Carbon nanotubes

By Shobbi Bagga

Definition: Carbon Nanotube and Carbon fiber

The history of carbon fiber goes way back

The history of carbon nanotube starts from 1991

Institute of Optics, University of Rochester

Carbon nanotube
CNT: Rolling-up a graphene sheet to form a tube

Schematic of a CNT

STM image of CNT

Institute of Optics, University of Rochester

Who found first nanotube?

1970: Morinobu Endo-- First carbon filaments of nanometer dimensions, as part of his PhD studies at the University of Orleans in France. He grew carbon fibers about 7 nm in diameter using a vapor-growth technique. Filaments were not recognized as nanotubes and were not studied.

1991:Sumio Iijima-- NEC Laboratory in Tsukuba-- used highresolution transmission electron microscopy to observe carbon nanotubes.

Graphite
Hexagonal graphite:

I.
II.

Graphite has a structure containing layers of atoms arranged at the corners of contiguous hexagons.
(not to be confused with hexagonal close packed).

III. The ease with which layers slide against each other is consistent with the much larger distance between carbon atoms in different layers (335 pm) than between carbon atoms in the same layer (142 pm).
IV. The lattice constant a = 246.6 pm V. C=669 pm

Graphite

How to roll the nanotube ?

1. A carbon nanotube is based on a twodimensional graphene sheet. 2. The chiral vector is defined on the hexagonal lattice as Ch = n1 + m2, 3. Chiral angle 4. Role/cap off

Different types of nanotubes

(n, 0) or (0, m) and have a chiral angle of 0, armchair nanotubes have (n, n) and a chiral angle of 30, while chiral nanotubes have general (n, m) values and a chiral angle of between 0 and 30.

Nanotubes are formed by rolling up a graphene sheet into a cylinder and capping each end with half of a fullerene molecule. Shown here is a (5, 5) armchair nanotube (top), a (9, 0) zigzag nanotube (middle) and a (10, 5) chiral nanotube. The diameter of the nanotubes depends on the values of n and m.

Picture of Carbon NanoTubes

Arc discharge method

Chemical vapor deposition

Place substrate in oven, heat to 600 C, and slowly add a carbon-bearing gas such as methane. As gas decomposes it frees up carbon atoms, which recombine in the form of NTs

Laser ablation (vaporization)

Blast graphite with intense laser pulses; use the laser pulses rather than electricity to generate carbon gas from which the NTs form; try various conditions until hit on one that produces prodigious amounts of SWNTs

Connect two graphite rods to a power supply, place them millimeters apart, and throw switch. At 100 amps, carbon vaporizes in a hot plasma.

Can produce SWNT and MWNTs with few structural defects

Easiest to scale to industrial production; long length

Primarily SWNTs, with a large diameter range that can be controlled by varying the reaction temperature By far the most costly, because requires expensive lasers

Tubes tend to be short with random sizes and directions

NTs are usually MWNTs and often riddled with defects

ARC DISCHARGE METHOD

The arc discharge technique generally involves the use of two high-purity graphite electrodes. The anode is either pure graphite or contains metals. In the latter case, the metals are mixed with the graphite powder and introduced in a hole made in the anode center. The electrodes are momentarily brought into contact and an arc is struck. The synthesis is carried out at low pressure (30-130 torr or 500 torr) in controlled atmosphere composed of inert and/or reactant gas. The distance between the electrodes is reduced until the flowing of a current (50150 A). The temperature in the inter-electrode zone is so high that carbon sublimes from the positive electrode (anode) that is consumed.

A constant gap between the anode and cathode is maintained by adjusting the position of the anode. A plasma is formed between the electrodes.

 The plasma can be stabilized for a long reaction time by controlling the distance between the electrodes by means of the voltage (2540 V) control. The reaction time varies from 3060 seconds to 210 minutes.
Various kinds of products are formed in different parts of the reactor: (1) large quantities of rubbery soot on the reactor walls; (2) web-like structures between the cathode and the chamber walls; (3) grey hard deposit at the end of cathode; and (4) spongy collaret around the cathodic deposit.

The metals usually utilized were Fe, Ni, Co, Mo, Y either alone or in mixture. Better results were obtained using bimetallic catalysts. Amorphous carbon, encapsulated metal nanoparticles, polyhedral carbon are also present in the product [14,15].
When no catalyst is used, only the soot and the deposit are formed. The soot contains fullerenes while MWNTs together with graphite carbon nanoparticles are found in the carbon deposit. The inner diameter of the MWNTs varies from 1 to 3 nm, the outer diameter varies in the range of 225 nm, the tube length does not exceed 1 m, and the tubes have closed tips. When metal catalysts are co-evaporated with carbon in the DC arc discharge, the core of the deposit contains MWNTs, metal filled MWNTs (FMWNTs), graphitic carbon nanoparticles(GNP), metal filled graphite carbon nanoparticles (FGNP) and metal nanoparticles (MNP), while the powder-like or spongy soot contains MWNTs, FMWNTs and SWNTs. The SWNTs have closed tips, are free of catalyst and are either isolated or in bundles. Most of the SWNTs have diameters of 1.11.4 nm and are several microns long. The collarette is mainly constituted of SWNTs (80%), isolated or in bundles, but it is only formed in the presence of certain catalysts.

 The physical and chemical factors influencing the arc discharge process are the carbon vapour concentration, carbon vapour dispersion in inert gas, temperature in the reactor, composition of catalyst, the addition of promoters and the presence of hydrogen.

These factors affect the nucleation and the growth of the nanotubes, their inner and outer diameters and the type of nanotubes (SWNTs, MWNTs). The amount of carbon nanoparticles was found to diminish when pure hydrogen was used during the reaction

The pressure of gases

The type of the produced material is demonstrated to be highly influenced by the applied pressure of the carrier and/or inert gas. Shi et al. observed that at their reaction conditions the pressure of He of 700 Torr gives high density of SWNT bundles with d = 2030 nm and length up to 15 microns. In contrast, applying a He pressure lower than 300 Torr the typical product was a mixture of fullerenes and metallofullerenes. Qiu and coworkers found that the formation process of DWNTs was highly sensitive to the composition of the catalyst and H2 pressure

Catalyst composition and carbon sources

Wang utilized polyvinylalcohol (PVA) and PVA/Fe mixture as catalyst. They found that the type of the product varies with the PVA/Fe ratio. When high concentration of PVA was used in the catalyst mixture high density of entangled MWNTs of diameters at about 60190 nm were obtained Oppositely, using high concentration of Fe spherical particles were synthesized and no MWNTs formation was observed. When only PVA was used MWNTs with diameters in the range of 3060 nm, sheet-like carbon structures and beaded carbon nanotubes were found. It may be due to the current variation during the synthesis. It is known that different rare-earth elements have strong influence on the quantity and the nanostructure of the SWNTs produced, e.g., Eu/Ni catalyst produced very few SWNTs with nanoparticles, while applying Ce/Ni catalyst small diameter SWNTs were obtained. However, Ni has an essential role in the synthesis of SWNTs by arc discharge method and the rareearth metals play the role of the co-catalyst.

 From the study of the series of experiments with various KCl contents it was found that the CNT formation increased by increasing the amount of KCl but it had an upper limit of 3 wt %. The KCl was replaced by other chemicals containing potassium or chloride to examine the role of these elements. It may be because chloride can act as promoter in the formation of carbon fragments containing sixor five-membered rings which could be identified as the initial fragmentscaps or nuclei.

 It has been favored that deionized water as reaction environment for the production of carbon nanotubes because the quality of the nanotubes produced in liquid N2 was good only at the top surface of the sample. In the lower areas some degradation mechanisms occurred which can be related to the fast and violent evaporation operating in liquid N2. Despite the extremely low temperature of liquid nitrogen, the strong evaporation resulting from the operation of the arc discharge does not allow good thermal exchange between the synthesized material and its surroundings. Therefore, liquid nitrogen provides less efficient cooling than deionized water does, and the MWCNTs produced exhibit distorted morphology and degraded structure. Consequently, another adequate liquid media must be found which has remarkable cooling ability but does not vaporize strongly during arc discharge

Types of arc discharge methods

Imasaka et al. reported on the intermittent arc discharge process in water producing carbon nano-onions and nanotubes. This technique permits several millisecond pulse duration which is much longer than that of the pulsed arc method with microsecond pulse duration. The product obtained was either a floating powder containing uniformly dispersed fine spherical particles, or a sediment composed of straight MWNTs with length in the range of 100500 nm and aggregated onion-like nanoparticles. Lee et al. synthesized CNTs by plasma rotating arc discharge process. They observed that the nanotube yield was increased as the rotation speed of the anode was increased and the collector became closer to the plasma. A remarkable study has been carried out very recently on the mechanism of formation of SWNT from acetylene on Ni nanoparticles using field emission microscopy (FEM). It was shown that the CNTs often rotate axially during growth following the screw-dislocation-like (SDL) model and this rotation is driven by the insertion of dimers. This scheme implies that there must be both longitudinal and rotational sliding between the nanoparticle and the edge of the CNT in order to give space to the newly accreted carbon dimers

Laser Ablation
Two types of laser devices are utilized nowadays for carbon nanotube production: lasers operating in pulsed mode on the one hand and lasers operating in continuous mode on the other hand, the latter generally providing a smaller influence. An example of the layout indicating the principle of a laser ablation device is given in Fig. A graphite pellet containing the catalyst is put in the middle of an inert gas-filled quartz tube placed in an oven maintained at a temperature of 1,200 C . The energy of the laser beam focused on the pellet permits it to vaporize and sublime the graphite by uniformly bombarding its surface. The carbon species swept by a flow of neutral gas are thereafter deposited as soot in different regions: on the conical water-cooled copper collector, on the quartz tube walls, and on the backside of the pellet.

Various improvements have been made to this device in order to increase the production efficiency. For example, Thess et al. employed a second pulsed laser that follows the initial impulsion but at a different frequency in order to ensure a more complete and efficient irradiation of the pellet. This second impulsion has the role of vaporizing the coarse aggregates issued from the first ablation and thereby making them participate in the active carbon feedstock involved in the nanotube growth.
Other modifications were brought by Rinzler et al. who inserted a second quartz tube of a smaller diameter coaxially disposed inside to the first one. This second tube has the role of reducing the vaporization zone and thereby permitting an increase in the quantity of sublimed carbon. They also arranged to place the graphite pellet on a revolving system so that the laser beam uniformly scans its whole surface. Other groups have realized that, as far as the target contains both the catalyst and the graphite, the latter evaporates in priority and the pellet surface becomes more and more metal rich, resulting in a decrease of the efficiency in nanotube formation in the course of the process. To solve this problem, Yudasaka et al. utilized two pellets facing each other, one entirely made from the graphite powder and the other from an alloy of transition metals (catalysts), and irradiated simultaneously.

A sketch of a synthesis reactor based on the vaporization of a target at a fixed temperature by a continuous CO2 laser beam ( = 10.6m) is shown in Fig. 3.10. The power can be varied from 100W to 1,600 W. The temperature of the target is measured with an optical pyrometer, and these measurements are used to regulate the laser power to maintain a constant vaporization temperature. The gas, heated by the contact with the target, acts as a local furnace and creates an extended hot zone, making an external furnace unnecessary. The gas is extracted through a silica pipe, and the solid products formed are carried away by the gas flow through the pipe and then collected on a filter. The synthesis yield is controlled by three parameters: the cooling rate of the medium where the active, secondary catalyst particles are formed, the residence time, and the temperature (in the 1,0002,100K range) at which SWNTs nucleate and grow But devices equipped with facilities to gather in situ data such as the target temperature are fewand, generally speaking, among the numerous parameters of the laser ablation synthesis technique. The most studied are the nature of the target, the nature and concentration of the catalysts, the nature of the neutral gas flow, and the temperature of the outer oven

Laser Ablation Results

In the absence of catalysts in the target, the soot collected mainly contains multiwall nanotubes (c-MWNTs). Their lengths can reach 300 nm. Their quantity and structure quality are dependent on the oven temperature. The best quality is obtained for an oven temperature set at 1,200 C. At lower oven temperatures, the structure quality decreases, and the nanotubes start presenting many defects [3.23]. As soon as small quantities (few percents or less) of transition metals (Ni, Co) playing the role of catalysts are incorporated into the graphite pellet, products yielded undergo significant modifications, and SWNTs are formed instead of MWNTs. The yield of SWNTs strongly depends on the type of metal catalyst used and is seen to increase with furnace temperature, among other factors. The SWNTs have remarkably uniform diameter and they self-organize into rope-like crystallites 520 nm in diameter and tens to hundreds of micrometers in length (Fig. 3.11).

 The ends of all SWNTs appear to be perfectly closed with hemispherical end caps showing no evidence of any as- sociated metal catalyst particle, although, as pointed out in Sect. 3.1, finding the two tips of a SWNT is rather challenging, considering the huge aspect ratio of the nanotube and their entanglement. Another feature of SWNTs produced with this technique is that they are supposedly cleaner than those produced employing other techniques, i. e., associated with a lower amount of an amorphous carbon phase, either coating the SWNTs or gathered into nanoparticles. Such an advantage, however, stands only for synthesis conditions specifically set to ensure high quality SWNTs. It can no longer be true when conditions are such that high yields are preferred, and SWNTs from electric arc may appear cleaner than SWNTs from laser vaporization .