You are on page 1of 33

CONTENTS

1. Introduction to Carbon Nanotubes 2. Carbon Nanotubes and Related Structures
2.1 Special properties of carbon nanotubes:

1 2 5

3. Classification of Carbon Nanotubes
3.1 Single-Walled Carbon Nanotubes (SWNTs) 3.2 Multi-Walled Carbon Nanotubes (MWNTs)

4. Synthesis of Carbon Nanotubes
4.1 Growth Mechanism 4.2 Arc discharge 4.3 Synthesis of SWNT 4.4 Synthesis of MWNT 4.5 Laser Ablation

9

5. Chemical Vapour Deposition
5.1 Plasma enhanced chemical vapour deposition 5.2 Vapour phase growth

17

6. Purification
6.1 Oxidation 6.2 Acid treatment 6.3 Annealing

20

7. Potential applications of CNTs
7.1 Energy storage 7.2 Hydrogen storage 7.3 Lithium intercalation 7.4 Electrochemical super capacitors 7.5 Field emitting devices 7.6 Transistors 7.7 Nanoprobes and sensors 7.8 Composite materials

23

8. Conclusion 9. References

28 29

1

1. Introduction to Carbon Nanotubes

Fig 1.1 Carbon nanotubes are one of the most commonly mentioned building blocks of nanotechnology. With one hundred times the tensile strength of steel, thermal conductivity better than all but the purest diamond, and electrical conductivity similar to copper, but with the ability to carry much higher currents, they seem to be a wonder material. However, there are some companies planning to produce hundreds of tons per year, while others seem to have extreme difficulty in producing grams. This depicts the uniqueness and specialty of this material. In fact nanotubes come in a variety of flavors: long, short, single-walled, multi-walled, and open, closed, with different types of spiral structure, etc. Each type has specific production costs and applications. Some have been produced in large quantities for years while others are being produced commercially with decent purity and in quantities

2

2. Carbon Nanotubes and Related Structures:

Fig 2.1 Carbon nanotubes were 'discovered' in 1991 by Sumio Lijima and are effectively long, thin cylinders of graphite, which is the material in a pencil or as the basis of some lubricants. Graphite is made up of layers of carbon atoms arranged in a hexagonal lattice, like chicken wire. Though the chicken wire structure itself is very strong, the layers themselves are not chemically bonded to each other but held together by weak forces called Vander Waals. It is the sliding across each other of these layers that gives graphite its lubricating qualities and makes the mark on a piece of paper as you draw your pencil over it. Sheets of chicken wire are rolled up into a cylinder and the loose wire ends are joined. The result is a tube that was described by Richard Smalley as "in one direction . . . the strongest damn thing you'll ever make in the universe". Their tensile strength is 100 times that of steel at one-sixth of the weight. They can conduct heat as efficiently as most Diamond (only diamond grown by deposition from a vapour is better), conduct electricity as efficiently as copper, yet also be semiconducting (like the materials that make up the chips in our computers). They can produce streams of electrons very efficiently (field emission), which can be used to create light in displays for televisions or computers, or even in domestic lighting, and they can enhance the fluorescence of materials they are close to. Their 3

Covalent chemical modification of either sidewalls or end caps has shown to be possible. general information on electron conductivity is referred to a review by Ajayan and Ebbesen10. where i is an integer and n and m are defining the nanotube.1 Special properties of carbon nanotubes: Electronic. and nanotube pretenders. The most important properties of CNTs and their molecular background are stated below . Carbon nanotube reactivity is directly related to the pi-orbital mismatch caused by an increased curvature. Nanotubes within nanotubes can act like miniature springs and they can even be stuffed with other materials. Nanotubes and their variants hold promise for storing fuels such as hydrogen or methanol for use in fuel cells and they make good supports for catalysts. direct investigation of chemical modifications on nanotube behavior is difficult as the crude nanotube samples are still not pure enough. enhanced as a direct result of the curvature of the CNT surface. The differences in conductivity can easily be derived from the grapheme sheet properties.electrical properties can be made to change in the presence of certain substances or as a result of mechanical stress. For the same reason. the solubility of CNTs in different solvents can be controlled this way.8 It was shown that a (n. a smaller nanotube diameter results in increased reactivity. There are different types of nanotubes. a distinction must be made between the sidewall and the end caps of a nanotube. Chemical reactivity. carbon nanotubes with a small diameter are either semi-conducting or metallic. 2. Depending on their chiral vector. molecular and structural properties of carbon nanotubes are determined to a large extent by their nearly one dimensional structure. Electrical conductivity. 4 . The differences in conducting properties are caused by the molecular structure that results in a different band structure and thus a different band gap. The chemical reactivity of a CNT is.m) nanotube is metallic as accounts that: n=m or (n-m) = 3i.9 for more. compared with a graphene sheet. For example. The resistance to conduction is determined by quantum mechanical aspects and was proved to be independent of the nanotube length. Therefore. Though.

Therefore. Use of the optical activity might result in optical devices in which CNTs play an important role. these compounds are potentially suitable for applications in composite materials that need anisotropic properties. Carbon nanotubes have a very large Young modulus in their axial direction. it is expected that other physical properties are influenced by these parameters too. Theoretical studies have revealed that the optical activity of chiral nanotubes disappears if the nanotubes become larger11. The nanotube as a whole is very flexible because of the great length. 5 . Therefore.Optical activity. Mechanical strength.

3. The aspect ratio (length divided by diameter) is typically greater than 100 and can be up to 10.2 Computational image of single-and multi walled nanotubes Carbon nanotubes can be classified as single-walled varieties (SWNTs) having a single cylindrical wall. 20 cm long SWNT strands were claimed to be made. 6 . Classification of Carbon Nanotubes Fig 3. and are generally microscopic rather than nanoscopic. i. The lengths of both types vary greatly. and multi-walled varieties (MWNTs) are having cylinders within cylinders.e. greater than 100 nanometers (a nanometer is a millionth of a millimeter). SWNTs strands of length 160 cm were also made. The joins between the nanotubes in this thread represent a weakness but heating the thread has been found to increase the strength significantly . Recently.1 Fig 3.2 millimeters in diameter but up to 30 centimeters long. Packs of relatively short carbon nanotubes can be drawn out into a bundle of fibers. depending on the way they are made. making a thread only 0.000.

3 Fig 3. The detailed mechanisms responsible for nanotube growth are still not fully understood and computer modeling is playing an increasing role in understanding the complexities.4 nanometers. SWNTs are more capable of being bent or flexed or twisted without breaking than their multiwall counterparts. They are basically tubes of graphite and are normally capped at the ends as shown Figure a . The objective of SWNT producers is to gain greater control over their diameters. lengths. which means that the flow of current through them can be stepped up or down by varying an electrical field.. Carbon 7 . They can be conducting. Their average diameter is around the 1. which is about as long as two silicon atoms side by side. although the caps can be removed.3.1 Single-Walled Carbon Nanotubes (SWNTs): Fig 3. that looks like a soccer ball and is named after the architect Buckminster Fuller (the word fullerene is used to refer to the variety of such molecular cages.2 nanometer mark and depends on the process used to create them. The theoretical minimum diameter of a carbon nanotube is around 0. like metal (often referred to as metallic nanotubes). Nanotubes can be to make extremely dense electronic circuitry in creating basic electronic structures from nanotubes i. some with more carbon atoms than buckminsterfullerene. and some with fewer). such as chirality. The volumes of SWNTs produced are currently small and the quality and purity are variable. a roughly spherical molecule made of sixty carbon atoms.4 These are much harder to make than the multiwalled variety. or semiconducting.e. and other properties. from transistors up to simple logic elements. The caps are made by mixing in some pentagons with the hexagons and are the reason that nanotubes are considered close cousins of buckminsterfullerene as shown in Figure b).

these being the chiral forms. Claims have now been made that it is possible to produce only the semi conducting kind (specifically. A more recent approach is simply to leave the mix of 8 . Additionally. Texas. of Houston.Nanotechnologies Inc. the zigzag form). The type of form a nanotube takes is the major determinant of its electrical properties. which is actually huge in comparison to amounts of SWNTs that have been made historically.5 Imagine a chicken wire fence out of which will be cut a rectangle to roll into a tube. is currently ramping up production to a half a kilogram a day. The rectangle can be cut with the sides vertical or at various angles. the sides can be lowered or raised.e. the fact that all known production methods created a mix of types has been considered one of the hurdles to be overcome if the electronic properties are to be exploited. and these represent the possible permutations of SWNTs as shown in Figure. when joining the sides together. often called zigzag and armchair and a variety of forms in which the Hexagons spiral up or down the tube with varying steepness. For along time. Additionally. whether the tube is semi conducting or conducting. Chirality: Fig 3. In some cases it will not be possible to make a tube such that the loose ends match and hexagons are formed. One such approach relies on vaporizing the conducting nanotubes with a strong electric current. but in other cases it will. The possibilities are two forms in which a pattern circles around the diameter of the tube. there are approaches that can yield only semi conducting nanotubes from a mix of semi conducting and conducting ones. leaving only the semi conducting kind behind. i.

Different shapes and arrangements with imaginative names such as bambootrunks. MWNTs are typically 100 times longer than they are wide and have outer diameters mostly in the tens of nanometers. their structures are less well understood than single wall nanotubes because of their greater complexity and variety. One of the major manufacturers of MWNTs. sea urchins. have also been observed under different processing conditions. does not even sell the nanotubes directly but pre-mixes with polymers for composites applications. 3. the different SWNTs that form the MWNT may have quite different structures (length and chirality). Other companies like Mitsui are also moving 9 . Many of the nanotube applications involve multi-walled nanotubes. necklaces or coils.6 Multi-walled carbon nanotubes are basically made out of SWNTs—concentric cylindrical graphitic tubes. Hyperion Catalysis.2 Multi-Walled Carbon Nanotubes (MWNTs): Fig 3. Although it is easier to produce significant quantities of MWNTs than SWNTs. But the negative side of MWNTs is that they have more defects than SWNTs and these diminish their desirable properties.nanotubes lying around for a while—the metallic ones are oxidized and become semi conducting. because they are easier to produce in large quantities at a reasonable price and have been available in decent amounts for much longer than SWNTs. The tubes involved typically have 8 to 15 walls and are around 10 nanometers wide and 10 micrometers long. In these more complex structures.

laser ablation and chemical vapour deposition. what favors commercial production. this method is very easy to scale up. a high-power laser beam impinges on a volume of carbon –containing feedstock gas (methane or carbon monoxide).into this field. Carbon nanotubes are generally produced by three main techniques. 4. 4. whereas arc discharge methods generally produce large quantities of impure material. as it is almost general for all techniques. The largest interest is in the newest methods for each technique and the possibilities of scaling up. chemical vapour deposition (CVD) results in MWNTs or poor quality SWNTs. In general. At the moment. typical conditions are stated at the sections of all the different techniques. arc discharge. First. Nanotubes self assemble from the resulting carbon vapour. The SWNTs produced with CVD have a large diameter range. Synthesis of Carbon Nanotubes Introduction: In this section. In the laser ablation technique. This is an indication that even these less impressive and exotic nanotubes hold promise of representing a sizable market in the near future. However. a vapour is created by an arc discharge between two carbon electrodes with or without catalyst. In arc discharge.1 Growth Mechanism: 10 . which can be poorly controlled. different techniques for nanotube synthesis and their current status are briefly explained. But on the other hand. laser ablation produces a small amount of clean nanotubes. the growth mechanism is explained. Though scientists are researching more economic ways to produce these structures.

filaments can form either by ‘extrusion (also known as base growth)’ in which the nanotube grows upwards from the metal particles that remain attached to the substrate. which accounts for the hollow core that is characteristic of these filaments.Fig 4. The exact atmospheric conditions depend on the technique used. 11 . One of the mechanisms consists out of three steps. C2. For supported metals. Secondly there is a slow graphitization of its wall. One theory13 postulates that metal catalyst particles are floating or are supported on graphite or another substrate. Depending on the size of the catalyst particles. MWNT will be grown on the C2-particles that are formed in the plasma. From this metastable carbide particle. This mechanism is based on in-situ TEM observations. In arc discharge. if no catalyst is present in the graphite. around and below the bisecting diameter. First a precursor to the formation of nanotubes and fullerenes. The carbon diffuses along the concentration gradient and precipitates on the opposite half. SWNT or MWNT are grown. and more than one mechanism might be operative during the formation of CNTs. later on. labeled ‘tip-growth’. or the particles detach and move at the head of the growing nanotube. However.1 The way in which nanotubes are formed is not exactly known. There are several theories on the exact growth mechanism for nanotubes. The actual growth of the nanotube seems to be the same for all the techniques mentioned. The growth mechanism is still a subject of controversy. these will be explained for each technique as they are specific for a technique. in which case the deposition will take place on only one half of the surface (this is the lower curvature side for the pear shaped particles). It presumes that the catalyst particles are spherical or pear-shaped. a rod like carbon is formed rapidly. it does not precipitate from the apex of the hemisphere. is formed on the surface of the metal catalyst particle.

The discharge vaporizes one of the carbon rods and forms a small rod shaped deposit on the other rod. initially used for producing C60 fullerenes. it is a technique that produces a mixture of components and requires separating nanotubes from the soot and the catalytic metals present in the crude product. is the most common and perhaps easiest way to produce carbon nanotubes as it is rather simple to undertake.2 The carbon arc discharge method. However. in an enclosure that is usually filled with inert gas (helium. Producing 12 .2 Arc discharge: Fig 4. Recent investigations have shown that it is also possible to create nanotubes with the arc method in liquid nitrogen14. This method creates nanotubes through arc-vaporization of two carbon rods placed end to end.4. separated by approximately 1mm. argon) at low pressure (between 50 and 700 mbar). A direct current of 50 to 100 A driven by approximately 20 V creates a high temperature discharge between the two electrodes.

which is shown in Figure. On the other hand. the anode has to be doped with metal catalyst. Affecting nanotube diameter in the arc process. These properties affect the speed with which the carbon and catalyst molecules diffuse and cool. Y or Mo. 4. such as Fe. Insight in the growth mechanism is increasing and measurements have shown that different diameter distributions have been found depending on the mixture of helium and argon. kind of gas.2 to 1. This implies that single-layer tubules nucleate and grow on metal particles in different sizes depending on the quenching rate in the plasma and it suggests that temperature and carbon and metal catalyst densities affect the diameter distribution of nanotubes. the current and system geometry. These mixtures have different diffusions coefficients and thermal conductivities. Two distinct methods of synthesis can be performed with the arc discharge apparatus. Ni. The quantity and quality of the nanotubes obtained depend on various parameters such as the metal concentration. Depending on the exact technique. it is possible to selectively grow SWNTs or MWNTs.a nanotube in high yield depends on the uniformity of the plasma arc and the temperature of the deposit form on the carbon electrode. even though they use the same elements.3 Synthesis of SWNT: If SWNTs are preferable. inert gas pressure. Co. Usually the diameter is in the range of 1. A couple of ways to improve the process of arc discharge are stated below. A lot of elements and mixtures of elements have been tested by various authors and it is noted that the results vary a lot. SWNTs have defects and purification is hard to perform. This is not surprising as experimental conditions differ. an advantage is that 13 . a) Inert gas The most common problems with SWNT synthesis are that the product contains a lot of metal catalyst.4 nm.

This was shown in an experiment in which different mixtures of inert gases were used. b) Optical plasma control A second way of control is plasma control by changing the anode to cathode distance (ACD). With a nickel and yttrium catalyst (C/Ni/Y is 94.the diameter can slightly be controlled by changing thermal transfer and diffusion. which improves nanotubes formation.2:1) the optimum nanotube yield was found at a pressure of 660 mbar for pure helium and 100 mbar for pure argon. when nickel/yttrium was used (C/Ni/Y was 94. one can simultaneously control the macroscopic and microscopic parameters of the nanotubes formed. But next to MWNTs a lot of side products are formed such as fullerenes. This enhances anode vaporization. with a lower thermal conductivity and diffusion coefficient. A linear fit of the average nanotube diameter showed a 0. Purifying the MWNTs.8:4. The ACD is adjusted in order to obtain strong visible vortices around the cathode. However 14 . gave SWNTs with a smaller diameter of approximately 1. Combined with controlling the argon-helium mixture. The nanotube diameter ranges from 1.4 Synthesis of MWNT: If both electrodes are graphite.2 nm diameter decrease per 10 % increase in argon helium ratio. and some graphite sheets. means loss of structure and disorders the walls.27 to 1.37 nanometer. and hence condensation of atomic carbon and metals between the plasma and the vicinity of the cathode can control nanotube diameter in the arc process. the main product will be MWNTs. 4. It appeared that argon.2:1) as catalyst.2 nm. amorphous carbon.8:4.

Because no catalyst is involved in this process. with this route mass production is also possible. possibly economical route to highly crystalline MWNTs is the arc-discharge method in liquid nitrogen14. b) Magnetic field synthesis: 15 . This means. There is a strong possibility that SWNTs can be produced with the same apparatus under different conditions. can be synthesized with a low amount of defects. a) Synthesis in liquid nitrogen Fig 4.3 A first.scientist is developing ways to gain pure MWNTs in a large-scale process without purification. Typical sizes for MWNTs are an inner diameter of 1-3 nm and an outer diameter of approximately 10 nm. there is no need for a heavy acidic purification step. the MWNT. The content of the MWNTs can be as high as 70 % of the reaction product. Analysis with Augerspectroscopy revealed that no nitrogen was incorporated in the MWNTs. For this option low pressures and expensive inert gasses are not needed.

4 Synthesis of MWNTs in a magnetic field gives defect-free and high purity MWNTs that can be applied as nanosized electric wires for device fabrication. Fig 4. Highly pure MWNTs (purity > 95 %) were obtained without further purification.5 Laser Ablation: 16 .Fig 4. In this case. the arc discharge synthesis was controlled by a magnetic field around the arc plasma.999 %) were used as electrodes.5 SEM images of MWNTs synthesized with (a) and without (b) the magnetic field 4. which disorders walls of MWNTs. Extremely pure graphite rods (purity > 99.

subsequent laser pulses excite fullerenes to emit C2 that adsorbs on 17 . As the vaporized species cool. From these initial clusters. The SWNTs formed in this case are bundled together by Vander Waals forces. possibly including fullerenes.6 In 1995. The catalysts also begin to condense. small carbon molecules and atoms quickly condense to form larger clusters. then expands and cools rapidly.Fig 4. but not exact similarities. Smalley's group at Rice University reported the synthesis of carbon nanotubes by laser vaporization. and attach to carbon clusters and prevent their closing into cage structures. in the comparison of the spectral emission of excited species in laser ablation of a composite graphite target with that of laser-irradiated C60 vapour.30 Catalysts may even open cage structures when they attach to them. as is the case when no catalysts are included in the target. It is also possible that the particles become that much coated with a carbon layer that they cannot absorb more and the nanotube stops growing. but more slowly at first. However. The laser vaporization apparatus used by Smalley's group is shown in Figure. The main difference between continuous and pulsed laser. There are some striking. tubular molecules grow into single-wall carbon nanotubes until the catalyst particles become too large. is that the pulsed laser demands a much higher light intensity (100 kW/cm2 compared with 12 kW/cm2). A very hot vapour plume forms. or until conditions have cooled sufficiently that carbon no longer can diffuse through or over the surface of the catalyst particles. This suggests that fullerenes are also produced by laser ablation of catalyst-filled graphite. A pulsed or continuous laser is used to vaporize a graphite target in an oven at 1200 °C.

and the reactions probably occur with the same mechanism. The Ni/Y mixture catalyst (Ni/Y is 4. Nanotubes produced Nanotubes produced by laser ablation are purer (up to about 90 % purity) than those produced in the arc discharge process. for example the Ni/Co catalyst with a pulsed laser at 1470 °C gives SWNTs with a diameter of 1.5 at.3-1. In the case of pure graphite electrodes. This might be due to very similar reaction conditions needed. In case of a continuous laser at 1200 °C and Ni/Y catalyst (Ni/Y is 2:0. Chemical Vapour Deposition: 18 .2/1) gave the best yield. MWNTs would be synthesized. but uniform SWNTs could be synthesized if a mixture of graphite with Co. see Figure. there is insufficient evidence to conclude this with certainty. Fe or Y was used instead of pure graphite. since the optimum background gas and catalyst mix is the same as in the arc discharge process. The size of the SWNTs ranges from 1-2 nm. 5.catalyst particles and feeds SWNT growth.4 nm were formed with 20. However. Ni. SWNT versus MWNT: The condensates obtained by laser ablation are contaminated with carbon nanotubes and carbon nanoparticles.4 nm26. Laser ablation is almost similar to arc discharge.30 % yield. SWNTs with an average diameter of 1. Laser vaporization results in a higher yield for SWNT synthesis and the nanotubes have better properties and a narrower size distribution than SWNTs produced by arc-discharge. %). SWNTs synthesized this way exist as 'ropes'.

such as plasma enhanced CVD. as well as the growth rate of the nanotubes can also be maintained. Typical yields for CVD are approximately 30%. 5. These are the basic principles of the CVD process. CVD carbon nanotube synthesis is essentially a two-step process consisting of a catalyst preparation step followed by the actual synthesis of the nanotube. the carbon diffuses towards the substrate. from which the nanotubes will grow.1 Plasma enhanced chemical vapour deposition: 19 . Control over the diameter. such as plasma or a resistively heated coil. Ammonia may be used as the etchant. vapour phase growth. The appropriate metal catalyst can preferentially grow single rather than multi-walled nanotubes. Then. as well as positional control on nanometrescale32. carbon monoxide and acetylene.Chemical vapour deposition (CVD) synthesis is achieved by putting a carbon source in the gas phase and using an energy source. alcohol catalytic CVD. can be achieved by using CVD. thermal chemical CVD. Carbon nanotubes will be formed if the proper parameters are maintained. different techniques for the carbon nanotubes synthesis with CVD have been developed. In the last decennia. The catalyst is generally prepared by sputtering a transition metal onto a substrate and then using either chemical etching or thermal annealing to induce catalyst particle nucleation. The temperatures for the synthesis of nanotubes by CVD are generally within the 650–900 C range3. Fe or Co) where it will bind. aero gel-supported CVD and laser assisted CVD. which is heated and coated with a catalyst (usually a first row transition metal such as Ni. Excellent alignment. Thermal annealing results in cluster formation on the substrate. The energy source is used to “crack” the molecule into reactive atomic carbon. Commonly used gaseous carbon sources include methane. to transfer energy to a gaseous carbon molecule.

A substrate is placed on the grounded electrode. The catalyst has a strong effect on the nanotube diameter.Fig 5. carbon nanotubes will be grown on the metal particles on the substrate by glow discharge generated from high frequency power. After nanoscopic fine metal particles are formed. Ni seems to be the most suitable pure-metal catalyst for the growth of aligned multiwall carbon nanotubes (MWNTs) 36. CO is supplied to the chamber during the discharge. The highest yield of carbon nanotubes achieved was about 50% and was obtained at relatively low temperatures (below 330o C). the reaction gas is supplied from the opposite plate. C2H6. such as Fe. C2H4. CH4. A carbon containing reaction gas. growth rate. SiO2. Figure shows a schematic diagram of a typical plasma CVD apparatus with a parallel plate electrode structure. such as C 2H2. wall thickness.1 The plasma enhanced CVD method generates a glow discharge in a chamber or a reaction furnace by a high frequency voltage applied to both electrodes. morphology and microstructure. The diameter of the MWNTs is approximately 15 nm. In order to form a uniform film. Catalytic metal. Ni and Co are used on for example a Si. or glass substrate using thermal CVD or sputtering. 20 .

39 Figure shows a schematic diagram of a vapour phase growth apparatus.5. directly supplying reaction gas and catalytic metal in the chamber without a substrate 39. decomposed carbons are absorbed and diffused to the catalytic metal particles. vaporization of catalytic carbon is maintained at a relatively low temperature.2 Vapour phase growth is a synthesis method of carbon nanotubes. In the first furnace. . Ferrocene is used as catalyst. The diameter of the carbon nanotubes by using vapour phase growth are in the range of 2 – 4 nm for SWNTs40 and between 70 and 100 nm for MWNTs.2 Vapour phase growth: Fig 5. Fine catalytic particles are formed and when they reach the second furnace. they are synthesized as carbon nanotubes. 21 . Two furnaces are placed in the reaction chamber. Here.

the second one will give a more homogeneous diameter or size distribution. The techniques that will be discussed are oxidation. fictionalization and Chromatography techniques. The common industrial techniques use strong oxidation and acid refluxing techniques. Basically. The techniques will be briefly explained in this chapter and if possible. the purification methods. ferromagnetic separation. The as-produced SWNT soot contains a lot of impurities. Also in the fundamental research. In this chapter the purification of SWNTs will be discussed. In this chapter several purification techniques of the SWNT will be discussed. are combined with other techniques. these techniques can be divided into two mainstreams. annealing. The main impurities in the soot are graphite (wrapped up) sheets. 22 . The first one will separate the SWNTs from the impurities. the SWNT samples also have to be as homogeneous as possible. micro filtration. as mentioned in the references. In order to understand the measurements better. structure selective and size selective separations. as pure as possible without changing them. amorphous carbon. the selectivity will be discussed. it is preferred to obtain SWNTs or the impurities. will be summarized in chronological order. Purification: A large problem with nanotube application is next to large-scale synthesis also the purification. which have an effect on the structure of the tubes. These impurities will interfere with most of the desired properties of the SWNTs.6. cutting. acid treatment. Because most of the techniques used. metal catalyst and the smaller fullerenes. ultrasonication.

it should be easy to see what procedures must be chosen in order to gain the wanted grade of SWNTs and the consequences of the technique on the sample. Techniques: 6. The main disadvantages of oxidation are that not only the impurities are oxidized. but also the SWNTs. These can easily oxidize all the components. is that these impurities are most commonly attached to the metal catalyst. SWNTs will also oxidize. With this table. such as metal content. These impurities have relatively more defects or a more open structure. such as H2O2 and H2SO4. For example. There are a couple of examples for clearing the metal surface. to prepare the sample for a metal removal step. environment. 23 .1 Oxidation Oxidative treatment of the SWNTs is a good way to remove carbonaceous impurities or to clear the metal surface. the metal content should certainly be taken into consideration. which also acts as oxidizing catalyst. The fact that metal acts as oxidizing catalyst. The first one is (mild) oxidizing in a wet environment with soluble oxidizing agents. the efficiency and the yield of the procedure are highly dependable on a lot of factors. These will only oxidize the defects and will clear the surface of the metal. Altogether. oxidizing agent and temperature. oxidation time. so the temperature and the time should be in good control. when looking at the oxidizing time. fixed air and pure oxygen oxidations. Another reason why impurity oxidation is preferred. even without catalyst.Characteristics of the techniques stated in this report. This is the case with thermal54. Luckily the damage to SWNTs is less than the damage to the impurities. when the temperature is raised above 600 °C.

It has no effect on the SWNTs and other carbon particles. Not only the carbon impurities are oxidized now. but when oxygen is used in wet atmosphere. The mild acid treatment65 (4 M HCl reflux) is basically the same as the HNO3 reflux. If a treatment in HCl is used. The high temperature also causes the graphitic carbon and the short fullerenes to pyrolyse. The microwaves will heat up the metal and will catalytically oxidize the carbon attached to the metal.63. 24 . First of all. the density of this surface increases and the surface covering carbon layer ruptures.66. the acid has also a little effect on the SWNTs and other carbon particles. The SWNTs remain in suspended form. Quite different from the oxidative techniques above is microwave heating. the metal catalyst stays intact during these processes. When using high temperature vacuum treatment61 (1873 K) the metal will be melted and can also be removed. When using a treatment in HNO3. but also the metal is partially oxidized and exposed. but here the metal has to be totally exposed to the acid to solvate it. the surface of the metal must be exposed by oxidation or sonication. the outer layer of the metal will be oxidised63.57. the acid only has an effect on the metal catalyst.2 Acid treatment In general the acid treatment will remove the metal catalyst. 6.Most commonly.3 Annealing Due to high temperatures (873 – 1873 K) the nanotubes will be rearranged and defects will be consumed 55. 6. The metal catalyst is then exposed to acid and solvated. Then.

Potential applications of CNTs: 7.7. which is the fastest on nanotubes following ideal Nernstian behaviour. smooth surface topology and perfect surface specificity.10 Electrochemical 25 . carbonaceous materials and carbon fiber electrodes are commonly used in fuel cells. Advantages of considering nanotubes for energy storage are their small dimensions. batteries and other electrochemical applications.1 Energy storage Graphite. The efficiency of fuel cells is determined by the electron transfer rate at the carbon electrodes.

In this case not a hydrogen molecule but an H atom is adsorbed. Because of their cylindrical and hollow geometry. satisfying a combination of both volume and weight limitations. This is called chemisorptions. It is reported that SWNTs were able to meet and sometimes exceed this level by using gas phase adsorption (physisorption). the Department of Energy has set storage requirements of 6. most experimental reports of high storage capacities are rather controversial so that it is difficult to assess the applications potential. it has been predicted that carbon nanotubes can store a liquid or a gas in the inner cores through a capillary effect.energy storage and gas phase intercalation will be described more thoroughly in the following chapters of the report.3 Lithium intercalation 26 . Yet. What lacks. Another possibility for hydrogen storage is electrochemical storage.5 % by weight as the minimum level for hydrogen fuel cells. For this reason. is a detailed understanding of the hydrogen storage mechanism and the effect of materials processing on this mechanism.2 Hydrogen storage The advantage of hydrogen as energy source is that its combustion product is water. 7. and nanometer-scale diameters. 7. In addition. hydrogen can be easily regenerated. The two commonly used means to store hydrogen are gas phase and electrochemical adsorption. As a threshold for economical storage. a suitable hydrogen storage system is necessary.

In this way. they are comprised two electrodes separated by an insulating material that is ionically conducting in electrochemical supercap devices.73 Generally speaking. The capacity is determined by the lithium saturation concentration of the electrode materials. They are comprised two electrodes separated by an insulating material that is ionically conducting in electrochemical devices.e. there is most interest in the double-layer super capacitors and redox super capacitors with different charge-storage modes. a large amount of charge injection occurs if only a small voltage is applied. fast charging time and a long cycle time.The basic principle of rechargeable lithium batteries is electrochemical intercalation and deintercalation of lithium in both electrodes. Typically. the nanotubes to short segments. SWNTs have shown to possess both highly reversible and irreversible capacities. cutting. 7. This charge injection is used for energy storage in nanotube supercapacitors. inter-tube channels and inner cores) are accessible for Li intercalation. Li-intercalation in nanotubes is still unsuitable for battery application. The capacity of an electrochemical super cap 27 . very large capacities result from the high nanotube surface area accessible to the electrolyte.4 Electrochemical super capacitors Super capacitors have a high capacitance and potentially applicable in electronic devices. this is the highest in nanotubes if all the interstitial sites (inter-shell Vander Waals spaces. An ideal battery has a high-energy capacity. i. This feature can potentially be reduced or eliminated by processing. Because this separation is about a nanometer for nanotubes in electrodes. For Li. Because of the large observed voltage hysteresis. The on capacity the of an electrochemical inversely depends separation between the charge on the electrode and the counter charge in the electrolyte.

a large amount of charge injection occurs if only a small voltage is applied. 7. a bottleneck in the use of nanotubes for applications is the dependence of the conductivity and emission stability of the nanotubes on the fabrication process and synthesis conditions. a structural integrity.73 Generally speaking. an ideal emitter is required to have a nanometer size diameter. The applied electric field must be very high in order to extract an electron. because their elongated shape ensures very large field amplification. However. gas discharge 28 . a high electrical conductivity. Because this separation is about a nanometer for nanotubes in electrodes.inversely depends on the separation between the charge on the electrode and the counter charge in the electrolyte.5 Field emitting devices If a solid is subjected to a sufficiently high electric field. a small energy spread and a large chemical stability. electrons near the Fermi level can be extracted from the solid by tunneling through the surface potential barrier. Furthermore. Carbon nanotubes possess all these properties. This emission current depends on the strength of the local electric field at the emission surface and its work function (which denotes the energy necessary to extract an electron from its highest bounded state into the vacuum level). Examples of potential applications for nanotubes as field emitting devices are flat panel displays. very large capacities result from the high nanotube surface area accessible to the electrolyte. In this way. there is most interest in the double-layer super capacitors and redox super capacitors with different charge-storage modes. For technological applications. This condition is fulfilled for carbon nanotubes. This charge injection is used for energy storage in nanotube supercapacitors. the emissive material should have a low threshold emission field and large stability at high current density.

However.6 Transistors The field-effect transistor – a three-terminal switching device can be constructed of only one semiconducting SWNT. working as a logical switch.73 A schematic representation of such a transistor is given in Figure. which iscovered by a layer of SiO2 300nmthick. due to their large length.tubes in telecom networks. electron guns for electron microscopes. AFM tips and microwave amplifiers. 7. which is the basic component of computers. The Si substrate.1 Figure A single semi-conducting nanotube is contacted by two electrodes. the nanotube can be switched from a conducting to an insulating state. Since MWNTtips are conducting. acts as a back-gate.7 Nanoprobes and sensors Because of their flexibility. Such carbon nanotube transistors can be coupled together. nanotubes can also be used in scanning probe instruments. 7. 29 . nanotube vibration. they can be used in STM and AFM instruments (Figure 4-2). Advantages are the improved resolution in comparison with conventional Si or metal tips and the tips do not suffer from crashes with the surfaces because of their high elasticity. will remain an important issue until shorter nanotubes can be grown controllably. Fig 7. By applying a voltage to a gate electrode.

they are ideal candidates for structural applications. Other applications are the following: · A pair of nanotubes can be used as tweezers to move nanoscale structures on surfaces. Because of this. However. The individual tubes can pull out by shearing and at last the whole rope will break. Ropes of SWNTs are also less strong. For example. In other directions.73 · Sheets of SWNTs can be used as electromechanical actuators. MWNTs are weaker because the individual cylinders slide with respect to each other. low weight. with potential applications in chemistry and biology. This happens at stresses far below the tensile strength of individual nanotubes. The main problem is to create a good interface between nanotubes and the polymer matrix. which contain NO2. · SWNTs may be used as miniaturised chemical sensors. the electrical resistance changes. mimicking the actuator mechanism present in natural muscles. NH3 or O2. and high performance composites. nanotubes can be used as molecular probes. 7.8 Composite materials Because of the stiffness of carbon nanotubes. nanotubes are highly flexible. as nanotubes are very smooth and 30 . Nanotubes also sustain large strains in tension without showing signs of fracture. SWNTs could have a Young’s Modulus of 1 MPa. there have not been many successful experiments that show that nanotubes are better fillers than the traditionally used carbon fibers. On exposure to environments. One of the most important applications of nanotubes based on their properties will be as reinforcements in composite materials.Nanotube tips can be modified chemically by attachment of functional groups. Theoretically. they may be used as reinforcements in high strength.

PPV (Poly-p-phenylenevinylene) filled with MWNTs and SWNTs is a composite.have a small diameter. an increased electrical conduction and better performance during compressive load. nanotube aggregates. Other advantages are the low density of the nanotubes. The most important thing we have to know about nanotubes for efficient use of them as reinforcing fibers is knowledge on how to manipulate the surfaces chemically to enhance interfacial behavior between the individual nanotubes and the matrix material 8. is filling of photoactive polymers with nanotubes. A main advantage of using nanotubes for structural polymer composites is that nanotube reinforcements will increase the toughness of the composites by absorbing energy during their highly flexible elastic behavior. behave different to loads than individual nanotubes do. However. which is an example of a non-structural application. which are very common. nanotube-polymer composites could be used also in other areas. Another benefit is that the composite is more robust than the pure polymer. they could be used in the biochemical field as membranes for molecular separations or for osteointegration (growth of bone cells). These composites show a large increase in conductivity with only a little loss in photoluminescence and electro-luminescence yields. Limiting factors for good load transfer could be sliding of cylinders in MWNTs and shearing of tubes in SWNT ropes. which is nearly the same as that of a polymer chain. Another possibility. Of course. which has been used for several experiments. For instance. Secondly. these areas are less explored. CONCLUSION 31 . To solve this problem the aggregates need to be broken up and dispersed or cross-linked to prevent slippage.

the versatility of nanotubes does suggest that they might one day rank as one of the most important materials ever discovered. 9.This review paper has focused the promise that the carbon nanotubes offer in their applications to different fields. References: 32 . Despite an inevitable element of hype. In years to come these carbon nanotubes could find their way into special materials like myriad and devices around us and quite probably make some of the leaders in this field. Also it shows the significant difference between the carbon nanotubes and the nano fibers.

Advances in Manufacturing & Industrial Engineering July 2007 Niraj Sinha & T.Y. CARBON NANOTUBES A REVIEW. 2. N. no.hpc.W. Carbon nanotube Composites..com/education/gallery/HOPG_ani. “International Materials Reviews 49” 31-43.Shivraj Narayan & Dr.org/resources/ 33 .ac. P. Yeow “Carbon Nanotubes for Biomedical Applications” IEEE transactions on Nanobioscience. 2004 http://www.nanoscience. Ramesh.html http://www.in/%7Eewels/img/science http://nanotechweb.J. June 2007 Harris.susx. vol 4.N.F.