extreme carbon nanotubes
but they are difficult to arrange in a three-dimensional,
high volume-density geometry. CNTs are readily aligned The observation of the longest carbon nanotubes grown
in a high density geometry (i.e., a vertically aligned so far are [35]
over 1/2 m (550 mm long) was reported
[21]
forest) but lack high charge density surfaces—the side- in 2013. These nanotubes were grown on Si sub-
walls of the CNTs are similar to the basal plane of strates using an improved chemical vapor deposition
graphene and exhibit low charge density except where (CVD) method and represent electrically uniform arrays
edge defects exist. Depositing a high density of graphene of single-walled carbon nanotubes.[1]
foliates along the length of aligned CNTs can signifi- The shortest carbon nanotube is the organic compound
cantly increase the total charge capacity per unit of nom- cycloparaphenylene, which was synthesized in early
inal area as compared to other carbon nanostructures.[22] 2009.[36][37]
2.2 Hardness
Cycloparaphenylene
The thinnest carbon nanotube is the armchair (2,2) CNT
with a diameter of 0.3 nm. This nanotube was grown
inside a multi-walled carbon nanotube. Assigning of car-
bon nanotube type was done by a combination of high-
resolution transmission electron microscopy (HRTEM),
Raman spectroscopy and density functional theory (DFT)
calculations.[38]
The thinnest freestanding single-walled carbon nanotube
is about 0.43 nm in diameter. Researchers suggested
that it can be either (5,1) or (4,2) SWCNT, but the ex-
act type of carbon nanotube remains questionable.[39]
(3,3), (4,3) and (5,1) carbon nanotubes (all about 0.4
nm in diameter) were unambiguously identified using
aberration-corrected high-resolution transmission elec-
tron microscopy inside double-walled CNTs.[40]
The highest density of CNTs was achieved in 2013, grown
on a conductive titanium-coated copper surface that was
coated with co-catalysts cobalt and molybdenum at lower
than typical temperatures of 450 °C. The tubes averaged
a height of 380 nm and a mass density of 1.6 g cm−3 .
The material showed ohmic conductivity (lowest resis-
tance ∼22 kΩ).[41][42]
2 Properties
2.1 Strength
See also: Mechanical properties of carbon nanotubes
Carbon nanotubes are the strongest and stiffest materi-
als yet discovered in terms of tensile strength and elastic
modulus respectively. This strength results from the
covalent sp2 bonds formed between the individual car-
bon atoms. In 2000, a multi-walled carbon nanotube
was tested to have a tensile strength of 63 gigapascals
(9,100,000 psi).[43] (For illustration, this translates into
the ability to endure tension of a weight equivalent to
6,422 kilograms-force (62,980 N; 14,160 lbf) on a ca-
ble with cross-section of 1 square millimetre (0.0016 sq
in).) Further studies, such as one conducted in 2008, re-
vealed that individual CNT shells have strengths of up
5
to ~100 gigapascals (15,000,000 psi), which is in agree-
ment with quantum/atomistic models.[44] Since carbon
nanotubes have a low density for a solid of 1.3 to 1.4
g/cm3 ,[45] its specific strength of up to 48,000 kN·m·kg−1
is the best of known materials, compared to high-carbon
steel’s 154 kN·m·kg−1 .
Under excessive tensile strain, the tubes will undergo
plastic deformation, which means the deformation is per-
manent. This deformation begins at strains of approxi-
mately 5% and can increase the maximum strain the tubes
undergo before fracture by releasing strain energy.
Although the strength of individual CNT shells is ex-
tremely high, weak shear interactions between adjacent
shells and tubes lead to significant reduction in the ef-
fective strength of multi-walled carbon nanotubes and
carbon nanotube bundles down to only a few GPa.[46]
This limitation has been recently addressed by applying
high-energy electron irradiation, which crosslinks inner
shells and tubes, and effectively increases the strength
of these materials to ~60 GPa for multi-walled carbon
nanotubes[44] and ~17 GPa for double-walled carbon nan-
otube bundles.[46]
CNTs are not nearly as strong under compression. Be-
cause of their hollow structure and high aspect ratio, they
tend to undergo buckling when placed under compres-
sive, torsional, or bending stress.[47]
E
Experimental observation; T Theoretical prediction
The above discussion referred to axial properties of
the nanotube, whereas simple geometrical considerations
suggest that carbon nanotubes should be much softer
in the radial direction than along the tube axis. In-
deed, TEM observation of radial elasticity suggested
that even the van der Waals forces can deform two
adjacent nanotubes.[56] Nanoindentation experiments,
performed by several groups on multiwalled carbon
nanotubes[57][58] and tapping/contact mode atomic force
microscope measurements performed on single-walled
carbon nanotubes,[59] indicated a Young’s modulus of the
order of several GPa, confirming that CNTs are indeed
rather soft in the radial direction.
2.2 Hardness
Standard single-walled carbon nanotubes can withstand
a pressure up to 25 GPa without [plastic/permanent] de-
formation. They then undergo a transformation to super-
hard phase nanotubes. Maximum pressures measured us-
ing current experimental techniques are around 55 GPa.
However, these new superhard phase nanotubes collapse
at an even higher, albeit unknown, pressure.
The bulk modulus of superhard phase nanotubes is 462
to 546 GPa, even higher than that of diamond (420 GPa
for single diamond crystal).[60]
6 2 PROPERTIES

2.3 Wettability affects its electrical properties. For a given (n,m) nan-
otube, if n = m, the nanotube is metallic; if n − m is a
The surface wettability of CNT is of importance for its multiple of 3, then the nanotube is semiconducting with
applications in various settings. Although the intrinsic a very small band gap, otherwise the nanotube is a mod-
contact angle of graphite is around 90°, the contact an- erate semiconductor. Thus all armchair (n = m) nan-
gles of most as-synthesized CNT arrays are over 160°, otubes are metallic, and nanotubes (6,4), (9,1), etc. are
exhibiting a superhydrophobic property. By applying a semiconducting.[63]
low voltage as low as 1.3V, the extreme water repellant However, this rule has exceptions, because curvature ef-
surface can be switched into superhydrophilic.[61] fects in small diameter tubes can strongly influence elec-
trical properties. Thus, a (5,0) SWCNT that should be
semiconducting in fact is metallic according to the calcu-
2.4 Kinetic properties lations. Likewise, zigzag and chiral SWCNTs with small
diameters that should be metallic have a finite gap (arm-
Multi-walled nanotubes are multiple concentric nan- chair nanotubes remain metallic).[63] In theory, metallic
otubes precisely nested within one another. These ex- nanotubes can carry an electric current density of 4 × 109
hibit a striking telescoping property whereby an inner A/cm2 , which is more than 1,000 times greater than those
nanotube core may slide, almost without friction, within of metals such as copper,[64] where for copper intercon-
its outer nanotube shell, thus creating an atomically per- nects current densities are limited by electromigration.
fect linear or rotational bearing. This is one of the first
true examples of molecular nanotechnology, the precise Because of its nanoscale cross-section, electrons prop-
positioning of atoms to create useful machines. Already, agate only along the tube’s axis. As a result, carbon
this property has been utilized to create the world’s small- nanotubes are frequently referred to as one-dimensional
est rotational motor.[62] Future applications such as a gi- conductors. The maximum electrical conductance of a
gahertz mechanical oscillator are also envisioned. single-walled carbon nanotube is 2G0 , where G0 = 2e2 /h
is the conductance of a single ballistic quantum chan-
nel.[65]
2.5 Electrical properties Intrinsic superconductivity has been reported,[66] al-
though other experiments found no evidence of this, leav-
ing the claim a subject of debate.[67]

2.6 Optical properties

Main article: Optical properties of carbon nanotubes

2.7 Thermal properties

Main article: Thermal properties of nanostructures

All nanotubes are expected to be very good thermal con-

ductors along the tube, exhibiting a property known as
"ballistic conduction", but good insulators laterally to the
tube axis. Measurements show that a SWNT has a room-
temperature thermal conductivity along its axis of about
3500 W·m−1 ·K−1 ;[68] compare this to copper, a metal well
known for its good thermal conductivity, which transmits
−1 −1
Band structures computed using tight binding approximation for 385 W·m ·K . A SWNT has a room-temperature ther-
(6,0) CNT (zigzag, metallic), (10,2) CNT (semiconducting) and mal conductivity across its axis (in the radial direction)
(10,10) CNT (armchair, metallic). of about 1.52 W·m−1 ·K−1 ,[69] which is about as thermally
conductive as soil. The temperature stability of carbon
Because of the symmetry and unique electronic struc- nanotubes is estimated to be up to 2800 °C in vacuum
ture of graphene, the structure of a nanotube strongly and about 750 °C in air.[70]
3.1 Toxicity 7

2.8 Defects Results of rodent studies collectively show that regardless

of the process by which CNTs were synthesized and the
As with any material, the existence of a crystallographic types and amounts of metals they contained, CNTs were
defect affects the material properties. Defects can occur capable of producing inflammation, epithelioid granu-
in the form of atomic vacancies. High levels of such de- lomas (microscopic nodules), fibrosis, and biochemi-
fects can lower the tensile strength by up to 85%. An cal/toxicological changes in the lungs.[76] Comparative
important example is the Stone Wales defect, which cre- toxicity studies in which mice were given equal weights
ates a pentagon and heptagon pair by rearrangement of of test materials showed that SWCNTs were more toxic
the bonds. Because of the very small structure of CNTs, than quartz, which is considered a serious occupational
the tensile strength of the tube is dependent on its weakest health hazard when chronically inhaled. As a control, ul-
segment in a similar manner to a chain, where the strength trafine carbon black was shown to produce minimal lung
of the weakest link becomes the maximum strength of the responses.[77]
chain. Carbon nanotubes deposit in the alveolar ducts by align-
Crystallographic defects also affect the tube’s electrical ing lengthwise with the airways; the nanotubes will of-
[78]
properties. A common result is lowered conductivity ten combine with metals. The needle-like fiber shape
through the defective region of the tube. A defect in of CNTs is similar to asbestos fibers. This raises the
armchair-type tubes (which can conduct electricity) can idea that widespread use of carbon nanotubes may lead to
cause the surrounding region to become semiconduct- pleural mesothelioma, a cancer of the lining of the lungs,
ing, and single monatomic vacancies induce magnetic or peritoneal mesothelioma, a cancer of the lining of the
properties.[71] abdomen (both caused by exposure to asbestos). A re-
cently published pilot study supports this prediction.[79]
Crystallographic defects strongly affect the tube’s ther-
Scientists exposed the mesothelial lining of the body cav-
mal properties. Such defects lead to phonon scattering,
ity of mice to long multiwalled carbon nanotubes and
which in turn increases the relaxation rate of the phonons.
observed asbestos-like, length-dependent, pathogenic be-
This reduces the mean free path and reduces the ther-
havior that included inflammation and formation of le-
mal conductivity of nanotube structures. Phonon trans-
sions known as granulomas. Authors of the study con-
port simulations indicate that substitutional defects such
clude:
as nitrogen or boron will primarily lead to scattering of
high-frequency optical phonons. However, larger-scale
defects such as Stone Wales defects cause phonon scatter- This is of considerable importance, be-
ing over a wide range of frequencies, leading to a greater cause research and business communities con-
reduction in thermal conductivity.[72] tinue to invest heavily in carbon nanotubes
for a wide range of products under the as-
sumption that they are no more hazardous than
graphite. Our results suggest the need for fur-
3 Safety and Health ther research and great caution before intro-
ducing such products into the market if long-
term harm is to be avoided.[79]
3.1 Toxicity
Although further research is required, the available data
See also: Fullerene § Safety and toxicity suggest that under certain conditions, especially those in-
volving chronic exposure, carbon nanotubes can pose a
[73][75][77][79]
The toxicity of carbon nanotubes has been an impor- serious risk to human health.
tant question in nanotechnology. As of 2007, such In 2014, experts from the International Agency for Re-
research had just begun. The data is still fragmen- search on Cancer (IARC) assessed the carcinogenicity of
tary and subject to criticism. Preliminary results high- CNTs, including SWCNTs and MWCNTs. No human
light the difficulties in evaluating the toxicity of this epidemiologic or cancer data was available to the IARC
heterogeneous material. Parameters such as structure, Working Group at the time, so the evaluation focused on
size distribution, surface area, surface chemistry, surface the results of in vivo animal studies assessing the carcino-
charge, and agglomeration state as well as purity of the genicity of SWCNTs and MWCNTs in rodents.
samples, have considerable impact on the reactivity of The Working Group concluded that there was sufficient
carbon nanotubes. However, available data clearly show evidence for the specific MWCNT type “MWCNT-7”,
that, under some conditions, nanotubes can cross mem- limited evidence for the two other types of MWCNTs
brane barriers, which suggests that, if raw materials reach with dimensions similar to MWCNT-7, and inadequate
the organs, they can induce harmful effects such as in- evidence for SWCNTs. Therefore, it was agreed to
flammatory and fibrotic reactions.[73][74] specifically classify MWCNT-7 as possibly carcinogenic
Under certain conditions CNTs can enter human cells and to humans (Group 2B) while the other forms of CNT,
accumulate in the cytoplasm, causing cell death.[75] namely SWCNT and other types of MWCNT, excluding
8 4 SYNTHESIS

MWCNT-7, were considered not classifiable as to their published guidance titled “Safe Handling and use of Car-
carcinogenicity to humans (Group 3) due to a lack of co- bon Nanotubes” which describes two approaches to man-
herent evidence.[80] aging the risks that include risk management with detailed
hazard analysis and exposure assessment as well as risk
management by using Control Banding.[89] The National
3.2 Epidemiology and Risk Management Institute for Occupational Safety and Health has also
published a document titled “Current Intelligence Bul-
Currently, there is a lack of epidemiological evidence letin 65: Occupational Exposure to Carbon Nanotubes
linking exposure to CNT to human health effects. To and Nanofibers” describes strategies for controlling work-
date, there have been only a handful of published epi- place exposures and implementing a medical surveillance
demiological studies that have solely examined the health program.[85]
effects related to the exposure of CNT, while sev-
These guidance documents generally advocate instituting
eral other studies are currently underway and yet to be
the principles of the Hierarchy of Hazard Control which
published.[81][82][83] With the limited amount of human
is a system used in industry to minimize or eliminate ex-
data, scientists are more reliant on the results of current
posure to hazards. The hazard controls in the hierarchy
animal toxicity studies to predict adverse health effects,
are, in order of decreasing effectiveness:
as well as applying what is already known about expo-
sures to other fibrous materials such as asbestos or fine
• Elimination
and ultra-fine particulates. This limitation of human data
has lead to the use of the precautionary principal, which • Substitution
urges workplaces to limit exposure levels to CNT as low
• Engineering Controls
as possibly achievable in the absence of known health ef-
[84]
fects data. • Administrative Controls
To date, several international government agencies, as • Personal Protective Equipment
well as individual authors, have developed occupational
exposure limits (OEL) to reduce the risk of any possi-
ble human health effects associated with workplace ex- 4 Synthesis
posures to CNT. The National Institute for Occupational
Safety and Health (NIOSH) conducted a risk assessment
using animal and other toxicological data relevant to as-
sessing the potential non-malignant adverse respiratory
effects of CNT and proposed an OEL of 1 μg/m3 ele-
mental carbon as a respirable mass 8-hour time-weighted
average (TWA) concentration.[85] Several individual au-
thors have also performed similar risk assessments using
animal toxicity data and have established inhalation ex-
posure limits ranging from 2.5 to 50 ug/m3 .[86]

3.3 Safety and Exposure Prevention

Occupational exposures that could potentially allow the
inhalation of CNT is of the greatest concern, especially
in situations where the CNT is handled in powder form
which can easily be aerosolized and inhaled. Also of
concern are any high-energy processes that are applied
to various CNT preparations such as the mixing or son-
ication of CNT in liquids as well as processes that cut
or drill into CNT based composites in downstream prod-
ucts. These types of high-energy processes will aerosolize
CNT which can then be inhaled.
Guidance for minimizing exposure and risk to CNT have
been published by several international agencies which
includes several documents from the British Health and powder of carbon nanotubes
Safety Executive titled “Using nanomaterials at work In-
cluding carbon nanotubes and other bio-persistent high Techniques have been developed to produce nanotubes
aspect ratio nanomaterials” and the “Risk Management of in sizable quantities, including arc discharge, laser abla-
Carbon Nanotubes”[87][88] Safe Work Australia has also tion, high-pressure carbon monoxide disproportionation,
4.3 Plasma torch
and chemical vapor deposition (CVD). Most of these
processes take place in a vacuum or with process gases.
CVD growth of CNTs can occur in vacuum or at atmo-
spheric pressure. Large quantities of nanotubes can be
synthesized by these methods; advances in catalysis and
continuous growth are making CNTs more commercially
viable.[90]
4.1 Arc discharge
Nanotubes were observed in 1991 in the carbon soot
of graphite electrodes during an arc discharge, by us-
ing a current of 100 amps, that was intended to produce
fullerenes.[91] However the first macroscopic production
of carbon nanotubes was made in 1992 by two researchers
at NEC's Fundamental Research Laboratory.[92] The
method used was the same as in 1991. During this pro-
cess, the carbon contained in the negative electrode sub-
limates because of the high-discharge temperatures.
The yield for this method is up to 30% by weight and it
produces both single- and multi-walled nanotubes with
lengths of up to 50 micrometers with few structural
defects.[45] Arc-discharge technique uses higher tempera-
tures (above 1,700 °C) for CNT synthesis which typically
causes the expansion of CNTs with fewer structural de-
fects in comparison with other methods.[93]
4.2 Laser ablation
In laser ablation, a pulsed laser vaporizes a graphite tar-
get in a high-temperature reactor while an inert gas is bled
into the chamber. Nanotubes develop on the cooler sur-
faces of the reactor as the vaporized carbon condenses.
A water-cooled surface may be included in the system to
collect the nanotubes.
This process was developed by Dr. Richard Smalley
and co-workers at Rice University, who at the time of
the discovery of carbon nanotubes, were blasting metals
with a laser to produce various metal molecules. When
they heard of the existence of nanotubes they replaced
the metals with graphite to create multi-walled carbon
nanotubes.[94] Later that year the team used a composite
of graphite and metal catalyst particles (the best yield was
from a cobalt and nickel mixture) to synthesize single-
walled carbon nanotubes.[95]
The laser ablation method yields around 70% and pro-
duces primarily single-walled carbon nanotubes with
a controllable diameter determined by the reaction
temperature. However, it is more expensive than either
arc discharge or chemical vapor deposition.[45]
The effective equation for few cycle optical pulse dynam-
ics was obtained by virtue of the Boltzmann collision-less
equation solution for conduction band electrons of semi-
conductor carbon nanotubes in the case when medium
with carbon nanotubes has spatially-modulated refractive
9
index.[96]
4.3 Plasma torch
Single-walled carbon nanotubes can also be synthesized
by a thermal plasma method. It was first invented in 2000
at INRS (Institut National de la Recherche Scientifique in
Varennes, Canada), by Olivier Smiljanic. In this method,
the aim is to reproduce the conditions prevailing in the
arc discharge and laser ablation approaches, but a carbon-
containing gas is used instead of graphite vapors to supply
the carbon necessary for the production of SWNT. Do-
ing so, the growth of SWNT is more efficient (decompos-
ing a carbon containing gas can be 10 times less energy-
consuming than graphite vaporization). It is also contin-
uous and occurs at low cost. To produce a continuous
process, a gas mixture composed of argon, ethylene and
ferrocene is introduced into a microwave plasma torch,
where it is atomized by the atmospheric pressure plasma,
which has the form of an intense 'flame'. The fumes cre-
ated by the flame are found to contain SWNT, metallic
and carbon nanoparticles and amorphous carbon.[97][98]
Another way to produce single-walled carbon nanotubes
with a plasma torch, is to use the induction thermal
plasma method, implemented in 2005 by groups from
the University of Sherbrooke and the National Research
Council of Canada.[99] The method is similar to arc-
discharge in that both use ionized gas to reach the high
temperature necessary to vaporize carbon-containing
substances and the metal catalysts necessary for the en-
suing nanotube growth. The thermal plasma is induced
by high frequency oscillating currents in a coil, and is
maintained in flowing inert gas. Typically, a feedstock
of carbon black and metal catalyst particles is fed into
the plasma, and then cooled down to form single-walled
carbon nanotubes. Different single-wall carbon nanotube
diameter distributions can be synthesized.
The induction thermal plasma method can produce up to
2 grams of nanotube material per minute, which is higher
than the arc-discharge or the laser ablation methods.
4.4 Chemical vapor deposition (CVD)
The catalytic vapor phase deposition of carbon was re-
ported in 1952[100] and 1959,[101] but it was not until
1993[102] that carbon nanotubes were formed by this pro-
cess. In 2007, researchers at the University of Cincinnati
(UC) developed a process to grow aligned carbon nan-
otube arrays of length 18 mm on a FirstNano ET3000
carbon nanotube growth system.[103]
During CVD, a substrate is prepared with a layer of metal
catalyst particles, most commonly nickel, cobalt,[104] iron,
or a combination.[105] The metal nanoparticles can also
be produced by other ways, including reduction of ox-
ides or oxides solid solutions. The diameters of the nan-
10 4 SYNTHESIS

the carbon nanotubes. However, alternative catalyst sup-

ports that are soluble in water have proven effective for
nanotube growth.[111]
If a plasma is generated by the application of a strong
electric field during growth (plasma-enhanced chemical
vapor deposition), then the nanotube growth will follow
the direction of the electric field.[112] By adjusting the
geometry of the reactor it is possible to synthesize ver-
tically aligned carbon nanotubes[113] (i.e., perpendicular
to the substrate), a morphology that has been of interest
to researchers interested in electron emission from nan-
otubes. Without the plasma, the resulting nanotubes are
often randomly oriented. Under certain reaction condi-
tions, even in the absence of a plasma, closely spaced nan-
otubes will maintain a vertical growth direction resulting
in a dense array of tubes resembling a carpet or forest.
Of the various means for nanotube synthesis, CVD shows
the most promise for industrial-scale deposition, be-
cause of its price/unit ratio, and because CVD is ca-
pable of growing nanotubes directly on a desired sub-
strate, whereas the nanotubes must be collected in the
other growth techniques. The growth sites are control-
lable by careful deposition of the catalyst.[114] In 2007,
a team from Meijo University demonstrated a high-
nanotubes being grown by plasma enhanced chemical vapor de-
position
efficiency CVD technique for growing carbon nanotubes
from camphor.[115] Researchers at Rice University, un-
til recently led by the late Richard Smalley, have con-
otubes that are to be grown are related to the size of centrated upon finding methods to produce large, pure
the metal particles. This can be controlled by patterned amounts of particular types of nanotubes. Their ap-
(or masked) deposition of the metal, annealing, or by proach grows long fibers from many small seeds cut from
plasma etching of a metal layer. The substrate is heated a single nanotube; all of the resulting fibers were found
to approximately 700 °C. To initiate the growth of nan- to be of the same diameter as the original nanotube
otubes, two gases are bled into the reactor: a process gas and are expected to be of the same type as the original
(such as ammonia, nitrogen or hydrogen) and a carbon- nanotube.[116]
containing gas (such as acetylene, ethylene, ethanol or
methane). Nanotubes grow at the sites of the metal cat- 4.4.1 Super-growth CVD
alyst; the carbon-containing gas is broken apart at the
surface of the catalyst particle, and the carbon is trans- Super-growth CVD (water-assisted chemical vapor depo-
ported to the edges of the particle, where it forms the sition) was developed by Kenji Hata, Sumio Iijima and
nanotubes. This mechanism is still being studied.[106] The co-workers at AIST, Japan.[117] In this process, the ac-
catalyst particles can stay at the tips of the growing nan- tivity and lifetime of the catalyst are enhanced by addi-
otube during growth, or remain at the nanotube base, de- tion of water into the CVD reactor. Dense millimeter-tall
pending on the adhesion between the catalyst particle and nanotube “forests”, aligned normal to the substrate, were
the substrate.[107] Thermal catalytic decomposition of hy- produced. The forests height could be expressed, as
drocarbon has become an active area of research and can
be a promising route for the bulk production of CNTs.
Fluidised bed reactor is the most widely used reactor for H(t) = βτo (1 − e−t/τo ).
CNT preparation. Scale-up of the reactor is the major
challenge.[108][109] In this equation, β is the initial growth rate and τo is the
[118]
CVD is the most widely used method for the produc- characteristic catalyst lifetime.
tion of carbon nanotubes.[110] For this purpose, the metal Their specific surface exceeds 1,000 m2 /g (capped) or
nanoparticles are mixed with a catalyst support such as 2,200 m2 /g (uncapped),[119] surpassing the value of 400–
MgO or Al2 O3 to increase the surface area for higher 1,000 m2 /g for HiPco samples. The synthesis efficiency
yield of the catalytic reaction of the carbon feedstock with is about 100 times higher than for the laser ablation
the metal particles. One issue in this synthesis route is method. The time required to make SWNT forests of
the removal of the catalyst support via an acid treatment, the height of 2.5 mm by this method was 10 minutes
which sometimes could destroy the original structure of in 2004. Those SWNT forests can be easily separated
4.6 Removal of catalysts 11

from the catalyst, yielding clean SWNT material (pu-
rity >99.98%) without further purification. For compari-
son, the as-grown HiPco CNTs contain about 5–35%[120]
of metal impurities; it is therefore purified through dis-
persion and centrifugation that damages the nanotubes.
Super-growth avoids this problem. Patterned highly orga-
nized single-walled nanotube structures were successfully
fabricated using the super-growth technique.
The mass density of super-growth CNTs is about 0.037
g/cm3 .[121][122] It is much lower than that of conventional
CNT powders (~1.34 g/cm3 ), probably because the latter
contain metals and amorphous carbon.
The super-growth method is basically a variation of CVD.
Therefore, it is possible to grow material containing
SWNT, DWNTs and MWNTs, and to alter their ratios
by tuning the growth conditions.[123] Their ratios change
by the thinness of the catalyst. Many MWNTs are in-
cluded so that the diameter of the tube is wide.[122]
The vertically aligned nanotube forests originate from a
“zipping effect” when they are immersed in a solvent and
dried. The zipping effect is caused by the surface tension
of the solvent and the van der Waals forces between the
carbon nanotubes. It aligns the nanotubes into a dense
material, which can be formed in various shapes, such as 4.7
sheets and bars, by applying weak compression during the
process. Densification increases the Vickers hardness by
about 70 times and density is 0.55 g/cm3 . The packed
carbon nanotubes are more than 1 mm long and have a
carbon purity of 99.9% or higher; they also retain the de-
sirable alignment properties of the nanotubes forest.[124]
4.6 Removal of catalysts
Nanoscale metal catalysts are important ingredients for
fixed- and fluidized-bed CVD synthesis of CNTs. They
allow increasing the growth efficiency of CNTs and may
give control over their structure and chirality.[135] Dur-
ing synthesis, catalysts can convert carbon precursors into
tubular carbon structures but can also form encapsulat-
ing carbon overcoats. Together with metal oxide sup-
ports they may therefore attach to or become incorpo-
rated into the CNT product.[136] The presence of metal
impurities can be problematic for many applications. Es-
pecially catalyst metals like nickel, cobalt or yttrium may
be of toxicological concern.[137] While unencapsulated
catalyst metals may be readily removable by acid washing,
encapsulated ones require oxidative treatment for open-
ing their carbon shell.[138] The effective removal of cat-
alysts, especially of encapsulated ones, while preserving
the CNT structure is a challenge and has been addressed
in many studies.[139][140] A new approach to break car-
bonaceaous catalyst encapsulations is based on rapid ther-
mal annealing.[141]
Application-related issues

4.5 Natural, incidental, and controlled

flame environments

Fullerenes and carbon nanotubes are not necessarily

products of high-tech laboratories; they are commonly
formed in such mundane places as ordinary flames,[125]
produced by burning methane,[126] ethylene,[127] and
benzene,[128] and they have been found in soot from both
indoor and outdoor air.[129] However, these naturally oc-
curring varieties can be highly irregular in size and qual-
ity because the environment in which they are produced
is often highly uncontrolled. Thus, although they can be
used in some applications, they can lack in the high de-
gree of uniformity necessary to satisfy the many needs of
both research and industry. Recent efforts have focused
on producing more uniform carbon nanotubes in con-
trolled flame environments.[130][131][132][133] Such meth-
ods have promise for large-scale, low-cost nanotube syn-
thesis based on theoretical models,[134] though they must Centrifuge tube with a solution of carbon nanotubes,
compete with rapidly developing large scale CVD pro- which were sorted by diameter using density-gradient
duction. ultracentrifugation.[142]
12
Many electronic applications of carbon nanotubes cru-
cially rely on techniques of selectively producing either
semiconducting or metallic CNTs, preferably of a certain
chirality. Several methods of separating semiconducting
and metallic CNTs are known, but most of them are not
yet suitable for large-scale technological processes. The
most efficient method relies on density-gradient ultra-
centrifugation, which separates surfactant-wrapped nan-
otubes by the minute difference in their density. This
density difference often translates into difference in the
nanotube diameter and (semi)conducting properties.[142]
Another method of separation uses a sequence of freez-
ing, thawing, and compression of SWNTs embedded
in agarose gel. This process results in a solution con-
taining 70% metallic SWNTs and leaves a gel contain-
ing 95% semiconducting SWNTs. The diluted solutions
separated by this method show various colors.[143][144]
The separated carbon nanotubes using this method have
been applied to electrodes, e.g. electric double-layer
capacitor.[145] Moreover, SWNTs can be separated by
the column chromatography method. Yield is 95% in
semiconductor type SWNT and 90% in metallic type
SWNT.[146]
In addition to separation of semiconducting and metallic
SWNTs, it is possible to sort SWNTs by length, diam-
eter, and chirality. The highest resolution length sort-
ing, with length variation of <10%, has thus far been
achieved by size exclusion chromatography (SEC) of
DNA-dispersed carbon nanotubes (DNA-SWNT).[147]
SWNT diameter separation has been achieved by density-
gradient ultracentrifugation (DGU)[148] using surfactant-
dispersed SWNTs and by ion-exchange chromatography
(IEC) for DNA-SWNT.[149] Purification of individual
chiralities has also been demonstrated with IEC of DNA-
SWNT: specific short DNA oligomers can be used to
isolate individual SWNT chiralities. Thus far, 12 chi-
ralities have been isolated at purities ranging from 70%
for (8,3) and (9,5) SWNTs to 90% for (6,5), (7,5) and
(10,5)SWNTs.[150] There have been successful efforts to
integrate these purified nanotubes into devices, e. g.
FETs.[151]
An alternative to separation is development of a selective
growth of semiconducting or metallic CNTs. Recently, a
new CVD recipe that involves a combination of ethanol
and methanol gases and quartz substrates resulting in hor-
izontally aligned arrays of 95–98% semiconducting nan-
otubes was announced.[152]
Nanotubes are usually grown on nanoparticles of mag-
netic metal (Fe, Co), which facilitates production of
electronic (spintronic) devices. In particular, control
of current through a field-effect transistor by mag-
netic field has been demonstrated in such a single-tube
nanostructure.[153]
6 CURRENT APPLICATIONS
5 Chemical modification
Main articles: Carbon nanotube chemistry and Selective
chemistry of single-walled nanotubes
Carbon nanotubes can be functionalized to attain desired
properties that can be used in a wide variety of applica-
tions. The two main methods of carbon nanotube func-
tionalization are covalent and non-covalent modifications.
Because of their hydrophobic nature, carbon nanotubes
tend to agglomerate hindering their dispersion is solvents
or viscous polymer melts. The resulting nanotube bundles
or aggregates reduce the mechanical performance of the
final composite. The surface of the carbon nanotubes can
be modified to reduce the hydrophobicity and improve
interfacial adhesion to a bulk polymer through chemical
attachment.[154]
6 Current applications
Current use and application of nanotubes has mostly been
limited to the use of bulk nanotubes, which is a mass of
rather unorganized fragments of nanotubes. Bulk nan-
otube materials may never achieve a tensile strength sim-
ilar to that of individual tubes, but such composites may,
nevertheless, yield strengths sufficient for many applica-
tions. Bulk carbon nanotubes have already been used as
composite fibers in polymers to improve the mechanical,
thermal and electrical properties of the bulk product.
• Easton-Bell Sports, Inc. have been in partner-
ship with Zyvex Performance Materials, using
CNT technology in a number of their bicycle
components—including flat and riser handlebars,
cranks, forks, seatposts, stems and aero bars.
• Zyvex Technologies has also built a 54' maritime
vessel, the Piranha Unmanned Surface Vessel, as a
technology demonstrator for what is possible using
CNT technology. CNTs help improve the structural
performance of the vessel, resulting in a lightweight
8,000 lb boat that can carry a payload of 15,000 lb
over a range of 2,500 miles.[155]
• Amroy Europe Oy manufactures Hybtonite car-
bon nanoepoxy resins where carbon nanotubes have
been chemically activated to bond to epoxy, result-
ing in a composite material that is 20% to 30%
stronger than other composite materials. It has been
used for wind turbines, marine paints and variety of
sports gear such as skis, ice hockey sticks, baseball
bats, hunting arrows, and surfboards.[156]
Other current applications include:
• tips for atomic force microscope probes[157]
7.2 Structural 13

• in tissue engineering, carbon nanotubes can act as that single-wall carbon nanotubes may help protect DNA
scaffolding for bone growth[158] molecules from damage by oxidation.[171]
A highly effective method of delivering carbon nanotubes
There is also ongoing research in using carbon nanotubes into cells is Cell squeezing, a high-throughput vector-free
as a scaffold for diverse microfabrication techniques.[159] microfluidic platform for intracellular delivery developed
at the Massachusetts Institute of Technology in the labs
of Robert S. Langer.[172]

7 Potential applications Carbon nanotubes have furthermore been grown inside

microfluidic channels for chemical analysis, based on
electrochromatography. Here, the high surface-area-to-
Main article: Potential applications of carbon nanotubes volume ratio and high hydrophobicity of CNTs are used
in order to greatly decrease the analysis time of small
The strength and flexibility of carbon nanotubes makes neutral molecules that typically require large bulky equip-
them of potential use in controlling other nanoscale struc- ment for analysis.[173][174]
tures, which suggests they will have an important role in
nanotechnology engineering. The highest tensile strength
of an individual multi-walled carbon nanotube has been 7.2 Structural
tested to be 63 GPa.[43] Carbon nanotubes were found
in Damascus steel from the 17th century, possibly help- Because of the carbon nanotube’s superior mechanical
ing to account for the legendary strength of the swords properties, many structures have been proposed ranging
made of it.[160][161] Recently, several studies have high- from everyday items like clothes and sports gear to com-
[175]
lighted the prospect of using carbon nanotubes as build- bat jackets and space elevators. However, the space
ing blocks to fabricate three-dimensional macroscopic elevator will require further efforts in refining carbon
(>1mm in all three dimensions) all-carbon devices. Lal- nanotube technology, as the practical tensile strength of
[45]
wani et al. have reported a novel radical initiated ther- carbon nanotubes must be greatly improved.
mal crosslinking method to fabricated macroscopic, free- For perspective, outstanding breakthroughs have already
standing, porous, all-carbon scaffolds using single- and been made. Pioneering work led by Ray H. Baughman at
multi-walled carbon nanotubes as building blocks.[13] the NanoTech Institute has shown that single and multi-
These scaffolds possess macro-, micro-, and nano- struc- walled nanotubes can produce materials with toughness
tured pores and the porosity can be tailored for specific unmatched in the man-made and natural worlds.[176][177]
applications. These 3D all-carbon scaffolds/architectures
maybe used for the fabrication of the next generation
of energy storage, supercapacitors, field emission tran-
sistors, high-performance catalysis, photovoltaics, and
biomedical devices and implants.

7.1 Biomedical

Researchers from Rice University and State University

of New York - Stony Brook have shown that the addi-
tion of low weight % of carbon nanotubes can lead to
significant improvements in the mechanical properties
of biodegradable polymeric nanocomposites for appli-
cations in tissue engineering including bone,[162][163][164] Carbon nanotubes being spun to form a yarn, CSIRO
cartilage,[165] muscle[166] and nerve tissue.[163][167] Dis-
persion of low weight % of graphene (~0.02 wt.%) re- Carbon nanotubes are also a promising material as build-
sults in significant increases in compressive and flexu-ing blocks in hierarchical composite materials given their
ral mechanical properties of polymeric nanocomposites.exceptional mechanical properties (~1 TPa in modulus,
Researchers at Rice University, Stony Brook University,
and ~100 GPa in strength). Initial attempts to incorporate
Radboud University Nijmegen Medical Centre and Uni- CNTs into hierarchical structures (such as yarns, fibres
versity of California, Riverside have shown that carbon
or films[178] ) has led to mechanical properties that were
nanotubes and their polymer nanocomposites are suitable
significantly lower than these potential limits. Windle et
scaffold materials for bone tissue engineering [14][158][168]
al. have used an in situ chemical vapor deposition (CVD)
and bone formation.[169][170] spinning method to produce continuous CNT yarns from
In November 2012 researchers at the American National CVD-grown CNT aerogels.[179][180] CNT yarns can also
Institute of Standards and Technology (NIST) proved be manufactured by drawing out CNT bundles from a
14 7 POTENTIAL APPLICATIONS

CNT forest and subsequently twisting to form the fibre The first nanotube integrated memory circuit was made in
(draw-twist method, see picture on right). The Win- 2004. One of the main challenges has been regulating the
dle group have fabricated CNT yarns with strengths as conductivity of nanotubes. Depending on subtle surface
high as ~9 GPa at small gage lengths of ~1 mm, how- features a nanotube may act as a plain conductor or as a
ever, strengths of only about ~1 GPa were reported at the semiconductor. A fully automated method has however
longer gage length of 20 mm.[181][182] The reason why fi- been developed to remove non-semiconductor tubes.[191]
bre strengths have been low compared to the strength of Another way to make carbon nanotube transistors has
individual CNTs is due to a failure to effectively trans- been to use random networks of them.[192] By doing so
fer load to the constituent (discontinuous) CNTs within
one averages all of their electrical differences and one
the fibre. One potential route for alleviating this prob- can produce devices in large scale at the wafer level.[193]
lem is via irradiation (or deposition) induced covalent
This approach was first patented by Nanomix Inc.[194]
inter-bundle and inter-CNT cross-linking to effectively (date of original application June 2002[195] ). It was first
'join up' the CNTs.[183] Espinosa et al. developed high
published in the academic literature by the United States
performance DWNT-polymer composite yarns by twist- Naval Research Laboratory in 2003 through independent
ing and stretching ribbons of randomly oriented bundles
research work. This approach also enabled Nanomix
of DWNTs thinly coated with polymeric organic com- to make the first transistor on a flexible and transparent
pounds. These DWNT-polymer yarns exhibited an un- substrate.[196][197]
usually high energy to failure of ~100 J·g−1 (comparable
Large structures of carbon nanotubes can be used for
to one of the toughest natural materials – spider silk[184] ),
and strength as high as ~1.4 GPa.[185] Effort is ongoing to thermal management of electronic circuits. An approx-
produce CNT composites that incorporate tougher matrix imately 1 mm–thick carbon nanotube layer was used as
materials, such as Kevlar, to further improve on the me- a special material to fabricate coolers, this material has
chanical properties toward those of individual CNTs. very low density, ~20 times lower weight than a similar
copper structure, while the cooling properties are similar
Because of the high mechanical strength of carbon nan- for the two materials.[198]
otubes, research is being made into weaving them into
clothes to create stab-proof and bulletproof clothing. The In 2013, researchers demonstrated a Turing-complete
[199][200][201]
nanotubes would effectively stop the bullet from penetrat- prototype micrometer-scale computer.
ing the body, although the bullet’s kinetic energy would Carbon nanotube transistors as logic-gate circuits with
likely cause broken bones and internal bleeding. [186] densities comparable to modern CMOS technology has
not yet been demonstrated.

7.3 Electrical circuits

Nanotube-based transistors, also known as carbon nan-

otube field-effect transistors (CNTFETs), have been
made that operate at room temperature and that are capa-
ble of digital switching using a single electron.[187] How-
ever, one major obstacle to realization of nanotubes has
been the lack of technology for mass production. In 2001
IBM researchers demonstrated how metallic nanotubes
can be destroyed, leaving semiconducting ones behind for
use as transistors. Their process is called “constructive
destruction,” which includes the automatic destruction of
defective nanotubes on the wafer.[188] This process, how-
ever, only gives control over the electrical properties on a
statistical scale.
The potential of carbon nanotubes was demonstrated in
2003 when room-temperature ballistic transistors with
ohmic metal contacts and high-k gate dielectric were re-
ported, showing 20–30x higher ON current than state-
of-the-art Si MOSFETs. This presented an important ad-
vance in the field as CNT was shown to potentially outper-
form Si. At the time, a major challenge was ohmic metal
contact formation. In this regard, palladium, which is a
high-work function metal was shown to exhibit Schottky
barrier-free contacts to semiconducting nanotubes with
diameters >1.7 nm.[189][190]
7.4 Electrical cables and wires
Wires for carrying electric current may be fabricated
from pure nanotubes and nanotube-polymer compos-
ites. It has already been demonstrated that carbon nan-
otube wires can successfully be used for power or data
transmission.[202] Recently small wires have been fabri-
cated with specific conductivity exceeding copper and
aluminum;[203][204] these cables are the highest conduc-
tivity carbon nanotube and also highest conductivity non-
metal cables. Recently, composite of carbon nanotube
and copper have been shown to exhibit nearly one hun-
dred times higher current-carrying-capacity than pure
copper or gold.[205] Significantly, the electrical conduc-
tivity of such a composite is similar to pure Cu. Thus, this
Carbon nanotube-copper (CNT-Cu) composite possesses
the highest observed current-carrying capacity among
electrical conductors. Thus for a given cross-section of
electrical conductor, the CNT-Cu composite can with-
stand and transport one hundred times higher current
compared to metals such as copper and gold.
7.7 Solar cells 15

7.5 Actuators per through a lamination process as a composite with

Li4Ti5O12 (LTO) or LiCoO2 (LCO). The paper sub-
Main article: Carbon nanotube actuators strate would function well as the separator for the battery,
where the CNT films function as the current collectors
for both the anode and the cathode. These rechargeable
The exceptional electrical and mechanical properties of
energy devices show potential in RFID tags, functional
carbon nanotubes have made them alternatives to the
packaging, or new disposable electronic applications.[210]
traditional electrical actuators for both microscopic and
macroscopic applications. Carbon nanotubes are very
good conductors of both electricity and heat, and they
7.7 Solar cells
are also very strong and elastic molecules in certain di-
rections.
One of the promising applications of single-walled car-
bon nanotubes (SWNTs) is their use in solar panels,
due to their strong UV/Vis-NIR absorption characteris-
7.6 Batteries
tics. Research has shown that they can provide a siz-
able increase in efficiency, even at their current unop-
Carbon nanotubes’ (CNTs) exciting electronic proper-
timized state. Solar cells developed at the New Jersey
ties have shown promise in the field of batteries, where
Institute of Technology use a carbon nanotube complex,
typically they are being experimented as a new elec-
formed by a mixture of carbon nanotubes and carbon
trode material, particularly the anode for lithium ion bat-
buckyballs (known as fullerenes) to form snake-like struc-
teries. This is due to the fact that the anode requires
tures. Buckyballs trap electrons, but they can't make elec-
a relatively high reversible capacity at a potential close
trons flow.[211] Add sunlight to excite the polymers, and
to metallic lithium, and a moderate irreversible capac-
the buckyballs will grab the electrons. Nanotubes, be-
ity, observed thus far only by graphite-based composites,
having like copper wires, will then be able to make the
such as CNTs. They have shown to greatly improve ca-
electrons or current flow.[212]
pacity and cyclability of lithium-ion batteries, as well as
the capability to be very effective buffering components, Additional research has been conducted on creating
alleviating the degradation of the batteries that is typi- SWNT hybrid solar panels to increase the efficiency fur-
cally due to repeated charging and discharging. Further, ther. These hybrids are created by combining SWNT’s
electronic transport in the anode can be greatly improved with photo-excitable electron donors to increase the num-
using highly metallic CNTs.[206] ber of electrons generated. It has been found that
the interaction between the photo-excited porphyrin and
More specifically, CNTs have shown reversible capac-
SWNT generates electro-hole pairs at the SWNT sur-
ities from 300 to 600 mAhg−1 , with some treatments
faces. This phenomenon has been observed experimen-
to them showing these numbers rise to up to 1000
tally, and contributes practically to an increase in effi-
mAhg−1 .[207] Meanwhile, graphite, which is most widely
ciency up to 8.5%.[213]
used as an anode material for these lithium batteries, has
shown capacities of only 320 mAhg−1 . By creating com- Further information: Carbon nanotubes in photovoltaics
posites out of the CNTs, scientists see much potential in
taking advantage of these exceptional capacities, as well
as their excellent mechanical strength, conductivities, and
low densities.[206] 7.8 Hydrogen storage
In addition to being able to store electrical energy, there
7.6.1 Paper batteries has been some research in using carbon nanotubes to
store hydrogen to be used as a fuel source. By taking ad-
A paper battery is a battery engineered to use a paper- vantage of the capillary effects of the small carbon nan-
thin sheet of cellulose (which is the major constituent of otubes, it is possible to condense gases in high density in-
regular paper, among other things) infused with aligned side single-walled nanotubes. This allows for gases, most
carbon nanotubes.[208] The potential for these devices is notably hydrogen (H2 ), to be stored at high densities with-
great, as they may be manufactured via a roll-to-roll pro- out being condensed into a liquid. Potentially, this stor-
cess, which would make it very low-cost, and they would age method could be used on vehicles in place of gas fuel
be lightweight, flexible, and thin. In order to produc- tanks for a hydrogen-powered car. A current issue re-
tively use paper electronics (or any thin electronic de- garding hydrogen-powered vehicles is the on-board stor-
vices), the power source must be equally thin, thus indi- age of the fuel. Current storage methods involve cooling
cating the need for paper batteries. Recently, it has been and condensing the H2 gas to a liquid state for storage
shown that surfaces coated with CNTs can be used to re- which causes a loss of potential energy (25–45%) when
place heavy metals in batteries.[209] More recently, func- compared to the energy associated with the gaseous state.
tional paper batteries have been demonstrated, where a Storage using SWNTs would allow one to keep the H2 in
lithium-ion battery is integrated on a single sheet of pa- its gaseous state, thereby increasing the storage efficiency.
16 7 POTENTIAL APPLICATIONS

This method allows for a volume to energy ratio slightly tized into elementary charges, i.e. electrons, and each
smaller to that of current gas powered vehicles, allowing such elementary charge needs a minimum space, a sig-
for a slightly lower but comparable range.[214] nificant fraction of the electrode surface is not available
An area of controversy and frequent experimentation re- for storage because the hollow spaces are not compatible
garding the storage of hydrogen by adsorption in carbon with the charge’s requirements. With a nanotube elec-
nanotubes is the efficiency by which this process occurs. trode the spaces may be tailored to size—few too large
The effectiveness of hydrogen storage is integral to its or too small—and consequently
[218]
the capacity should be
use as a primary fuel source since hydrogen only contains increased considerably.
about one fourth the energy per unit volume as gasoline.
Studies however show that what is the most important is
the surface area of the materials used. Hence activated 7.10 Radar absorption
carbon with surface area of 2600 m2/g can store up to
5,8% w/w. In all these carbonaceous materials, hydro- Main article: Radar-absorbent material
gen is stored by physisorption at 70-90K.[215]
Radars work in the microwave frequency range, which
can be absorbed by MWNTs. Applying the MWNTs
7.8.1 Experimental capacity to the aircraft would cause the radar to be absorbed and
therefore seem to have a smaller radar cross-section. One
One experiment[216] sought to determine the amount of such application could be to paint the nanotubes onto the
hydrogen stored in CNTs by utilizing elastic recoil detec- plane. Recently there has been some work done at the
tion analysis (ERDA). CNTs (primarily SWNTs) were University of Michigan regarding carbon nanotubes use-
synthesized via chemical vapor disposition (CVD) and fulness as stealth technology on aircraft. It has been found
subjected to a two-stage purification process including that in addition to the radar absorbing properties, the nan-
air oxidation and acid treatment, then formed into flat, otubes neither reflect nor scatter visible light, making it
uniform discs and exposed to pure, pressurized hydrogen essentially invisible at night, much like painting current
at various temperatures. When the data was analyzed, it stealth aircraft black except much more effective. Cur-
was found that the ability of CNTs to store hydrogen de- rent limitations in manufacturing, however, mean that
creased as temperature increased. Moreover, the highest current production of nanotube-coated aircraft is not pos-
hydrogen concentration measured was ~0.18%; signifi- sible. One theory to overcome these current limitations
cantly lower than commercially viable hydrogen storage is to cover small particles with the nanotubes and sus-
needs to be. A separate experimental work performed pend the nanotube-covered particles in a medium such
by using a gravimetric method also revealed the maxi- as paint, which can then be applied to a surface, like a
mum hydrogen uptake capacity of CNTs to be as low as stealth aircraft.[219]
0.2%.[217]

7.8.2 Limitations on efficient hydrogen adsorption
The biggest obstacle to efficient hydrogen storage us-
ing CNTs is the purity of the nanotubes. To achieve
maximum hydrogen adsorption, there must be minimum
graphene, amorphous carbon, and metallic deposits in the
nanotube sample. Current methods of CNT synthesis re-
quire a purification step. However, even with pure nan-
otubes, the absorption capacity is only maximized under
high pressures, which are undesirable in commercial fuel
tanks.
7.9 Supercapacitor
Main article: Supercapacitor
MIT Research Laboratory of Electronics uses nanotubes
to improve supercapacitors. The activated charcoal used
in conventional ultracapacitors has many small hollow
spaces of various size, which create together a large sur-
face to store electric charge. But as charge is quan-
7.11 Textile
The previous studies on the use of CNTs for textile func-
tionalization were focused on fiber spinning for improv-
ing physical and mechanical properties.[220][221][222] Re-
cently a great deal of attention has been focused on coat-
ing CNTs on textile fabrics. Various methods have been
employed for modifying fabrics using CNTs. Shim et
al. produced intelligent e-textiles for Human Biomonitor-
ing using a polyelectrolyte-based coating with CNTs.[223]
Additionally, Panhuis et al. dyed textile material by im-
mersion in either a poly (2-methoxy aniline-5-sulfonic
acid) PMAS polymer solution or PMAS-SWNT disper-
sion with enhanced conductivity and capacitance with a
durable behavior.[224] In another study, Hu and cowork-
ers coated single-walled carbon nanotubes with a sim-
ple “dipping and drying” process for wearable electronics
and energy storage applications.[225] In the recent study,
Li and coworkers using elastomeric separator and al-
most achieved a fully stretchable supercapacitor based on
buckled single-walled carbon nanotube macrofilms. The
electrospun polyurethane was used and provided sound
mechanical stretchability and the whole cell achieve ex-
7.15 Water treatment
cellent charge-discharge cycling stability.[226] CNTs have
an aligned nanotube structure and a negative surface
charge. Therefore, they have similar structures to direct
dyes, so the exhaustion method is applied for coating and
absorbing CNTs on the fiber surface for preparing mul-
tifunctional fabric including antibacterial, electric con-
ductive, flame retardant and electromagnetic absorbance
properties.[227][228][229]
7.12 Optical power detectors
A spray-on mixture of carbon nanotubes and ceramic
demonstrates unprecedented ability to resist damage
while absorbing laser light. Such coatings that absorb as
the energy of high-powered lasers without breaking down
are essential for optical power detectors that measure the
output of such lasers. These are used, for example, in
military equipment for defusing unexploded mines. The
composite consists of multiwall carbon nanotubes and a
ceramic made of silicon, carbon and nitrogen. Includ-
ing boron boosts the breakdown temperature. The nan-
otubes and graphene-like carbon transmit heat well, while
the oxidation-resistant ceramic boosts damage resistance.
Creating the coating involves dispersing the nanotubes in
toluene, to which a clear liquid polymer containing boron
was added. The mixture was heated to 1,100 °C (2,010
°F). The result is crushed into a fine powder, dispersed
again in toluene and sprayed in a thin coat on a copper
surface. The coating absorbed 97.5 percent of the light
from a far-infrared laser and tolerated 15 kilowatts per
square centimeter for 10 seconds. Damage tolerance is
about 50 percent higher than for similar coatings, e.g.,
nanotubes alone and carbon paint.[230][231]
7.13 Acoustics
Carbon nanotubes have also been applied in the acous-
tics(such as loudspeaker and earphone). In 2008
it was shown that a sheet of nanotubes can oper-
ate as a loudspeaker if an alternating current is ap-
plied. The sound is not produced through vibration but
thermoacoustically.[232][233] In 2013, a carbon nanotube
(CNT) thin yarn thermoacoustic earphone together with
CNT thin yarn thermoacoustic chip was demonstrated
by a research group of Tsinghua-Foxconn Nanotechnol-
ogy Research Center in Tsinghua University,[234] using a
Si-based semi-conducting technology compatible fabri-
cation process.
7.14 Environmental remediation
A CNT nano-structured sponge (nanosponge) containing
sulfur and iron is more effective at soaking up water con-
taminants such as oil, fertilizers, pesticides and pharma-
ceuticals. Their magnetic properties make them easier to
retrieve once the clean-up job is done. The sulfur and iron
17
increases sponge size to around 2 centimetres (0.79 in). It
also increases porosity due to beneficial defects, creating
buoyancy and reusability. Iron, in the form of ferrocene
makes the structure easier to control and enables recovery
using magnets. Such nanosponges increase the absorp-
tion of the toxic organic solvent dichlorobenzene from
water by 3.5 times. The sponges can absorb vegetable oil
up to 150 times their initial weight and can absorb engine
oil as well.[235][236]
Earlier, a magnetic boron-doped MWNT nanosponge
that could absorb oil from water. The sponge was
grown as a forest on a substrate via chemical vapor dis-
position. Boron puts kinks and elbows into the tubes
as they grow and promotes the formation of covalent
bonds. The nanosponges retain their elastic property af-
ter 10,000 compressions in the lab. The sponges are both
superhydrophobic, forcing them to remain at the water’s
surface and oleophilic, drawing oil to them.[237][238]
7.15 Water treatment
It has been shown that carbon nanotubes exhibit strong
adsorption affinities to a wide range of aromatic and
aliphatic contaminants in water,[239][240][241] due to their
large and hydrophobic surface areas. They also showed
similar adsorption capacities as activated carbons in the
presence of natural organic matter.[242] As a result, they
have been suggested as promising adsorbents for removal
of contaminant in water and wastewater treatment sys-
tems.
Moreover, membranes made out of carbon nanotube ar-
rays have been suggested as switchable molecular sieves,
with sieving and permeation features that can be dynam-
ically activated/deactivated by either pore size distribu-
tion (passive control) or external electrostatic fields (ac-
tive control).[243]
7.16 Other applications
Carbon nanotubes have been implemented in nanoelec-
tromechanical systems, including mechanical memory el-
ements (NRAM being developed by Nantero Inc.) and
nanoscale electric motors (see Nanomotor or Nanotube
nanomotor).
Carboxyl-modified single-walled carbon nanotubes (so
called zig-zag, armchair type) can act as sensors of atoms
and ions of alkali metals Na, Li, K.[244] In May 2005,
Nanomix Inc. placed on the market a hydrogen sensor
that integrated carbon nanotubes on a silicon platform.
Since then, Nanomix has been patenting many such sen-
sor applications, such as in the field of carbon dioxide, ni-
trous oxide, glucose, DNA detection, etc. End of 2014,
Tulane University researchers have tested Nanomix’s fast
and fully automated point of care diagnostic system in
Sierra Leone to help for rapid testing for Ebola. Nanomix
18 8 DISCOVERY

announced that a product could be launched within three Candida albicans has been used in combination with car-
to six months. bon nanotubes (CNT) to produce stable electrically con-
Eikos Inc of Franklin, Massachusetts and Unidym Inc. ductive bio-nano-composite tissue materials that have
[251]
of Silicon Valley, California are developing transparent, been used as temperature sensing elements.
electrically conductive films of carbon nanotubes to re- The SWNT production company OCSiAl developed a
place indium tin oxide (ITO). Carbon nanotube films are series of masterbatches for industrial use of single-wall
substantially more mechanically robust than ITO films, CNTs in multiple types of rubber blends and tires, with
making them ideal for high-reliability touchscreens and initial trials showing increases in hardness, viscosity, ten-
flexible displays. Printable water-based inks of carbon sile strain resistance and resistance to abrasion while re-
nanotubes are desired to enable the production of these ducing elongation and compression[252] In tires the three
films to replace ITO.[245] Nanotube films show promise primary characteristics of durability, fuel efficiency and
for use in displays for computers, cell phones, PDAs, and traction were improved using SWNTs. The develop-
ATMs. ment of rubber masterbatches built on earlier work by the
A nanoradio, a radio receiver consisting of a single nan- Japanese National Institute of Advanced Industrial Sci-
otube, was demonstrated in 2007. ence & Technology showing rubber to be a viable candi-
date for improvement with SWNTs.[253]
A flywheel made of carbon nanotubes could be spun at ex-
tremely high velocity on a floating magnetic axis in a vac- Introducing MWNTs to polymers can improve flame[254] re-
uum, and potentially store energy at a density approach- tardancy and retard thermal degradation of polymer.
ing that of conventional fossil fuels. Since energy can be The results confirmed that combination of MWNTs and
added to and removed from flywheels very efficiently in ammonium polyphosphates [255] show a synergistic effect for
the form of electricity, this might offer a way of storing improving flame retardancy.
electricity, making the electrical grid more efficient and
variable power suppliers (like wind turbines) more useful
in meeting energy needs. The practicality of this depends 8 Discovery
heavily upon the cost of making massive, unbroken nan-
otube structures, and their failure rate under stress.
See also: Timeline of carbon nanotubes
Carbon nanotube springs have the potential to indefinitely
store elastic potential energy at ten times the density of
The true identity of the discoverers of carbon nanotubes
lithium-ion batteries with flexible charge and discharge
is a subject of some controversy.[256] For years, scientists
rates and extremely high cycling durability.
assumed that Sumio Iijima of NEC had discovered car-
Ultra-short SWNTs (US-tubes) have been used as bon nanotubes in 1991. He published a paper describ-
nanoscaled capsules for delivering MRI contrast agents ing his discovery which initiated a flurry of excitement
in vivo.[246] and could be credited by inspiring the many scientists
Carbon nanotubes provide a certain potential for metal- now studying applications of carbon nanotubes. Though
free catalysis of inorganic and organic reactions. For Iijima has been given much of the credit for discovering
instance, oxygen groups attached to the surface of car- carbon nanotubes, it turns out that the timeline of [256] car-
bon nanotubes have the potential to catalyze oxida- bon nanotubes goes back much further than 1991.
tive dehydrogenations[247] or selective oxidations.[248] In 1952 L. V. Radushkevich and V. M. Lukyanovich
Nitrogen-doped carbon nanotubes may replace platinum published clear images of 50 nanometer diameter tubes
catalysts used to reduce oxygen in fuel cells. A forest of made[100] of carbon in the Soviet Journal of Physical Chem-
vertically aligned nanotubes can reduce oxygen in alka- istry. This discovery was largely unnoticed, as the ar-
line solution more effectively than platinum, which has ticle was published in Russian, and Western scientists’
been used in such applications since the 1960s. Here, the access to Soviet press was limited during the Cold War.
nanotubes have the added benefit of not being subject to Before they came to be known as carbon nanotubes, in
carbon monoxide poisoning. [249] 1976, Morinobu Endo of CNRS observed hollow tubes
of rolled up graphite sheets synthesised by a chemical
Wake Forest University engineers are using multiwalled vapour-growth technique.[257] The first specimens ob-
carbon nanotubes to enhance the brightness of field- served would later come to be known as single-walled car-
induced polymer electroluminescent technology, poten- bon nanotubes (SWNTs).[258] The three scientists have
tially offering a step forward in the search for safe, pleas- been the first ones to show images of a nanotube with a
ing, high-efficiency lighting. In this technology, moldable solitary graphene wall.[256]
polymer matrix emits light when exposed to an electric
current. It could eventually yield high-efficiency lights Endo, in his early review of vapor-phase-grown carbon
without the mercury vapor of compact fluorescent lamps fibers (VPCF), also reminded us that he had observed a
or the bluish tint of some fluorescents and LEDs, which hollow tube, linearly extended [259]
with parallel carbon layer
has been linked with circadian rhythm disruption. [250] faces near the fiber core. This appears to be the ob-
servation of multi-walled carbon nanotubes at the center
 19

of the fiber.[258] The mass-produced MWCNTs today are • Buckypaper

strongly related to the VPGCF developed by Endo.[258] In
fact, they call it the “Endo-process”, out of respect for his • Carbide-derived carbon
early work and patents.[258][260] • Carbon nanocone
In 1979, John Abrahamson presented evidence of car-
• Carbon nanofibers
bon nanotubes at the 14th Biennial Conference of Car-
bon at Pennsylvania State University. The conference • Carbon nanoparticles
paper described carbon nanotubes as carbon fibers that
were produced on carbon anodes during arc discharge. A • Carbon nanoscrolls
characterization of these fibers was given as well as hy-
• Carbon nanotube chemistry
potheses for their growth in a nitrogen atmosphere at low
pressures.[261] • Colossal carbon tube
In 1981, a group of Soviet scientists published the re- • Diamond nanothread
sults of chemical and structural characterization of car-
bon nanoparticles produced by a thermocatalytical dis- • Filamentous carbon
proportionation of carbon monoxide. Using TEM images
and XRD patterns, the authors suggested that their “car- • Graphene oxide paper
bon multi-layer tubular crystals” were formed by rolling • List of software for nanostructures modeling
graphene layers into cylinders. They speculated that by
rolling graphene layers into a cylinder, many different • Molecular modelling
arrangements of graphene hexagonal nets are possible.
• Nanoflower
They suggested two possibilities of such arrangements:
circular arrangement (armchair nanotube) and a spiral, • Ninithi (nanotube modelling software)
helical arrangement (chiral tube).[262]
• Organic semiconductor
In 1987, Howard G. Tennent of Hyperion Catalysis was
issued a U.S. patent for the production of “cylindrical dis- • Selective chemistry of single-walled nanotubes
crete carbon fibrils” with a “constant diameter between
about 3.5 and about 70 nanometers..., length 102 times • Silicon nanotubes
the diameter, and an outer region of multiple essentially • Timeline of carbon nanotubes
continuous layers of ordered carbon atoms and a distinct
inner core....”[263] • Vantablack, a substance produced in 2014; the
blackest substance known
Iijima’s discovery of multi-walled carbon nanotubes in
the insoluble material of arc-burned graphite rods in
1991[264] and Mintmire, Dunlap, and White’s indepen-
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11 External links
• Nanohedron.com image gallery with carbon nan-
otubes
• The Nanotube site. Last updated 2009.05.03
• EU Marie Curie Network CARBIO: Multifunc-
tional carbon nanotubes for biomedical applications
• Carbon nanotube on arxiv.org
• C60 and Carbon Nanotubes a short video explaining
how nanotubes can be made from modified graphite
sheets and the three different types of nanotubes that
are formed
• Carbon Nanotubes & Buckyballs.
• The Wondrous World of Carbon Nanotubes
• Learning module for Bandstructure of Carbon Nan-
otubes and Nanoribbons
• Durability of carbon nanotubes and their potential to
cause inflammation by Dr Megan Osmond and oth-
ers. (SafeWork Australia, May 2011). This was a
collaboration between the Institute of Occupational
Medicine, Edinburgh University and CSIRO in Aus-
tralia.
• NT06 Seventh International Conference on the Sci-
ence and Application of Nanotubes
• NT05 Sixth International Conference on the Science
and Application of Nanotubes
• Selection of free-download articles on carbon nan-
otubes
• First computer made of carbon nanotubes is un-
veiled (BBC News) 2013-09-25
• Research using carbon nanotubes for microfabrica-
tion and in other applications
32 12 TEXT AND IMAGE SOURCES, CONTRIBUTORS, AND LICENSES

12 Text and image sources, contributors, and licenses

12.1 Text
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Awbull, Sheephugger, LilHelpa, Prsomani, Xqbot, Mesudhanshu, Hochung4, Capricorn42, Drilnoth, Ganaren, P99am, Anna Frode-
siak, Teabagger69696969, Ugglebot, Frosted14, RibotBOT, Nanoshel, Techtracker, Adrignola, Jjm2052, GliderMaven, Redrimshot86,
Prari, FrescoBot, Nmedard, Kdn1982, Caficionado, Thatsjustnotcricket, ZenerV, Rustin313, Hunsik, Citation bot 1, Gil987, Pinethicket,
Matthieu.berthome, Jonesey95, DWCNT, Zoid62, MondalorBot, Serols, Casimir9999, Anoniemoos, Orenburg1, TobeBot, Trappist the
monk, Reaper Eternal, Earthandmoon, Somnath2, Dedcreature, Kt57, Elikrieg, RjwilmsiBot, Azure777, Bento00, Bossypenguin, Strea-
padair, SonyaCollier, Zac2d, Wwara~enwiki, EmausBot, John of Reading, Urianway, Beatnik8983, NemethOH, Aprilsola, Dewritech,
TheWhiteness24, GoingBatty, Pavlo Chemist, Tommy2010, K6ka, Porterf, Hedles, Lent1999, Alushing, Hhhippo, ZéroBot, Fæ, Bollyjeff,
Stanford96, Rassaei, Yiosie2356, Can You Prove That You're Human, Sthubertus, GenghisOwns, AManWithNoPlan, Gz33, Wingman4l7,
TyA, Haydaleemc2, Langmuir33, Tls60, Rangoon11, CMMCNT, Mister Mormon, Senator2029, Whoop whoop pull up, ClueBot NG,
Popproject3, Toughpkh, Incompetence, SusikMkr, Eric Wieser, Zaargg, Yuehai1981, Helpful Pixie Bot, JohnSRoberts99, KD888, Bib-
code Bot, BG19bot, Shi2011, Mohamed CJ, Micronanolab, Arigatous, Tiscando, MusikAnimal, Sbellucci, Pre-searcher, Rank50Unlocked,
Aisteco, PennyF, Kingdbu, Hatef2000, BattyBot, Googol30, Cyberbot II, ChrisGualtieri, BRStoner, Sumanneu, Dexbot, Vanwyhkp, Steve
the pie man, Leafonesky, Daniyal866, Andyhowlett, Richard Lozier, Ilovebmw, ZX95, Reatlas, Shadout mapes, Pcgamelover4life, Bc-
chakra, Akash.sadashivpeth, Mrsquirrel dh, Luot, Kroegerjens, Jakec, DavidLeighEllis, CensoredScribe, MarinaVladivostok, Ginsuloft,
Manul, StainlessSteelScorpion, Free2KnowFree2Think, Anrnusna, Stamptrader, Jim7022003, Matsci2, Yshaoya, Cousteau, Baghalion,
Wyn.junior, Monkbot, SkateTier, Baltazarbar, Osmiljanic, Sumajillela516, CoolAsFinnBro, Ankit.sqz, Jwill530, Matfas, Anoonymoouse,
Xinlistevens, Glalwani06, Julietdeltalima, Wiki Typewriter, Ardent1F, DCGE, Somethingorother78910, Mediavalia, Lyarsky, Turbograph-
ics, Spectro Guru, Toshithomas, Ogapul, Emily Temple-Wood (NIOSH), User000name, Belluccinext, RikiTikiT, Fluffychacham, Kas-
parBot, Carey821, Ctacebu4, Vicol, Wangsimin0000, Yuki uno, Ali eatmadi, Latosh Boris, Erindesilva, Karbokation, Carbonnanotube,
Michelleisatwin, Adamantanon, Mahdishesami, Mdahm85, Gongwool, Alan.taylor2013, Vivienstewart and Anonymous: 902
12.2 Images 33

12.2 Images
• File:3D_carbon_scaffolds.PNG Source: https://upload.wikimedia.org/wikipedia/commons/5/53/3D_carbon_scaffolds.PNG License:
CC BY-SA 4.0 Contributors: Own work Original artist: Glalwani06
• File:C60-rods.png Source: https://upload.wikimedia.org/wikipedia/commons/0/09/C60-rods.png License: CC-BY-SA-3.0 Contributors:
? Original artist: ?
• File:CNTSEM.JPG Source: https://upload.wikimedia.org/wikipedia/commons/9/9b/CNTSEM.JPG License: CC BY-SA 3.0 Contribu-
tors: Own work (Original text: I created this work entirely by myself.) Original artist: Materialscientist (talk)
• File:CNTnames.png Source: https://upload.wikimedia.org/wikipedia/commons/3/35/CNTnames.png License: Public domain Contribu-
tors: ? Original artist: ?
• File:CSIRO_ScienceImage_1074_Carbon_nanotubes_being_spun_to_form_a_yarn.jpg Source: https://upload.wikimedia.org/
wikipedia/commons/a/a3/CSIRO_ScienceImage_1074_Carbon_nanotubes_being_spun_to_form_a_yarn.jpg License: CC BY 3.0
Contributors: http://www.scienceimage.csiro.au/image/1074 Original artist: division, CSIRO
• File:Carbon_nanotube_bands.gif Source: https://upload.wikimedia.org/wikipedia/commons/0/01/Carbon_nanotube_bands.gif Li-
cense: CC BY 3.0 Contributors: CNTBands simulator on www.nanoHUB.org. Link: http://nanohub.org/resources/8807 Original artist:
Saumitra R Mehrotra & Gerhard Klimeck
• File:Chiraltube.png Source: https://upload.wikimedia.org/wikipedia/commons/d/da/Chiraltube.png License: Public domain Contribu-
tors: http://www.ncnr.nist.gov/staff/taner/nanotube/types.html Original artist: Taner Yildirim (The National Institute of Standards and
Technology - NIST)
• File:CntHAADF.jpg Source: https://upload.wikimedia.org/wikipedia/commons/2/22/CntHAADF.jpg License: CC BY-SA 3.0 Contrib-
utors: Own work (Original text: I created this work entirely by myself.) Original artist: Materialscientist (talk)
• File:Cnt_diameter_effect.jpg Source: https://upload.wikimedia.org/wikipedia/commons/f/fc/Cnt_diameter_effect.jpg License: Public
domain Contributors: NSF Original artist: Hersam
• File:Commons-logo.svg Source: https://upload.wikimedia.org/wikipedia/en/4/4a/Commons-logo.svg License: CC-BY-SA-3.0 Contribu-
tors: ? Original artist: ?
• File:Cycloparaphenylene.PNG Source: https://upload.wikimedia.org/wikipedia/commons/f/f7/Cycloparaphenylene.PNG License: CC
BY-SA 3.0 Contributors: Own work Original artist: Materialscientist
• File:Edit-clear.svg Source: https://upload.wikimedia.org/wikipedia/en/f/f2/Edit-clear.svg License: Public domain Contributors: The
Tango! Desktop Project. Original artist:
The people from the Tango! project. And according to the meta-data in the file, specifically: “Andreas Nilsson, and Jakub Steiner (although
minimally).”
• File:Folder_Hexagonal_Icon.svg Source: https://upload.wikimedia.org/wikipedia/en/4/48/Folder_Hexagonal_Icon.svg License: Cc-by-
sa-3.0 Contributors: ? Original artist: ?
• File:Fullerene_Nanogears_-_GPN-2000-001535.jpg Source: https://upload.wikimedia.org/wikipedia/commons/b/b6/Fullerene_
Nanogears_-_GPN-2000-001535.jpg License: Public domain Contributors: Great Images in NASA: Home - info - pic Original artist:
NASA
• File:Kohlenstoffnanoroehre_Animation.gif Source: https://upload.wikimedia.org/wikipedia/commons/7/76/Kohlenstoffnanoroehre_
Animation.gif License: CC-BY-SA-3.0 Contributors: German Wikipedia, original upload 29. Dez 2004 by APPER Original artist: Original
hochgeladen von Schwarzm am 30. Aug 2004; Selbst gemacht mit C4D/Cartoonrenderer, GNU FDL
• File:Multi-walled_Carbon_Nanotube.png Source: https://upload.wikimedia.org/wikipedia/commons/b/bc/Multi-walled_Carbon_
Nanotube.png License: CC BY-SA 3.0 Contributors: Own work Original artist: Eric Wieser
• File:Mutr-nanotubes1.jpg Source: https://upload.wikimedia.org/wikipedia/commons/d/d0/Mutr-nanotubes1.jpg License: CC BY-SA
3.0 Contributors: Own work Original artist: Shaddack
• File:NanoBud.JPG Source: https://upload.wikimedia.org/wikipedia/commons/0/00/NanoBud.JPG License: CC BY-SA 3.0 Contributors:
Own work Original artist: Arkady Krasheninnikov
• File:PICT0111.JPG Source: https://upload.wikimedia.org/wikipedia/commons/b/b1/PICT0111.JPG License: Public domain Contribu-
tors: Own work Original artist: polyparadigm (talk · contribs)
• File:SEM_of_carbon_nanotubes_with_graphene_foliates_of_varying_density,_deposited_via_microwave_plasma_enhanced_
CVD.tif Source: https://upload.wikimedia.org/wikipedia/commons/f/ff/SEM_of_carbon_nanotubes_with_graphene_foliates_of_
varying_density%2C_deposited_via_microwave_plasma_enhanced_CVD.tif License: CC BY-SA 3.0 Contributors: Own work Original
artist: BRStoner
• File:Space_elevator_structural_diagram.png Source: https://upload.wikimedia.org/wikipedia/commons/a/ad/Space_elevator_
structural_diagram.png License: CC-BY-SA-3.0 Contributors: ? Original artist: ?
• File:Symbol_list_class.svg Source: https://upload.wikimedia.org/wikipedia/en/d/db/Symbol_list_class.svg License: Public domain Con-
tributors: ? Original artist: ?

12.3 Content license

• Creative Commons Attribution-Share Alike 3.0