Climatic change on carbon nanotubes – Carbon nanotubes have many characteristics that promise to revolutionize the world of structural materials. There are different ways to grow carbon nanotubes, especially the CVD technique, which allows obtaining SWCNT’s on a silicon surface. These SWCNT can be carried from the silicon surface to another surface, as HOPG, without suffering changes on their properties. That means nanomanipulation of carbon nanotubes.
Carbon Nanotubes
The intent of this section is to convey a general understanding of what carbon Nanotubes are, how they are produced, their many unique and interesting properties, markets, and applications.
In 1980 we knew of only three forms of carbon, namely diamond, graphite, and amorphous carbon. Today we know there is a whole family of other forms of carbon. The first to be discovered was the hollow, cage-like buckminsterfullerene molecule - also known as the buckyball, or the C60 fullerene. There are now thirty or more forms of fullerenes, and also an extended family of linear molecules, carbon nanotubes. C60 is the first spherical carbon molecule, with carbon atoms arranged in a soccer ball shape. In the structure there are 60 carbon atoms and a number of five-membered rings isolated by six-membered rings. The second, slightly elongated, spherical carbon molecule in the same group resembles a rugby ball, has seventy carbon atoms and is known as C70. C70’s structure has extra six-membered carbon rings, but there are also a large number of other potential structures containing the same number of carbon atoms. Their particular shapes depend on whether five-membered rings are isolated or not, or whether seven-membered rings are present. Many other forms of fullerenes up to and beyond C120 have been characterized, and it is possible to make other fullerene structures with five-membered rings in different positions and sometimes adjoining one another. The important fact for nanotechnology is that useful dopant atoms can be placed inside the hollow fullerene ball. Atoms contained within the fullerene are said to be endohedral. Of course they can also be bonded to fullerenes outside the ball as salts, if the fullerene can gain electrons. Endohedral fullerenes can be produced in which metal atoms are captured within the fullerene cages. Theory shows that the maximum electrical conductivity is to be expected for endohedral metal atoms, which will transfer three electrons to the fullerene. Fullerenes can be dispersed on the surface as a monolayer. That is, there is only one layer of molecules, and they are said to be mono dispersed. Provided fullerenes can be placed in very specific locations, they may be aligned to form a fullerene wire. Systems with appropriate material inside the fullerene ball are conducting and are of particular interest because they can be deposited to produce bead-like conducting circuits. Combining endohedrally doped structures with non-doped structures changes the actual composition of a fullerene wire, so that it may be tailored in-situ during patterning. Hence within a single wire, insulating and conducting regions may be precisely defined. One-dimensional junction engineering becomes realistic with fullerenes. Possibly more important than fullerenes are Carbon nanotubes, which are related to graphite. The molecular structure of graphite resembles stacked, one-atom-thick sheets of chicken wire - a planar network of interconnected hexagonal rings of carbon atoms. In conventional graphite, the sheets of carbon are stacked on top of one another, allowing them to easily slide over each other. That is why graphite is not hard, but it feels greasy, and can be used as a lubricant. When graphene sheets are rolled into a cylinder and their edges joined, they form CNTs. Only the tangents of the graphitic planes come into contact with each other, and hence their properties are more like those of a molecule. CNTs come in a variety of diameters, lengths, and functional group content. CNTs today are available for industrial applications in bulk quantities up metric ton quantities from Cheap Tubes. Several CNT manufacturers have >100 ton per year production capacity for multi walled nanotubes. A nanotube may consist of one tube of graphite, a one-atom thick single-wall nanotube, or a number of concentric tubes called multiwalled nanotubes. When viewed with a transmission electron microscope these tubes appear as planes. Whereas single walled nanotubes appear as two planes, in multi walled nanotubes more than two planes are observed, and can be seen as a series of parallel lines. There are different types of CNTs, because the graphitic sheets can be rolled in different ways. The three types of CNTs are Zigzag, Armchair, and Chiral. It is possible to recognize zigzag, armchair, and chiral CNTs just by following the pattern across the diameter of the tubes, and analyzing their cross-sectional structure. Multi walled nanotubes can come in an even more complex array of forms, because each concentric single-walled nanotube can have different structures, and hence there are a variety of sequential arrangements. The simplest sequence is when concentric layers are identical but different in diameter. However, mixed variants are possible, consisting of two or more types of concentric CNTs arranged in different orders. These can have either regular layering or random layering. The structure of the nanotube influences its properties - including electrical and thermal conductivity, density, and lattice structure. Both type and diameter are important. The wider the diameter of the nanotube, the more it behaves like graphite. The narrower the diameter of the nanotube, the more its intrinsic properties depends upon its specific type.
Applications.
The special nature of carbon combined with the molecular perfection of single-walled nanotubes to endow them with exceptional material properties, such as very high electrical and thermal conductivity, strength, stiffness, and toughness. No other element in the periodic table bonds to itself in an extended network with the strength of the carbon-carbon bond. The delocalized pi-electron donated by each atom is free to move about the entire structure, rather than remain with its donor atom, giving rise to the first known molecule with metallic-type electrical conductivity. Furthermore, the high-frequency carbon-carbon bonds vibrations provide an intrinsic thermal conductivity higher than even diamond. In most conventional materials, however, the actual observed material properties - strength, electrical conductivity, etc. - are degraded very substantially by the occurrence of defects in their structure. For example, high-strength steel typically fails at only about 1% of its theoretical breaking strength. CNTs, however, achieve values very close to their theoretical limits because of their molecular perfection of structure.
This aspect is part of the unique story of CNTs. CNTs are an example of true nanotechnology: they are under 100 nanometers in diameter, but are molecules that can be manipulated chemically and physically in very useful ways. They open an incredible range of applications in materials science, electronics, chemical processing, energy management, and many other fields. CNTs have extraordinary electrical conductivity, heat conductivity, and mechanical properties. They are probably the best electron field-emitter possible. They are polymers of pure carbon and can be reacted and manipulated using the well-known and the tremendously rich chemistry of carbon. This provides opportunity to modify their structure, and to optimize their solubility and dispersion. Very significantly, CNTs are molecularly perfect, which means that they are normally free of property-degrading flaws in the nanotube structure. Their material properties can therefore approach closely the very high levels intrinsic to them. These extraordinary characteristics give CNTs potential in numerous applications.
a) Field Emission
CNTs are the best known field emitters of any material. This is understandable, given their high electrical conductivity, and the incredible sharpness of their tip. The smaller the tip’s radius of curvature, the more concentrated the electric field will be, leading to increased field emission. The sharpness of the tip also means that they emit at especially low voltage, an important fact for building low-power electrical devices that utilize this feature. CNTs can carry an astonishingly high current density. Furthermore, the current is extremely stable. An immediate application of this behavior receiving considerable interest is in field-emission flat-panel displays. Instead of a single electron gun, as in a traditional cathode ray tube display, in CNT-based displays there is a separate nanotube electron gun for each individual pixel in the display. Their high current density, low turn-on and operating voltages, and steady, long-lived behavior make CNTs very attractive field emitters in this application. Other applications utilizing the field-emission characteristics of CNTs include general types of low-voltage cold-cathode lighting sources, lightning arrestors, and electron microscope sources.
b) Conductive or Reinforced Plastics
Much of the history of plastics over the last half-century has involved their use as a replacement for metals. For structural applications, plastics have made tremendous headway, but not where electrical conductivity is required, because plastics are very good electrical insulators. This deficiency is overcome by loading plastics up with conductive fillers, such as carbon black and larger graphite fibers. The loading required to provide the necessary conductivity using conventional fillers is typically high, however, resulting in heavy parts, and more importantly, plastic parts whose structural properties are highly degraded. It is well-established that the higher the aspect ratio of the filler particles, the lower the loading required to achieve a given level of conductivity.
CNTs are ideal in this sense, since they have the highest aspect ratio of any carbon fiber. In addition, their natural tendency to form ropes provides inherently very long conductive pathways even at ultra-low loadings. Applications that exploit this behavior of CNTs include EMI/RFI shielding composites; coatings for enclosures, gaskets, and other uses such as electrostatic dissipation; antistatic materials, transparent conductive coatings; and radar-absorbing materials for stealth applications.
A lot of automotive plastics companies are using CNTs as well. CNTs have been added into the side mirror plastics on automobiles in the US since the late 1990s. I have seen forecasts predicting that GM alone will consume over 500 pounds of CNT masterbatches in 2006 for using in all areas of automotive plastics. Masterbatches normally contain 20 wt% cnts which are already very well dispersed. Manufacturers then need to perform a “let down” or dilution procedure prior to using the masterbatch in production
c) Energy Storage
CNTs have the intrinsic characteristics desired in material used as electrodes in batteries and capacitors, two technologies of rapidly increasing importance. CNTs have a tremendously high surface area, good electrical conductivity, and very importantly, their linear geometry makes their surface highly accessible to the electrolyte.
Research has shown that CNTs have the highest reversible capacity of any carbon material for use in lithium ion batteries. In addition, CNTs are outstanding materials for super capacitor electrodes and are now being marketed for this application. CNTs also have applications in a variety of fuel cell components. They have a number of properties, including high surface area and thermal conductivity, which make them useful as electrode catalyst supports in PEM fuel cells. Because of their high electrical conductivity, they may also be used in gas diffusion layers, as well as current collectors. CNTs' high strength and toughness-to-weight characteristics may also prove valuable as part of composite components in fuel cells that are deployed in transport applications, where durability is extremely important
This aspect is part of the unique story of CNTs. CNTs are an example of true nanotechnology: they are under 100 nanometers in diameter, but are molecules that can be manipulated chemically and physically in very useful ways. They open an incredible range of applications in materials science, electronics, chemical processing, energy management, and many other fields. CNTs have extraordinary electrical conductivity, heat conductivity, and mechanical properties. They are probably the best electron field-emitter possible. They are polymers of pure carbon and can be reacted and manipulated using the well-known and the tremendously rich chemistry of carbon. This provides opportunity to modify their structure, and to optimize their solubility and dispersion. Very significantly, CNTs are molecularly perfect, which means that they are normally free of property-degrading flaws in the nanotube structure. Their material properties can therefore approach closely the very high levels intrinsic to them. These extraordinary characteristics give CNTs potential in numerous applications.
a) Field Emission
CNTs are the best known field emitters of any material. This is understandable, given their high electrical conductivity, and the incredible sharpness of their tip. The smaller the tip’s radius of curvature, the more concentrated the electric field will be, leading to increased field emission. The sharpness of the tip also means that they emit at especially low voltage, an important fact for building low-power electrical devices that utilize this feature. CNTs can carry an astonishingly high current density. Furthermore, the current is extremely stable. An immediate application of this behavior receiving considerable interest is in field-emission flat-panel displays. Instead of a single electron gun, as in a traditional cathode ray tube display, in CNT-based displays there is a separate nanotube electron gun for each individual pixel in the display. Their high current density, low turn-on and operating voltages, and steady, long-lived behavior make CNTs very attractive field emitters in this application. Other applications utilizing the field-emission characteristics of CNTs include general types of low-voltage cold-cathode lighting sources, lightning arrestors, and electron microscope sources.
b) Conductive or Reinforced Plastics
Much of the history of plastics over the last half-century has involved their use as a replacement for metals. For structural applications, plastics have made tremendous headway, but not where electrical conductivity is required, because plastics are very good electrical insulators. This deficiency is overcome by loading plastics up with conductive fillers, such as carbon black and larger graphite fibers. The loading required to provide the necessary conductivity using conventional fillers is typically high, however, resulting in heavy parts, and more importantly, plastic parts whose structural properties are highly degraded. It is well-established that the higher the aspect ratio of the filler particles, the lower the loading required to achieve a given level of conductivity.
CNTs are ideal in this sense, since they have the highest aspect ratio of any carbon fiber. In addition, their natural tendency to form ropes provides inherently very long conductive pathways even at ultra-low loadings. Applications that exploit this behavior of CNTs include EMI/RFI shielding composites; coatings for enclosures, gaskets, and other uses such as electrostatic dissipation; antistatic materials, transparent conductive coatings; and radar-absorbing materials for stealth applications.
A lot of automotive plastics companies are using CNTs as well. CNTs have been added into the side mirror plastics on automobiles in the US since the late 1990s. I have seen forecasts predicting that GM alone will consume over 500 pounds of CNT masterbatches in 2006 for using in all areas of automotive plastics. Masterbatches normally contain 20 wt% cnts which are already very well dispersed. Manufacturers then need to perform a “let down” or dilution procedure prior to using the masterbatch in production
c) Energy Storage
CNTs have the intrinsic characteristics desired in material used as electrodes in batteries and capacitors, two technologies of rapidly increasing importance. CNTs have a tremendously high surface area, good electrical conductivity, and very importantly, their linear geometry makes their surface highly accessible to the electrolyte.
Research has shown that CNTs have the highest reversible capacity of any carbon material for use in lithium ion batteries. In addition, CNTs are outstanding materials for super capacitor electrodes and are now being marketed for this application. CNTs also have applications in a variety of fuel cell components. They have a number of properties, including high surface area and thermal conductivity, which make them useful as electrode catalyst supports in PEM fuel cells. Because of their high electrical conductivity, they may also be used in gas diffusion layers, as well as current collectors. CNTs' high strength and toughness-to-weight characteristics may also prove valuable as part of composite components in fuel cells that are deployed in transport applications, where durability is extremely important
d) Conductive Adhesives and Connectors
The same properties that make CNTs attractive as conductive fillers for use in electromagnetic shielding, ESD materials, etc., make them attractive for electronics packaging and interconnection applications, such as adhesives, potting compounds, coaxial cables, and other types of connectors.
e) Molecular Electronics
The idea of building electronic circuits out of the essential building blocks of materials - molecules - has seen a revival the past few years, and is a key component of nanotechnology. In any electronic circuit, but particularly as dimensions shrink to the nanoscale, the interconnections between switches and other active devices become increasingly important. Their geometry, electrical conductivity, and ability to be precisely derived, make CNTs the ideal candidates for the connections in molecular electronics. In addition, they have been demonstrated as switches themselves.
There are already companies such as Nantero from Woburn, MA that are already making CNT based non-volitle random access memory for PC’s. A lot of research is being done to design CNT based transistors as well.
f) Thermal Materials
The record-setting anisotropic thermal conductivity of CNTs is enabling many applications where heat needs to move from one place to another. Such an application is found in electronics, particularly heat sinks for chips used in advanced computing, where uncooled chips now routinely reach over 100oC. The technology for creating aligned structures and ribbons of CNTs [D.Walters, et al., Chem. Phys. Lett. 338, 14 (2001)] is a step toward realizing incredibly efficient heat conduits. In addition, composites with CNTs have been shown to dramatically increase their bulk thermal conductivity, even at very small loadings.
g) Structural Composites
The superior properties of CNTs are not limited to electrical and thermal conductivities, but also include mechanical properties, such as stiffness, toughness, and strength. These properties lead to a wealth of applications exploiting them, including advanced composites requiring high values of one or more of these properties.
The same properties that make CNTs attractive as conductive fillers for use in electromagnetic shielding, ESD materials, etc., make them attractive for electronics packaging and interconnection applications, such as adhesives, potting compounds, coaxial cables, and other types of connectors.
e) Molecular Electronics
The idea of building electronic circuits out of the essential building blocks of materials - molecules - has seen a revival the past few years, and is a key component of nanotechnology. In any electronic circuit, but particularly as dimensions shrink to the nanoscale, the interconnections between switches and other active devices become increasingly important. Their geometry, electrical conductivity, and ability to be precisely derived, make CNTs the ideal candidates for the connections in molecular electronics. In addition, they have been demonstrated as switches themselves.
There are already companies such as Nantero from Woburn, MA that are already making CNT based non-volitle random access memory for PC’s. A lot of research is being done to design CNT based transistors as well.
f) Thermal Materials
The record-setting anisotropic thermal conductivity of CNTs is enabling many applications where heat needs to move from one place to another. Such an application is found in electronics, particularly heat sinks for chips used in advanced computing, where uncooled chips now routinely reach over 100oC. The technology for creating aligned structures and ribbons of CNTs [D.Walters, et al., Chem. Phys. Lett. 338, 14 (2001)] is a step toward realizing incredibly efficient heat conduits. In addition, composites with CNTs have been shown to dramatically increase their bulk thermal conductivity, even at very small loadings.
g) Structural Composites
The superior properties of CNTs are not limited to electrical and thermal conductivities, but also include mechanical properties, such as stiffness, toughness, and strength. These properties lead to a wealth of applications exploiting them, including advanced composites requiring high values of one or more of these properties.
h) Fibers and Fabrics
Fibers spun of pure CNTs have recently been demonstrated and are undergoing rapid development, along with CNT composite fibers. Such super-strong fibers will have many applications including body and vehicle armor, transmission line cables, woven fabrics and textiles.
i) Catalyst Support
CNTs intrinsically have an enormously high surface area; in fact, for single walled nanotubes every atom is not just on one surface - each atom is on two surfaces, the inside and the outside of the nanotube! Combined with the ability to attach essentially any chemical species to their sidewalls this provides an opportunity for unique catalyst supports. Their electrical conductivity may also be exploited in the search for new catalysts and catalytic behavior.
j) CNT Ceramics
A ceramic material reinforced with carbon nanotubes has been made by materials scientists at UC Davis. The new material is far tougher than conventional ceramics, conducts electricity and can both conduct heat and act as a thermal barrier, depending on the orientation of the nanotubes. Ceramic materials are very hard and resistant to heat and chemical attack, making them useful for applications such as coating turbine blades, but they are also very brittle.
The researchers mixed powdered alumina (aluminum oxide) with 5 to 10 percent carbon nanotubes and a further 5 percent finely milled niobium. The researchers treated the mixture with an electrical pulse in a process called spark-plasma sintering. This process consolidates ceramic powders more quickly and at lower temperatures than conventional processes.
The new material has up to five times the fracture toughness -- resistance to cracking under stress -- of conventional alumina. The material shows electrical conductivity seven times that of previous ceramics made with nanotubes. It also has interesting thermal properties, conducting heat in one direction, along the alignment of the nanotubes, but reflecting heat at right angles to the nanotubes, making it an attractive material for thermal barrier coatings.
k) Biomedical Applications
The exploration of CNTs in biomedical applications is just underway, but has significant potential. Since a large part of the human body consists of carbon, it is generally thought of as a very biocompatible material. Cells have been shown to grow on CNTs, so they appear to have no toxic effect. The cells also do not adhere to the CNTs, potentially giving rise to applications such as coatings for prosthetics and surgical implants. The ability to functionalize the sidewalls of CNTs also leads to biomedical applications such as vascular stents, and neuron growth and regeneration. It has also been shown that a single strand of DNA can be bonded to a nanotube, which can then be successfully inserted into a cell; this has potential applications in gene therapy.
l) Air, Water and Gas Filtration
Many researchers and corporations have already developed CNT based air and water filtration devices. It has been reported that these filters can not only block the smallest particles but also kill most bacteria. This is another area where CNTs have already been commercialized and products are on the market now. Someday CNTs may be used to filter other liquids such as fuels and lubricants as well.
A lot of research is being done in the development of CNT based air and gas filtration. Filtration has been shown to be another area where it is cost effective to use CNTs already. The research I’ve seen suggests that 1 gram of MWNTs can be dispersed onto 1 sq ft of filter media. Manufacturers can get their cost down to 35 cents per gram of purified MWNTs when purchasing ton quantities.
m) Other Applications
Some commercial products on the market today utilizing CNTs include stain resistant textiles, CNT reinforced tennis rackets and baseball bats. Companies like Kraft foods are heavily funding cnt based plastic packaging. Food will stay fresh longer if the packaging is less permeable to atmosphere. Coors Brewing company has developed new plastic beer bottles that stay cold for longer periods of time. Samsung already has CNT based flat panel displays on the market. A lot of companies are looking forward to being able to produce transparent conductive coatings and phase out ITO coatings. Samsung uses align SWNTs in the transparent conductive layer of their display manufacturing process.
Fibers spun of pure CNTs have recently been demonstrated and are undergoing rapid development, along with CNT composite fibers. Such super-strong fibers will have many applications including body and vehicle armor, transmission line cables, woven fabrics and textiles.
i) Catalyst Support
CNTs intrinsically have an enormously high surface area; in fact, for single walled nanotubes every atom is not just on one surface - each atom is on two surfaces, the inside and the outside of the nanotube! Combined with the ability to attach essentially any chemical species to their sidewalls this provides an opportunity for unique catalyst supports. Their electrical conductivity may also be exploited in the search for new catalysts and catalytic behavior.
j) CNT Ceramics
A ceramic material reinforced with carbon nanotubes has been made by materials scientists at UC Davis. The new material is far tougher than conventional ceramics, conducts electricity and can both conduct heat and act as a thermal barrier, depending on the orientation of the nanotubes. Ceramic materials are very hard and resistant to heat and chemical attack, making them useful for applications such as coating turbine blades, but they are also very brittle.
The researchers mixed powdered alumina (aluminum oxide) with 5 to 10 percent carbon nanotubes and a further 5 percent finely milled niobium. The researchers treated the mixture with an electrical pulse in a process called spark-plasma sintering. This process consolidates ceramic powders more quickly and at lower temperatures than conventional processes.
The new material has up to five times the fracture toughness -- resistance to cracking under stress -- of conventional alumina. The material shows electrical conductivity seven times that of previous ceramics made with nanotubes. It also has interesting thermal properties, conducting heat in one direction, along the alignment of the nanotubes, but reflecting heat at right angles to the nanotubes, making it an attractive material for thermal barrier coatings.
k) Biomedical Applications
The exploration of CNTs in biomedical applications is just underway, but has significant potential. Since a large part of the human body consists of carbon, it is generally thought of as a very biocompatible material. Cells have been shown to grow on CNTs, so they appear to have no toxic effect. The cells also do not adhere to the CNTs, potentially giving rise to applications such as coatings for prosthetics and surgical implants. The ability to functionalize the sidewalls of CNTs also leads to biomedical applications such as vascular stents, and neuron growth and regeneration. It has also been shown that a single strand of DNA can be bonded to a nanotube, which can then be successfully inserted into a cell; this has potential applications in gene therapy.
l) Air, Water and Gas Filtration
Many researchers and corporations have already developed CNT based air and water filtration devices. It has been reported that these filters can not only block the smallest particles but also kill most bacteria. This is another area where CNTs have already been commercialized and products are on the market now. Someday CNTs may be used to filter other liquids such as fuels and lubricants as well.
A lot of research is being done in the development of CNT based air and gas filtration. Filtration has been shown to be another area where it is cost effective to use CNTs already. The research I’ve seen suggests that 1 gram of MWNTs can be dispersed onto 1 sq ft of filter media. Manufacturers can get their cost down to 35 cents per gram of purified MWNTs when purchasing ton quantities.
m) Other Applications
Some commercial products on the market today utilizing CNTs include stain resistant textiles, CNT reinforced tennis rackets and baseball bats. Companies like Kraft foods are heavily funding cnt based plastic packaging. Food will stay fresh longer if the packaging is less permeable to atmosphere. Coors Brewing company has developed new plastic beer bottles that stay cold for longer periods of time. Samsung already has CNT based flat panel displays on the market. A lot of companies are looking forward to being able to produce transparent conductive coatings and phase out ITO coatings. Samsung uses align SWNTs in the transparent conductive layer of their display manufacturing process.
