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Carbon nanotube

Not to be confused with Carbon fiber. Carbon nanotubes (CNTs) are allotropes of car-

. Carbon nanotubes ( CNTs ) are allotropes of car- Rotating single-walled zigzag carbon nanotube bon

bon with a cylindrical nanostructure. Nanotubes have been constructed with length-to-diameter ratio of up to 132,000,000:1, [1] significantly larger than for any other material. These cylindrical carbon molecules have un- usual properties, which are valuable for nanotechnology, electronics, optics and other fields of materials science and technology. In particular, owing to their extraordi- nary thermal conductivity and mechanical and electrical properties, carbon nanotubes find applications as addi- tives to various structural materials. For instance, nan- otubes form a tiny portion of the material(s) in some (pri- marily carbon fiber) baseball bats, golf clubs, car parts or damascus steel. [2][3]

Nanotubes are members of the fullerene structural fam- ily. Their name is derived from their long, hollow struc- ture with the walls formed by one-atom-thick sheets of carbon, called graphene. These sheets are rolled at spe- cific and discrete ("chiral") angles, and the combina- tion of the rolling angle and radius decides the nanotube properties; for example, whether the individual nanotube shell is a metal or semiconductor. Nanotubes are cate- gorized as single-walled nanotubes (SWNTs) and multi- walled nanotubes (MWNTs). Individual nanotubes nat- urally align themselves into “ropes” held together by van der Waals forces, more specifically, pi-stacking.

Applied quantum chemistry, specifically, orbital hy-

1

bridization best describes chemical bonding in nanotubes. The chemical bonding of nanotubes is composed en- tirely of sp 2 bonds, similar to those of graphite. These bonds, which are stronger than the sp 3 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).

1.2 Single-walled

Armchair (n,n) i.e.: m=n

The translation vector is bent, while the chiral vector stays straight

Graphene nanoribbon

The chiral vector is bent, while the translation vector stays straight

Zigzag (n,0)

Chiral (n,m)

n and m can be counted at the end of the tube

Graphene nanoribbon

Most single-walled nanotubes (SWNTs) have a diame- ter of close to 1 nanometer, and can be many millions of times longer. The structure of a SWNT can be concep- tualized by wrapping a one-atom-thick layer of graphite called graphene into a seamless cylinder. The way the graphene sheet is wrapped is represented by a pair of in- dices (n,m). The integers n and m denote the number of unit vectors along two directions in the honeycomb crystal lattice of graphene. If m = 0, the nanotubes are called zigzag nanotubes, and if n = m, the nanotubes are called armchair nanotubes. Otherwise, they are called chiral.

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1 TYPES OF CARBON NANOTUBES AND RELATED STRUCTURES

2 1 TYPES OF CARBON NANOTUBES AND RELATED STRUCTURES The ( n , m ) nanotube

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 a 1 and a 2 are the unit vectors of graphene in real space.

and a 2 are the unit vectors of graphene in real space. A scanning tunneling microscopy

A scanning tunneling microscopy image of single-walled carbon

nanotube

SWNTs are an important variety of carbon nanotube be- 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.

to The Global Market for Carbon Nanotubes report. A transmission electron microscopy image of a

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

bon nanotube

1.3 Multi-walled

image of a single-walled car- bon nanotube 1.3 Multi-walled The diameter of an ideal nanotube can

The diameter of an ideal nanotube can be calculated from its (n,m) indices as follows

A scanning electron microscopy image of carbon nanotubes bun- dles

d =

Multi-walled nanotubes (MWNTs) consist of multiple

rolled layers (concentric tubes) of graphene. There are two models that can be used to describe the structures

a

π (n 2 + nm + m 2 ) = 78.3 ((n + m) 2 nm)pm,

of multi-walled nanotubes. In the Russian Doll model,

where a = 0.246 nm.

sheets of graphite are arranged in concentric cylinders,

e.g., a (0,8) single-walled nanotube (SWNT) within a

1.5 Nanobud

3

1.5 Nanobud 3 Triple-walled armchair carbon nanotube larger (0,17) single-walled nanotube. In the Parchment model, a

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- ducting. Because of statistical probability and restrictions on the relative diameters of the individual tubes, one of the shells, and thus the whole MWNT, is usually a zero- gap metal.

Double-walled carbon nanotubes (DWNTs) form a spe- cial class of nanotubes because their morphology and properties are similar to those of SWNTs but their re- sistance to chemicals is significantly improved. This is especially important when functionalization is required (this means grafting of chemical functions at the surface of the nanotubes) to add new properties to the CNT. In the case of SWNTs, covalent functionalization will break 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 the outer wall is modified. DWNT synthesis on the gram- 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

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

and radius of the tube. [ 1 1 ] [ 1 2 ] 1.5 Nanobud A

A stable nanobud structure

Carbon nanobuds are a newly created material combining two previously discovered allotropes of carbon: carbon nanotubes and fullerenes. In this new material, fullerene- like “buds” are covalently bonded to the outer sidewalls of the underlying carbon nanotube. This hybrid material has useful properties of both fullerenes and carbon nanotubes. In particular, they have been found to be exceptionally good field emitters. In composite materials, the attached fullerene molecules may function as molecular anchors preventing slipping of the nanotubes, thus improving the composite’s mechanical properties.

1.6 Three-dimensional carbon nanotube architectures

1.6 Three-dimensional carbon nanotube architectures 3D carbon scaffolds Recently, several studies have

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

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1 TYPES OF CARBON NANOTUBES AND RELATED STRUCTURES

method to fabricate macroscopic, free-standing, porous, all-carbon scaffolds using single- and multi-walled car- bon nanotubes as building blocks. [13] These scaffolds pos- sess macro-, micro-, and nano- structured pores and the porosity can be tailored for specific applications. These 3D all-carbon scaffolds/architectures may be used for the fabrication of the next generation of energy stor- age, supercapacitors, field emission transistors, high- performance catalysis, photovoltaics, and biomedical de- vices and implants. [14]

1.7 Graphenated carbon nanotubes (g- CNTs)

[ 1 4 ] 1.7 Graphenated carbon nanotubes (g- CNTs) SEM series of graphenated CNTs with

SEM series of graphenated CNTs with varying foliate density

Graphenated CNTs are a relatively new hybrid that com- bines graphitic foliates grown along the sidewalls of mul- tiwalled or bamboo style CNTs. Yu et al. [15] reported on “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 enhanced supercapacitor performance. Hsu et al. further reported on similar structures formed on carbon fiber pa- per, also for use in supercapacitor applications. [17] Pham et al. [18][19] also reported a similar structure, namely “graphene-carbon nanotube hybrids”, grown directly onto carbon fiber paper to form an integrated, binder free, high surface area conductive catalyst support for Proton Ex- change Membrane Fuel Cells electrode applications with enhanced performance and durability. The foliate den- sity can vary as a function of deposition conditions (e.g. temperature and time) with their structure ranging from few layers of graphene (< 10) to thicker, more graphite- like. [20]

The fundamental advantage of an integrated graphene- 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, but they are difficult to arrange in a three-dimensional, high volume-density geometry. CNTs are readily aligned in a high density geometry (i.e., a vertically aligned forest) [21] but lack high charge density surfaces—the side- walls of the CNTs are similar to the basal plane of graphene and exhibit low charge density except where edge defects exist. Depositing a high density of graphene foliates along the length of aligned CNTs can signifi- cantly increase the total charge capacity per unit of nom- inal area as compared to other carbon nanostructures. [22]

1.8 Nitrogen-doped carbon nanotubes

Nitrogen doped carbon nanotubes (N-CNTs) can be pro-

duced through five main methods, chemical vapor de- position, [23][24] high-temperature and high-pressure reac- tions, gas-solid reaction of amorphous carbon with NH 3

at high temperature, [25] solid reaction, [26] and solvother-

mal synthesis. [27]

N-CNTs can also be prepared by a CVD method of py- rolyzing melamine under Ar at elevated temperatures of 800–980 °C. However synthesis by CVD of melamine results in the formation of bamboo-structured CNTs. XPS spectra of grown N-CNTs reveal nitrogen in five 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- ide nanoparticle deposition which can further enhance storage capacity, especially in anode materials for Li-ion batteries. [28] However boron-doped nanotubes have been shown to make batteries with triple capacity. [29]

1.9 Peapod

A carbon peapod [30][31] is a novel hybrid carbon material

which traps fullerene inside a carbon nanotube. It can possess interesting magnetic properties with heating and irradiation. It can also be applied as an oscillator during theoretical investigations and predictions. [32][33]

1.10 Cup-stacked carbon nanotubes

Cup-stacked carbon nanotubes (CSCNTs) differ from other quasi-1D carbon structures, which normally behave

as quasi-metallic conductors of electrons. CSCNTs ex-

hibit semiconducting behaviors due to the stacking mi-

crostructure of graphene layers. [34]

1.11 Extreme carbon nanotubes

The observation of the longest carbon nanotubes grown so far are over 1/2 m (550 mm long) was reported in 2013. [35] These nanotubes were grown on Si sub- strates using an improved chemical vapor deposition

(CVD) method and represent electrically uniform arrays

of single-walled carbon nanotubes. [1]

The shortest carbon nanotube is the organic compound cycloparaphenylene, which was synthesized in early

2009. [36][37]

2.2 Hardness

5

2.2 Hardness 5 Cycloparaphenylene The thinnest carbon nanotube is the armchair (2,2) CNT with a diameter

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

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 sp 2 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

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/cm 3 , [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]

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2 PROPERTIES

2.3 Wettability

The surface wettability of CNT is of importance for its applications in various settings. Although the intrinsic contact angle of graphite is around 90°, the contact an- gles of most as-synthesized CNT arrays are over 160°, exhibiting a superhydrophobic property. By applying a low voltage as low as 1.3V, the extreme water repellant surface can be switched into superhydrophilic. [61]

2.4 Kinetic properties

Multi-walled nanotubes are multiple concentric nan- otubes precisely nested within one another. These ex- hibit a striking telescoping property whereby an inner nanotube core may slide, almost without friction, within its outer nanotube shell, thus creating an atomically per- fect linear or rotational bearing. This is one of the first true examples of molecular nanotechnology, the precise positioning of atoms to create useful machines. Already, this property has been utilized to create the world’s small- est rotational motor. [62] Future applications such as a gi- gahertz mechanical oscillator are also envisioned.

2.5 Electrical properties

oscillator are also envisioned. 2.5 Electrical properties Band structures computed using tight binding approximation

Band structures computed using tight binding approximation for (6,0) CNT (zigzag, metallic), (10,2) CNT (semiconducting) and (10,10) CNT (armchair, metallic).

Because of the symmetry and unique electronic struc- ture of graphene, the structure of a nanotube strongly

affects its electrical properties. For a given (n,m) nan- otube, if n = m, the nanotube is metallic; if n m is a multiple of 3, then the nanotube is semiconducting with a very small band gap, otherwise the nanotube is a mod- erate semiconductor. Thus all armchair (n = m) nan- otubes are metallic, and nanotubes (6,4), (9,1), etc. are semiconducting. [63]

However, this rule has exceptions, because curvature ef- 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- lations. Likewise, zigzag and chiral SWCNTs with small diameters that should be metallic have a finite gap (arm- chair nanotubes remain metallic). [63] In theory, metallic nanotubes can carry an electric current density of 4 × 10 9 A/cm 2 , which is more than 1,000 times greater than those of metals such as copper, [64] where for copper intercon- nects current densities are limited by electromigration.

Because of its nanoscale cross-section, electrons prop- agate only along the tube’s axis. As a result, carbon nanotubes are frequently referred to as one-dimensional conductors. The maximum electrical conductance of a single-walled carbon nanotube is 2G 0 , where G 0 =2e 2 /h is the conductance of a single ballistic quantum chan- nel. [65]

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

2.7 Thermal properties

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 385 W·m 1 ·K 1 . A SWNT has a room-temperature ther- mal conductivity across its axis (in the radial direction) of about 1.52 W·m 1 ·K 1 , [69] which is about as thermally conductive as soil. The temperature stability of carbon nanotubes is estimated to be up to 2800 °C in vacuum and about 750 °C in air. [70]

3.1 Toxicity

7

2.8 Defects

As with any material, the existence of a crystallographic defect affects the material properties. Defects can occur in the form of atomic vacancies. High levels of such de- fects can lower the tensile strength by up to 85%. An important example is the Stone Wales defect, which cre- ates a pentagon and heptagon pair by rearrangement of the bonds. Because of the very small structure of CNTs, the tensile strength of the tube is dependent on its weakest segment in a similar manner to a chain, where the strength of the weakest link becomes the maximum strength of the chain.

Crystallographic defects also affect the tube’s electrical properties. A common result is lowered conductivity through the defective region of the tube. A defect in armchair-type tubes (which can conduct electricity) can cause the surrounding region to become semiconduct- ing, and single monatomic vacancies induce magnetic properties. [71]

Crystallographic defects strongly affect the tube’s ther- mal properties. Such defects lead to phonon scattering, which in turn increases the relaxation rate of the phonons. This reduces the mean free path and reduces the ther- mal conductivity of nanotube structures. Phonon trans- port simulations indicate that substitutional defects such 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- ing over a wide range of frequencies, leading to a greater reduction in thermal conductivity. [72]

3 Safety and Health

3.1 Toxicity

The toxicity of carbon nanotubes has been an impor- tant question in nanotechnology. As of 2007, such research had just begun. The data is still fragmen- tary and subject to criticism. Preliminary results high- light the difficulties in evaluating the toxicity of this heterogeneous material. Parameters such as structure, size distribution, surface area, surface chemistry, surface charge, and agglomeration state as well as purity of the samples, have considerable impact on the reactivity of carbon nanotubes. However, available data clearly show that, under some conditions, nanotubes can cross mem- brane barriers, which suggests that, if raw materials reach the organs, they can induce harmful effects such as in- flammatory and fibrotic reactions. [73][74]

Under certain conditions CNTs can enter human cells and accumulate in the cytoplasm, causing cell death. [75]

Results of rodent studies collectively show that regardless of the process by which CNTs were synthesized and the types and amounts of metals they contained, CNTs were capable of producing inflammation, epithelioid granu- lomas (microscopic nodules), fibrosis, and biochemi- cal/toxicological changes in the lungs. [76] Comparative toxicity studies in which mice were given equal weights of test materials showed that SWCNTs were more toxic than quartz, which is considered a serious occupational health hazard when chronically inhaled. As a control, ul- trafine carbon black was shown to produce minimal lung responses. [77]

Carbon nanotubes deposit in the alveolar ducts by align- ing lengthwise with the airways; the nanotubes will of- ten combine with metals. [78] The needle-like fiber shape of CNTs is similar to asbestos fibers. This raises the idea that widespread use of carbon nanotubes may lead to pleural mesothelioma, a cancer of the lining of the lungs, or peritoneal mesothelioma, a cancer of the lining of the abdomen (both caused by exposure to asbestos). A re- cently published pilot study supports this prediction. [79] Scientists exposed the mesothelial lining of the body cav- ity of mice to long multiwalled carbon nanotubes and observed asbestos-like, length-dependent, pathogenic be- havior that included inflammation and formation of le- sions known as granulomas. Authors of the study con- clude:

This is of considerable importance, be- cause research and business communities con- 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- ther research and great caution before intro- ducing such products into the market if long- term harm is to be avoided. [79]

Although further research is required, the available data suggest that under certain conditions, especially those in- volving chronic exposure, carbon nanotubes can pose a serious risk to human health. [73][75][77][79]

In 2014, experts from the International Agency for Re- search on Cancer (IARC) assessed the carcinogenicity of CNTs, including SWCNTs and MWCNTs. No human epidemiologic or cancer data was available to the IARC Working Group at the time, so the evaluation focused on the results of in vivo animal studies assessing the carcino- genicity of SWCNTs and MWCNTs in rodents.

The Working Group concluded that there was sufficient evidence for the specific MWCNT type “MWCNT-7”, limited evidence for the two other types of MWCNTs with dimensions similar to MWCNT-7, and inadequate evidence for SWCNTs. Therefore, it was agreed to specifically classify MWCNT-7 as possibly carcinogenic to humans (Group 2B) while the other forms of CNT, namely SWCNT and other types of MWCNT, excluding

8

4 SYNTHESIS

MWCNT-7, were considered not classifiable as to their carcinogenicity to humans (Group 3) due to a lack of co- herent evidence. [80]

3.2 Epidemiology and Risk Management

Currently, there is a lack of epidemiological evidence linking exposure to CNT to human health effects. To date, there have been only a handful of published epi- demiological studies that have solely examined the health effects related to the exposure of CNT, while sev- eral other studies are currently underway and yet to be published. [81][82][83] With the limited amount of human data, scientists are more reliant on the results of current animal toxicity studies to predict adverse health effects, as well as applying what is already known about expo- sures to other fibrous materials such as asbestos or fine and ultra-fine particulates. This limitation of human data has lead to the use of the precautionary principal, which urges workplaces to limit exposure levels to CNT as low as possibly achievable in the absence of known health ef- fects data. [84]

To date, several international government agencies, as 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- 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/m 3 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/m 3 . [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 Safety Executive titled “Using nanomaterials at work In- cluding carbon nanotubes and other bio-persistent high aspect ratio nanomaterials” and the “Risk Management of Carbon Nanotubes” [87][88] Safe Work Australia has also

published guidance titled “Safe Handling and use of Car- bon Nanotubes” which describes two approaches to man- 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 Institute for Occupational Safety and Health has also published a document titled “Current Intelligence Bul- letin 65: Occupational Exposure to Carbon Nanotubes and Nanofibers” describes strategies for controlling work- place exposures and implementing a medical surveillance program. [85]

These guidance documents generally advocate instituting the principles of the Hierarchy of Hazard Control which is a system used in industry to minimize or eliminate ex- posure to hazards. The hazard controls in the hierarchy are, in order of decreasing effectiveness:

Elimination

Substitution

Engineering Controls

Administrative Controls

4 Synthesis

Controls • Personal Protective Equipment 4 Synthesis powder of carbon nanotubes Techniques have been developed to

powder of carbon nanotubes

Techniques have been developed to produce nanotubes in sizable quantities, including arc discharge, laser abla- tion, high-pressure carbon monoxide disproportionation,

4.3

Plasma torch

9

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

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

10 4 SYNTHESIS nanotubes being grown by plasma enhanced chemical vapor de- position otubes that are

nanotubes being grown by plasma enhanced chemical vapor de- position

otubes that are to be grown are related to the size of the metal particles. This can be controlled by patterned (or masked) deposition of the metal, annealing, or by plasma etching of a metal layer. The substrate is heated to approximately 700 °C. To initiate the growth of nan- otubes, two gases are bled into the reactor: a process gas (such as ammonia, nitrogen or hydrogen) and a carbon- containing gas (such as acetylene, ethylene, ethanol or methane). Nanotubes grow at the sites of the metal cat- alyst; the carbon-containing gas is broken apart at the surface of the catalyst particle, and the carbon is trans- ported to the edges of the particle, where it forms the nanotubes. This mechanism is still being studied. [106] The catalyst particles can stay at the tips of the growing nan- otube during growth, or remain at the nanotube base, de- pending on the adhesion between the catalyst particle and the substrate. [107] Thermal catalytic decomposition of hy- 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 CNT preparation. Scale-up of the reactor is the major challenge. [108][109]

CVD is the most widely used method for the produc- tion of carbon nanotubes. [110] For this purpose, the metal nanoparticles are mixed with a catalyst support such as MgO or Al 2 O 3 to increase the surface area for higher yield of the catalytic reaction of the carbon feedstock with the metal particles. One issue in this synthesis route is the removal of the catalyst support via an acid treatment, which sometimes could destroy the original structure of

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- 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- centrated upon finding methods to produce large, pure amounts of particular types of nanotubes. Their ap- proach grows long fibers from many small seeds cut from

a single nanotube; all of the resulting fibers were found

to be of the same diameter as the original nanotube and are expected to be of the same type as the original nanotube. [116]

4.4.1 Super-growth CVD

Super-growth CVD (water-assisted chemical vapor depo- sition) was developed by Kenji Hata, Sumio Iijima and co-workers at AIST, Japan. [117] In this process, the ac- tivity and lifetime of the catalyst are enhanced by addi- tion of water into the CVD reactor. Dense millimeter-tall nanotube “forests”, aligned normal to the substrate, were produced. The forests height could be expressed, as

H(t) = βτ o (1 e t/τ o ).

In this equation, β is the initial growth rate and τ o is the

characteristic catalyst lifetime. [118]

Their specific surface exceeds 1,000 m 2 /g (capped) or 2,200 m 2 /g (uncapped), [119] surpassing the value of 400– 1,000 m 2 /g for HiPco samples. The synthesis efficiency

is about 100 times higher than for the laser ablation

method. The time required to make SWNT forests of the height of 2.5 mm by this method was 10 minutes 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/cm 3 . [121][122] It is much lower than that of conventional CNT powders (~1.34 g/cm 3 ), 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 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/cm 3 . 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]

4.5 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 compete with rapidly developing large scale CVD pro- duction.

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]

4.7 Application-related issues

mal annealing. [ 1 4 1 ] 4.7 Application-related issues Centrifuge tube with a solution of

Centrifuge tube with a solution of carbon nanotubes, which were sorted by diameter using density-gradient ultracentrifugation. [142]

12

6 CURRENT APPLICATIONS

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]

5 Chemical modification

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 scaffolding for bone growth [158]

There is also ongoing research in using carbon nanotubes as a scaffold for diverse microfabrication techniques. [159]

7 Potential applications

The strength and flexibility of carbon nanotubes makes them of potential use in controlling other nanoscale struc- 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 tested to be 63 GPa. [43] Carbon nanotubes were found in Damascus steel from the 17th century, possibly help- ing to account for the legendary strength of the swords made of it. [160][161] Recently, several studies have high- lighted the prospect of using carbon nanotubes as build- ing blocks to fabricate three-dimensional macroscopic (>1mm in all three dimensions) all-carbon devices. Lal- wani et al. have reported a novel radical initiated ther- mal crosslinking method to fabricated macroscopic, free- standing, porous, all-carbon scaffolds using single- and multi-walled carbon nanotubes as building blocks. [13] These scaffolds possess macro-, micro-, and nano- struc- tured pores and the porosity can be tailored for specific 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] cartilage, [165] muscle [166] and nerve tissue. [163][167] Dis- persion of low weight % of graphene (~0.02 wt.%) re- sults in significant increases in compressive and flexu- ral mechanical properties of polymeric nanocomposites. Researchers at Rice University, Stony Brook University, Radboud University Nijmegen Medical Centre and Uni- versity of California, Riverside have shown that carbon nanotubes and their polymer nanocomposites are suitable scaffold materials for bone tissue engineering [14][158][168] and bone formation. [169][170]

In November 2012 researchers at the American National Institute of Standards and Technology (NIST) proved

that single-wall carbon nanotubes may help protect DNA molecules from damage by oxidation. [171]

A highly effective method of delivering carbon nanotubes

into cells is Cell squeezing, a high-throughput vector-free microfluidic platform for intracellular delivery developed

Carbon nanotubes have furthermore been grown inside microfluidic channels for chemical analysis, based on electrochromatography. Here, the high surface-area-to- volume ratio and high hydrophobicity of CNTs are used in order to greatly decrease the analysis time of small neutral molecules that typically require large bulky equip- ment for analysis. [173][174]

7.2 Structural

Because of the carbon nanotube’s superior mechanical properties, many structures have been proposed ranging from everyday items like clothes and sports gear to com- bat jackets and space elevators. [175] However, the space elevator will require further efforts in refining carbon nanotube technology, as the practical tensile strength of carbon nanotubes must be greatly improved. [45]

For perspective, outstanding breakthroughs have already been made. Pioneering work led by Ray H. Baughman at the NanoTech Institute has shown that single and multi- walled nanotubes can produce materials with toughness unmatched in the man-made and natural worlds. [176][177]

man-made and natural worlds. [ 1 7 6 ] [ 1 7 7 ] Carbon nanotubes

Carbon nanotubes being spun to form a yarn, CSIRO

Carbon nanotubes are also a promising material as build- ing blocks in hierarchical composite materials given their exceptional mechanical properties (~1 TPa in modulus, and ~100 GPa in strength). Initial attempts to incorporate CNTs into hierarchical structures (such as yarns, fibres or films [178] ) has led to mechanical properties that were significantly lower than these potential limits. Windle et al. have used an in situ chemical vapor deposition (CVD) spinning method to produce continuous CNT yarns from CVD-grown CNT aerogels. [179][180] CNT yarns can also be manufactured by drawing out CNT bundles from a

14

7 POTENTIAL APPLICATIONS

CNT forest and subsequently twisting to form the fibre (draw-twist method, see picture on right). The Win- dle group have fabricated CNT yarns with strengths as high as ~9 GPa at small gage lengths of ~1 mm, how- ever, strengths of only about ~1 GPa were reported at the longer gage length of 20 mm. [181][182] The reason why fi- bre strengths have been low compared to the strength of individual CNTs is due to a failure to effectively trans- fer load to the constituent (discontinuous) CNTs within the fibre. One potential route for alleviating this prob- lem is via irradiation (or deposition) induced covalent inter-bundle and inter-CNT cross-linking to effectively 'join up' the CNTs. [183] Espinosa et al. developed high performance DWNT-polymer composite yarns by twist- ing and stretching ribbons of randomly oriented bundles of DWNTs thinly coated with polymeric organic com- pounds. These DWNT-polymer yarns exhibited an un- usually high energy to failure of ~100 J·g 1 (comparable to one of the toughest natural materials – spider silk [184] ), and strength as high as ~1.4 GPa. [185] Effort is ongoing to produce CNT composites that incorporate tougher matrix materials, such as Kevlar, to further improve on the me- chanical properties toward those of individual CNTs.

Because of the high mechanical strength of carbon nan- otubes, research is being made into weaving them into clothes to create stab-proof and bulletproof clothing. The nanotubes would effectively stop the bullet from penetrat- ing the body, although the bullet’s kinetic energy would likely cause broken bones and internal bleeding. [186]

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]

The first nanotube integrated memory circuit was made in 2004. One of the main challenges has been regulating the conductivity of nanotubes. Depending on subtle surface features a nanotube may act as a plain conductor or as a semiconductor. A fully automated method has however been developed to remove non-semiconductor tubes. [191]

Another way to make carbon nanotube transistors has been to use random networks of them. [192] By doing so one averages all of their electrical differences and one can produce devices in large scale at the wafer level. [193] This approach was first patented by Nanomix Inc. [194] (date of original application June 2002 [195] ). It was first published in the academic literature by the United States Naval Research Laboratory in 2003 through independent research work. This approach also enabled Nanomix to make the first transistor on a flexible and transparent substrate. [196][197]

Large structures of carbon nanotubes can be used for thermal management of electronic circuits. An approx- imately 1 mm–thick carbon nanotube layer was used as a special material to fabricate coolers, this material has very low density, ~20 times lower weight than a similar copper structure, while the cooling properties are similar for the two materials. [198]

In 2013, researchers demonstrated a Turing-complete prototype micrometer-scale computer. [199][200][201] Carbon nanotube transistors as logic-gate circuits with densities comparable to modern CMOS technology has not yet been demonstrated.

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

The exceptional electrical and mechanical properties of carbon nanotubes have made them alternatives to the traditional electrical actuators for both microscopic and macroscopic applications. Carbon nanotubes are very good conductors of both electricity and heat, and they are also very strong and elastic molecules in certain di- rections.

7.6 Batteries

Carbon nanotubes’ (CNTs) exciting electronic proper- ties have shown promise in the field of batteries, where typically they are being experimented as a new elec- trode material, particularly the anode for lithium ion bat- teries. This is due to the fact that the anode requires a relatively high reversible capacity at a potential close

to metallic lithium, and a moderate irreversible capac-

ity, observed thus far only by graphite-based composites, such as CNTs. They have shown to greatly improve ca- pacity and cyclability of lithium-ion batteries, as well as the capability to be very effective buffering components, alleviating the degradation of the batteries that is typi- cally due to repeated charging and discharging. Further, electronic transport in the anode can be greatly improved using highly metallic CNTs. [206]

More specifically, CNTs have shown reversible capac- ities from 300 to 600 mAhg 1 , with some treatments to them showing these numbers rise to up to 1000 mAhg 1 . [207] Meanwhile, graphite, which is most widely

used as an anode material for these lithium batteries, has shown capacities of only 320 mAhg 1 . By creating com- 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]

7.6.1 Paper batteries

A paper battery is a battery engineered to use a paper-

thin sheet of cellulose (which is the major constituent of regular paper, among other things) infused with aligned carbon nanotubes. [208] The potential for these devices is great, as they may be manufactured via a roll-to-roll pro- cess, which would make it very low-cost, and they would be lightweight, flexible, and thin. In order to produc- tively use paper electronics (or any thin electronic de- vices), the power source must be equally thin, thus indi- cating the need for paper batteries. Recently, it has been shown that surfaces coated with CNTs can be used to re- place heavy metals in batteries. [209] More recently, func- tional paper batteries have been demonstrated, where a lithium-ion battery is integrated on a single sheet of pa-

per through a lamination process as a composite with Li4Ti5O12 (LTO) or LiCoO2 (LCO). The paper sub- 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 energy devices show potential in RFID tags, functional packaging, or new disposable electronic applications. [210]

7.7 Solar cells

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- tics. Research has shown that they can provide a siz- able increase in efficiency, even at their current unop- timized state. Solar cells developed at the New Jersey Institute of Technology use a carbon nanotube complex, formed by a mixture of carbon nanotubes and carbon buckyballs (known as fullerenes) to form snake-like struc- tures. Buckyballs trap electrons, but they can't make elec- trons flow. [211] Add sunlight to excite the polymers, and the buckyballs will grab the electrons. Nanotubes, be- having like copper wires, will then be able to make the electrons or current flow. [212]

Additional research has been conducted on creating SWNT hybrid solar panels to increase the efficiency fur- ther. These hybrids are created by combining SWNT’s with photo-excitable electron donors to increase the num- ber of electrons generated. It has been found that the interaction between the photo-excited porphyrin and SWNT generates electro-hole pairs at the SWNT sur- faces. This phenomenon has been observed experimen- tally, and contributes practically to an increase in effi- ciency up to 8.5%. [213]

Further information: Carbon nanotubes in photovoltaics

7.8 Hydrogen storage

In addition to being able to store electrical energy, there has been some research in using carbon nanotubes to store hydrogen to be used as a fuel source. By taking ad- vantage of the capillary effects of the small carbon nan- otubes, it is possible to condense gases in high density in- side single-walled nanotubes. This allows for gases, most notably hydrogen (H 2 ), to be stored at high densities with- out being condensed into a liquid. Potentially, this stor- age method could be used on vehicles in place of gas fuel tanks for a hydrogen-powered car. A current issue re- garding hydrogen-powered vehicles is the on-board stor- age of the fuel. Current storage methods involve cooling and condensing the H 2 gas to a liquid state for storage which causes a loss of potential energy (25–45%) when compared to the energy associated with the gaseous state. Storage using SWNTs would allow one to keep the H2 in its gaseous state, thereby increasing the storage efficiency.

16

7 POTENTIAL APPLICATIONS

This method allows for a volume to energy ratio slightly smaller to that of current gas powered vehicles, allowing for a slightly lower but comparable range. [214]

An area of controversy and frequent experimentation re- garding the storage of hydrogen by adsorption in carbon nanotubes is the efficiency by which this process occurs. The effectiveness of hydrogen storage is integral to its use as a primary fuel source since hydrogen only contains 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 carbon with surface area of 2600 m2/g can store up to 5,8% w/w. In all these carbonaceous materials, hydro- gen is stored by physisorption at 70-90K. [215]

7.8.1 Experimental capacity

One experiment [216] sought to determine the amount of hydrogen stored in CNTs by utilizing elastic recoil detec- tion analysis (ERDA). CNTs (primarily SWNTs) were synthesized via chemical vapor disposition (CVD) and subjected to a two-stage purification process including air oxidation and acid treatment, then formed into flat, uniform discs and exposed to pure, pressurized hydrogen at various temperatures. When the data was analyzed, it was found that the ability of CNTs to store hydrogen de- creased as temperature increased. Moreover, the highest hydrogen concentration measured was ~0.18%; signifi- cantly lower than commercially viable hydrogen storage needs to be. A separate experimental work performed by using a gravimetric method also revealed the maxi- mum hydrogen uptake capacity of CNTs to be as low as 0.2%. [217]

tized into elementary charges, i.e. electrons, and each such elementary charge needs a minimum space, a sig- nificant fraction of the electrode surface is not available

for storage because the hollow spaces are not compatible

with the charge’s requirements. With a nanotube elec-

trode the spaces may be tailored to size—few too large

or too small—and consequently the capacity should be increased considerably. [218]

7.10 Radar absorption

Main article: Radar-absorbent material

Radars work in the microwave frequency range, which can be absorbed by MWNTs. Applying the MWNTs to the aircraft would cause the radar to be absorbed and therefore seem to have a smaller radar cross-section. One such application could be to paint the nanotubes onto the plane. Recently there has been some work done at the University of Michigan regarding carbon nanotubes use- fulness as stealth technology on aircraft. It has been found that in addition to the radar absorbing properties, the nan- otubes neither reflect nor scatter visible light, making it essentially invisible at night, much like painting current stealth aircraft black except much more effective. Cur- rent limitations in manufacturing, however, mean that current production of nanotube-coated aircraft is not pos- sible. One theory to overcome these current limitations is to cover small particles with the nanotubes and sus- pend the nanotube-covered particles in a medium such as paint, which can then be applied to a surface, like a stealth aircraft. [219]

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

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

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

in conventional ultracapacitors has many small hollow buckled single-walled carbon nanotube macrofilms. The

electrospun polyurethane was used and provided sound mechanical stretchability and the whole cell achieve ex-

spaces of various size, which create together a large sur- face to store electric charge. But as charge is quan-

MIT Research Laboratory of Electronics uses nanotubes to improve supercapacitors. The activated charcoal used

7.15

Water treatment

17

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

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

to six months.

Eikos Inc of Franklin, Massachusetts and Unidym Inc.

of Silicon Valley, California are developing transparent,

electrically conductive films of carbon nanotubes to re- place indium tin oxide (ITO). Carbon nanotube films are substantially more mechanically robust than ITO films, making them ideal for high-reliability touchscreens and flexible displays. Printable water-based inks of carbon nanotubes are desired to enable the production of these films to replace ITO. [245] Nanotube films show promise for use in displays for computers, cell phones, PDAs, and ATMs.

A nanoradio, a radio receiver consisting of a single nan-

otube, was demonstrated in 2007.

A flywheel made of carbon nanotubes could be spun at ex-

tremely high velocity on a floating magnetic axis in a vac- uum, and potentially store energy at a density approach- ing that of conventional fossil fuels. Since energy can be added to and removed from flywheels very efficiently in the form of electricity, this might offer a way of storing 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

heavily upon the cost of making massive, unbroken nan- otube structures, and their failure rate under stress.

Carbon nanotube springs have the potential to indefinitely store elastic potential energy at ten times the density of lithium-ion batteries with flexible charge and discharge rates and extremely high cycling durability.

Ultra-short SWNTs (US-tubes) have been used as

nanoscaled capsules for delivering MRI contrast agents

in vivo. [246]

Carbon nanotubes provide a certain potential for metal- free catalysis of inorganic and organic reactions. For instance, oxygen groups attached to the surface of car- bon nanotubes have the potential to catalyze oxida- tive dehydrogenations [247] or selective oxidations. [248] Nitrogen-doped carbon nanotubes may replace platinum catalysts used to reduce oxygen in fuel cells. A forest of vertically aligned nanotubes can reduce oxygen in alka- line solution more effectively than platinum, which has been used in such applications since the 1960s. Here, the nanotubes have the added benefit of not being subject to carbon monoxide poisoning. [249]

Wake Forest University engineers are using multiwalled carbon nanotubes to enhance the brightness of field- induced polymer electroluminescent technology, poten-

tially offering a step forward in the search for safe, pleas- ing, high-efficiency lighting. In this technology, moldable polymer matrix emits light when exposed to an electric current. It could eventually yield high-efficiency lights without the mercury vapor of compact fluorescent lamps

or the bluish tint of some fluorescents and LEDs, which

has been linked with circadian rhythm disruption. [250]

Candida albicans has been used in combination with car- bon nanotubes (CNT) to produce stable electrically con- ductive bio-nano-composite tissue materials that have been used as temperature sensing elements. [251]

The SWNT production company OCSiAl developed a series of masterbatches for industrial use of single-wall CNTs in multiple types of rubber blends and tires, with initial trials showing increases in hardness, viscosity, ten- sile strain resistance and resistance to abrasion while re- ducing elongation and compression [252] In tires the three primary characteristics of durability, fuel efficiency and traction were improved using SWNTs. The develop- ment of rubber masterbatches built on earlier work by the Japanese National Institute of Advanced Industrial Sci- ence & Technology showing rubber to be a viable candi- date for improvement with SWNTs. [253]

Introducing MWNTs to polymers can improve flame re- tardancy and retard thermal degradation of polymer. [254] The results confirmed that combination of MWNTs and ammonium polyphosphates show a synergistic effect for improving flame retardancy. [255]

8 Discovery

The true identity of the discoverers of carbon nanotubes is a subject of some controversy. [256] For years, scientists assumed that Sumio Iijima of NEC had discovered car- bon nanotubes in 1991. He published a paper describ- ing his discovery which initiated a flurry of excitement and could be credited by inspiring the many scientists now studying applications of carbon nanotubes. Though Iijima has been given much of the credit for discovering carbon nanotubes, it turns out that the timeline of car- bon nanotubes goes back much further than 1991. [256] In 1952 L. V. Radushkevich and V. M. Lukyanovich published clear images of 50 nanometer diameter tubes made of carbon in the Soviet Journal of Physical Chem- istry. [100] This discovery was largely unnoticed, as the ar- ticle was published in Russian, and Western scientists’ access to Soviet press was limited during the Cold War. Before they came to be known as carbon nanotubes, in 1976, Morinobu Endo of CNRS observed hollow tubes of rolled up graphite sheets synthesised by a chemical vapour-growth technique. [257] The first specimens ob- served would later come to be known as single-walled car- bon nanotubes (SWNTs). [258] The three scientists have been the first ones to show images of a nanotube with a solitary graphene wall. [256]

Endo, in his early review of vapor-phase-grown carbon fibers (VPCF), also reminded us that he had observed a hollow tube, linearly extended with parallel carbon layer faces near the fiber core. [259] 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 strongly related to the VPGCF developed by Endo. [258] In fact, they call it the “Endo-process”, out of respect for his early work and patents. [258][260]

In 1979, John Abrahamson presented evidence of car- bon nanotubes at the 14th Biennial Conference of Car- bon at Pennsylvania State University. The conference paper described carbon nanotubes as carbon fibers that were produced on carbon anodes during arc discharge. A characterization of these fibers was given as well as hy- potheses for their growth in a nitrogen atmosphere at low pressures. [261]

In 1981, a group of Soviet scientists published the re- sults of chemical and structural characterization of car- bon nanoparticles produced by a thermocatalytical dis- proportionation of carbon monoxide. Using TEM images and XRD patterns, the authors suggested that their “car- bon multi-layer tubular crystals” were formed by rolling graphene layers into cylinders. They speculated that by rolling graphene layers into a cylinder, many different arrangements of graphene hexagonal nets are possible. They suggested two possibilities of such arrangements:

circular arrangement (armchair nanotube) and a spiral, helical arrangement (chiral tube). [262]

In 1987, Howard G. Tennent of Hyperion Catalysis was

issued a U.S. patent for the production of “cylindrical dis- crete carbon fibrils” with a “constant diameter between

about 3.5 and about 70 nanometers length 10 2 times

, the diameter, and an outer region of multiple essentially continuous layers of ordered carbon atoms and a distinct

inner core ”

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- dent prediction that if single-walled carbon nanotubes could be made, then they would exhibit remarkable con- ducting properties [265] helped create the initial buzz that

is now associated with carbon nanotubes. Nanotube Institute of Environmental Health Sciences (NIEHS) as research accelerated greatly following the independent quoted. discoveries [266][267] by Bethune at IBM and Iijima at NEC

This article incorporates public domain text from National

Ninithi (nanotube modelling software)

Vantablack, a substance produced in 2014; the blackest substance known

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[263]

of single-walled carbon nanotubes and methods to specif- ically produce them by adding transition-metal catalysts to the carbon in an arc discharge. The arc discharge tech- nique was well-known to produce the famed Buckminster fullerene on a preparative scale, [268] and these results ap- peared to extend the run of accidental discoveries relating to fullerenes. The discovery of nanotubes remains a con- tentious issue. Many believe that Iijima’s report in 1991 is of particular importance because it brought carbon nan- otubes into the awareness of the scientific community as

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