Images

Tiny spaces have formed inside titanium dioxide nanocrystals, as shown in this SEM image. The square structure of these inside spaces, which measure between 20 nm and 40 nm, is due to the crystalline structure of the material. (Image: L. Nasi, IMEM (CNR), Parma. Artwork: Lucia Covi)
SEM image of a work sample on a magnesium oxide surface using FIB. The diameter of the hole measures approximate. 4 µm. (Image: G.C. Gazzadi, A. Spessot, S3 (INFM-CNR), Modena. Artwork: Lucia Covi)
SEM image of a micron sized trench (10 x 20 x14 µm³) in a Cu/SiO₂/Si multilayer, obtained through FIB milling. The precision of this technique allows the visualization of ultrathin (tens of nanometers) layers. (Image: G.C.Gazzadi, S.Frabboni, S3 (INFM-CNR), Modena. Artwork: Lucia Covi)
Scanning electron microscope (SEM) image of quantum dots fabricated through electron beam lithography and subsequent dry-chemical etching on a quasi bidimensional layer (GaAl heterostructure). These structures are used to study the behavior of electrons, which are confined into tiny spaces – approximate. 10 electrons per dot. The diameter of each quantum dot is 200 nm (which means that a billion of these structure easily fit on the tip of your finger). (Image: C.P. Garcia, V. Pellegrini , NEST (INFM), Pisa. Artwork: Lucia Covi)
Top view of a hole carved in a polyethylene surface. During a series of experiments the use of a FIB has proven to be very versatile and capable of carving various materials, including plastic. (Image: G.C. Gazzadi, S3 (INFM-CNR), Modena. Artwork: Lucia Covi)
Developing new instruments to be able to "see" at the nanoscale is a research field in itself. Shown here is the tip of an atomic force microscope (AFM), one of the foremost tools for imaging, measuring and manipulating matter at the nanoscale. Here, a platinum electrode measuring one hundredth of a nanometer has been deposited on the tip of this pyramid shaped AFM tip via focused ion beam (FIB) deposition. (Image: C. Menozzi, G.C. Gazzadi, S3 (INFM-CNR), Modena. Artwork: Lucia Covi)

Applications of CNT

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.

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 .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.

Production methods

There are a number of methods of making CNTs and fullerenes. Fullerenes were first observed after vaporizing graphite with a short-pulse, high-power laser, however this was not a practical method for making large quantities. CNTs have probably been around for a lot longer than was first realized, and may have been made during various carbon combustion and vapor deposition processes, but electron microscopy at that time was not advanced enough to distinguish them from other types of tubes. The first method for producing CNTs and fullerenes in reasonable quantities – was by applying an electric current across two carbonaceous electrodes in an inert gas atmosphere. This method is called plasma arcing. It involves the evaporation of one electrode as cations followed by deposition at the other electrode. This plasma-based process is analogous to the more familiar electroplating process in a liquid medium. Fullerenes and CNTs are formed by plasma arcing of carbonaceous materials, particularly graphite. The fullerenes appear in the soot that is formed, while the CNTs are deposited on the opposing electrode. Another method of nanotube synthesis involves plasma arcing in the presence of cobalt with a 3% or greater concentration. As noted above, the nanotube product is a compact cathode deposit of rod like morphology. However when cobalt is added as a catalyst, the nature of the product changes to a web, with strands of 1mm or so thickness that stretch from the cathode to the walls of the reaction vessel. The mechanism by which cobalt changes this process is unclear, however one possibility is that such metals affect the local electric fields and hence the formation of the five-membered rings.

a) Arc Method
The carbon arc discharge method, initially used for producing C60 fullerenes, is the most common and perhaps easiest way to produce CNTs, as it is rather simple. However, it is a technique that produces a complex mixture of components, and requires further purification - to separate the CNTs from the soot and the residual catalytic metals present in the crude product. This method creates CNTs through arc-vaporization of two carbon rods placed end to end, separated by approximately 1mm, in an enclosure that is usually filled with inert gas at low pressure. Recent investigations have shown that it is also possible to create CNTs with the arc method in liquid nitrogen. A direct current of 50 to 100 A, driven by a potential difference of approximately 20 V, creates a high temperature discharge between the two electrodes. The discharge vaporizes the surface of one of the carbon electrodes, and forms a small rod-shaped deposit on the other electrode. Producing CNTs in high yield depends on the uniformity of the plasma arc, and the temperature of the deposit forming on the carbon electrode.

b) Laser Method
In 1996 CNTs were first synthesized using a dual-pulsed laser and achieved yields of >70wt% purity. Samples were prepared by laser vaporization of graphite rods with a 50:50 catalyst mixture of Cobalt and Nickel at 1200°C in flowing argon, followed by heat treatment in a vacuum at 1000°C to remove the C60 and other fullerenes. The initial laser vaporization pulse was followed by a second pulse, to vaporize the target more uniformly. The use of two successive laser pulses minimizes the amount of carbon deposited as soot. The second laser pulse breaks up the larger particles ablated by the first one, and feeds them into the growing nanotube structure. The material produced by this method appears as a mat of “ropes”, 10-20nm in diameter and up to 100µm or more in length. Each rope is found to consist primarily of a bundle of single walled nanotubes, aligned along a common axis. By varying the growth temperature, the catalyst composition, and other process parameters, the average nanotube diameter and size distribution can be varied. Arc-discharge and laser vaporization are currently the principal methods for obtaining small quantities of high quality CNTs. However, both methods suffer from drawbacks. The first is that both methods involve evaporating the carbon source, so it has been unclear how to scale up production to the industrial level using these approaches. The second issue relates to the fact that vaporization methods grow CNTs in highly tangled forms, mixed with unwanted forms of carbon and/or metal species. The CNTs thus produced are difficult to purify, manipulate, and assemble for building nanotube-device architectures for practical applications.

c) Chemical Vapor Deposition
Chemical vapor deposition of hydrocarbons over a metal catalyst is a classical method that has been used to produce various carbon materials such as carbon fibers and filaments. for over twenty years. Large amounts of CNTs can be formed by catalytic CVD of acetylene over Cobalt and iron catalysts supported on silica or zeolite. The carbon deposition activity seems to relate to the cobalt content of the catalyst, whereas the CNTs’ selectivity seems to be a function of the pH in catalyst preparation. Fullerenes and bundles of single walled nanotubes were also found among the multi walled nanotubes produced on the carbon/zeolite catalyst. Some researchers are experimenting with the formation of CNTs from ethylene. Supported catalysts such as iron, cobalt, and nickel, containing either a single metal or a mixture of metals, seem to induce the growth of isolated single walled nanotubes or single walled nanotubes bundles in the ethylene atmosphere. The production of single walled nanotubes, as well as double-walled CNTs, on molybdenum and molybdenum-iron alloy catalysts has also been demonstrated. CVD of carbon within the pores of a thin alumina template with or without a Nickel catalyst has been achieved. Ethylene was used with reaction temperatures of 545°C for Nickel-catalyzed CVD, and 900°C for an uncatalyzed process. The resultant carbon nanostructures have open ends, with no caps. Methane has also been used as a carbon source. In particular it has been used to obtain ‘nanotube chips’ containing isolated single walled nanotubes at controlled locations. High yields of single walled nanotubes have been obtained by catalytic decomposition of an H2/CH4 mixture over well-dispersed metal particles such as Cobalt, Nickel, and Iron on magnesium oxide at 1000°C. It has been reported that the synthesis of composite powders containing well-dispersed CNTs can be achieved by selective reduction in an H2/CH4 atmosphere of oxide solid solutions between a non-reducible oxide such as Al2O3 or MgAl2O4 and one or more transition metal oxides. The reduction produces very small transition metal particles at a temperature of usually >800°C. The decomposition of CH4 over the freshly formed nanoparticles prevents their further growth, and thus results in a very high proportion of single walled nanotubes and fewer multi walled nanotubes.

d) Ball Milling
Ball milling and subsequent annealing is a simple method for the production of CNTs. Although it is well established that mechanical attrition of this type can lead to fully nano porous microstructures, it was not until a few years ago that CNTs of carbon and boron nitride were produced from these powders by thermal annealing. Essentially the method consists of placing graphite powder into a stainless steel container along with four hardened steel balls. The container is purged, and argon is introduced. The milling is carried out at room temperature for up to 150 hours. Following milling, the powder is annealed under an inert gas flow at temperatures of 1400°C for six hours. The mechanism of this process is not known, but it is thought that the ball milling process forms nanotube nuclei, and the annealing process activates nanotube growth. Research has shown that this method produces more multi walled nanotubes and few single walled nanotubes.

e) Other Methods
CNTs can also be produced by diffusion flame synthesis, electrolysis, use of solar energy, heat treatment of a polymer, and low-temperature solid pyrolysis. In flame synthesis, combustion of a portion of the hydrocarbon gas provides the elevated temperature required, with the remaining fuel conveniently serving as the required hydrocarbon reagent. Hence the flame constitutes an efficient source of both energy and hydrocarbon raw material. Combustion synthesis has been shown to be scalable for high-volume commercial production.

Properties of CNT

This section tries to give an overview of the many useful and unique properties of CNTs.
a) Electrical Conductivity
CNTs can be highly conducting, and hence can be said to be metallic. Their conductivity has been shown to be a function of their chirality, the degree of twist as well as their diameter. CNTs can be either metallic or semi-conducting in their electrical behavior. Conductivity in MWNTs is quite complex. Some types of “armchair”-structured CNTs appear to conduct better than other metallic CNTs. Furthermore, interwall reactions within multi walled nanotubes have been found to redistribute the current over individual tubes non-uniformly. However, there is no change in current across different parts of metallic single-walled nanotubes. The behavior of the ropes of semi-conducting single walled nanotubes is different, in that the transport current changes abruptly at various positions on the CNTs.
The conductivity and resistivity of ropes of single walled nanotubes has been measured by placing electrodes at different parts of the CNTs. The resistivity of the single walled nanotubes ropes was of the order of 10–4 ohm-cm at 27°C. This means that single walled nanotube ropes are the most conductive carbon fibers known. The current density that was possible to achieve was 10-7 A/cm2, however in theory the single walled nanotube ropes should be able to sustain much higher stable current densities, as high as 10-13 A/cm2. It has been reported that individual single walled nanotubes may contain defects. Fortuitously, these defects allow the single walled nanotubes to act as transistors. Likewise, joining CNTs together may form transistor-like devices. A nanotube with a natural junction (where a straight metallic section is joined to a chiral semiconducting section) behaves as a rectifying diode – that is, a half-transistor in a single molecule. It has also recently been reported that single walled nanotubes can route electrical signals at speeds up to 10 GHz when used as interconnects on semi-conducting devices.
b) Strength and Elasticity
The carbon atoms of a single sheet of graphite form a planar honeycomb lattice, in which each atom is connected via a strong chemical bond to three neighboring atoms. Because of these strong bonds, the basal plane elastic modulus of graphite is one of the largest of any known material. For this reason, CNTs are expected to be the ultimate high-strength fibers. Single walled nanotubes are stiffer than steel, and are very resistant to damage from physical forces. Pressing on the tip of a nanotube will cause it to bend, but without damage to the tip. When the force is removed, the nanotube returns to its original state. This property makes CNTs very useful as probe tips for very high-resolution scanning probe microscopy. Quantifying these effects has been rather difficult, and an exact numerical value has not been agreed upon.
Using atomic force microscopy, the unanchored ends of a freestanding nanotube can be pushed out of their equilibrium position, and the force required to push the nanotube can be measured. The current Young’s modulus value of single walled nanotubes is about 1 TeraPascal, but this value has been widely disputed, and a value as high as 1.8 Tpa has been reported. Other values significantly higher than that have also been reported. The differences probably arise through different experimental measurement techniques. Others have shown theoretically that the Young’s modulus depends on the size and chirality of the single walled nanotubes, ranging from 1.22 Tpa to 1.26 Tpa. They have calculated a value of 1.09 Tpa for a generic nanotube. However, when working with different multi walled nanotubes, others have noted that the modulus measurements of multi walled nanotubes using AFM techniques do not strongly depend on the diameter. Instead, they argue that the modulus of the multi walled nanotubes correlates to the amount of disorder in the nanotube walls. Not surprisingly, when multi walled nanotubes break, the outermost layers break first.
c) Thermal Conductivity and Expansion
CNTs have been shown to exhibit superconductivity below 20°K (aaprox. -253°C). Research suggests that these exotic strands, already heralded for their unparalleled strength and unique ability to adopt the electrical properties of either semiconductors or perfect metals, may someday also find applications as miniature heat conduits in a host of devices and materials. The strong in-plane graphitic carbon - carbon bonds make them exceptionally strong and stiff against axial strains. The almost zero in-plane thermal expansion but large inter-plane expansion of single walled nanotubes implies strong in-plane coupling and high flexibility against non-axial strains.
Many applications of CNTs, such as in nanoscale molecular electronics, sensing and actuating devices, or as reinforcing additive fibers in functional composite materials, have been proposed. Reports of several recent experiments on the preparation and mechanical characterization of CNT-polymer composites have also appeared. These measurements suggest modest enhancements in strength characteristics of CNT-embedded matrixes as compared to bare polymer matrixes. Preliminary experiments and simulation studies on the thermal properties of CNTs show very high thermal conductivity. It is expected, therefore, that nanotube reinforcements in polymeric materials may also significantly improve the thermal and thermomechanical properties of the composites.
d) Field Emission
Field emission results from the tunneling of electrons from a metal tip into vacuum, under application of a strong electric field. The small diameter and high aspect ratio of CNTs is very favorable for field emission. Even for moderate voltages, a strong electric field develops at the free end of supported CNTs because of their sharpness. This was observed by de Heer and co-workers at EPFL in 1995. He also immediately realized that these field emitters must be superior to conventional electron sources and might find their way into all kind of applications, most importantly flat-panel displays. It is remarkable that after only five years Samsung actually realized a very bright color display, which will be shortly commercialized using this technology. Studying the field emission properties of multi walled nanotubes, Bonard and co-workers at EPFL observed that together with electrons, light is emitted as well. This luminescence is induced by the electron field emission, since it is not detected without applied potential. This light emission occurs in the visible part of the spectrum, and can sometimes be seen with the naked eye.
e) High Aspect Ratio
CNTs represent a very small, high aspect ratio conductive additive for plastics of all types. Their high aspect ratio means that a lower loading of CNTs is needed compared to other conductive additives to achieve the same electrical conductivity. This low loading preserves more of the polymer resins’ toughness, especially at low temperatures, as well as maintaining other key performance properties of the matrix resin. CNTs have proven to be an excellent additive to impart electrical conductivity in plastics. Their high aspect ratio, about 1000:1 imparts electrical conductivity at lower loadings, compared to conventional additive materials such as carbon black, chopped carbon fiber, or stainless steel fiber.
f) Highly Absorbent
The large surface area and high absorbency of CNTs make them ideal candidates for use in air, gas, and water filtration. A lot of research is being done in replacing activated charcoal with CNTs in certain ultra high purity applications.

Current Applications

Presently nanotechnology is being applied to the following fields.

a) Sunscreens and Cosmetics
Nanosized titanium dioxide and zinc oxide are currently used in some sunscreens, as they absorb and reflect ultraviolet (UV) rays and yet are transparent to visible light and so are more appealing to the consumer. Nanosized iron oxide is present in some lipsticks as a pigment but it is our understanding that it is not used by the European cosmetics sector. The use of nanoparticles in cosmetics has raised a number of concerns about consumer safety.
b) Composites
An important use of nanoparticles and nanotubes is in composites, materials that combine one or more separate components and which are designed to exhibit overall the best properties of each component. This multi-functionality applies not only to mechanical properties, but extends to optical, electrical and magnetic ones. Currently, carbon fibres and bundles of multi-walled CNTs are used in polymers to control or enhance conductivity, with applications such as antistatic packaging. The use of individual CNTs in composites is a potential long-term application. A particular type of nanocomposite is where nanoparticles act as fillers in a matrix; for example, carbon black used as a filler to reinforce car tyres. However, particles of carbon black can range from tens to hundreds of nanometres in size, so not all carbon black falls within our definition of nanoparticles.
c) Clays
Clays containing naturally occurring nanoparticles have long been important as construction materials and are undergoing continuous improvement. Clay particle based composites – containing plastics and nano-sized flakes of clay – are also finding applications such as use in car bumpers.
d) Coatings and Surfaces
Coatings with thickness controlled at the nano- or atomic scale have been in routine production for some time, for example in molecular beam epitaxy or metal oxide chemical vapor depositionfor optoelectonic devices, or in catalytically active and chemically functionalized surfaces. Recently developed applications include the self-cleaning window, which is coated in highly activated titanium dioxide, engineered to be highly hydrophobic (water repellent) and antibacterial, and coatings based on nanoparticulate oxides that catalytically destroy chemical agents. Wear and scratch-resistant hard coatings are significantly improved by nanoscale intermediate layers (or multilayers) between the hard outer layer and the substrate material. The intermediate layers give good bonding and graded matching of elastic and thermal properties, thus improving adhesion. A range of enhanced textiles, such as breathable, waterproof and stainresistant fabrics, have been enabled by the improved control of porosity at the nanoscale and surface roughness in a variety of polymers and inorganics.
e) Tougher and Harder Cutting Tools
Cutting tools made of nanocrystalline materials, such as tungsten carbide, tantalum carbide and titanium carbide, are more wear and erosion-resistant, and last longer than their conventional (large-grained) counterparts. They are finding applications in the drills used to bore holes in circuit boards.

Nanoscale in Three Dimensions

Fullerenes (carbon 60)
In the mid-1980s a new class of carbon material was discovered called carbon 60 (C60).Harry Kroto and Richard Smalley, the experimental chemists who discovered C60 named it "buckminsterfullerene", in recognition of the architect Buckminster Fuller, who was well-known for building geodesic domes, and the term fullerenes was then given to any closed carbon cage. C60 are spherical molecules about 1nm in diameter, comprising 60 carbon atoms arranged as 20 hexagons and 12 pentagons: the configuration of a football. In 1990, a technique to produce larger quantities of C60 was developed by resistively heating graphite rods in a helium atmosphere. Several applications are envisaged for fullerenes, such as miniature ‘ball bearings’ to lubricate surfaces, drug delivery vehicles and in electronic circuits.

Dendrimers
Dendrimers are spherical polymeric molecules, formed through a nanoscale hierarchical self-assembly process. There are many types of dendrimer; the smallest is several nanometres in size. Dendrimers are used in conventional applications such as coatings and inks, but they also have a range of interesting properties which could lead to useful applications. For example, dendrimers can act as nanoscale carrier molecules and as such could be used in drug delivery. Environmental clean-up could be assisted by dendrimers as they can trap metal ions, which could then be filtered out of water with ultra-filtration techniques.

Quantum Dots
Nanoparticles of semiconductors (quantum dots) were theorized in the 1970s and initially created in the early 1980s. If semiconductor particles are made small enough, quantum effects come into play, which limit the energies at which electrons and holes (the absence of an electron) can exist in the particles. As energy is related to wavelength (or colour), this means that the optical properties of the particle can be finely tuned depending on its size. Thus, particles can be made to emit or absorb specific wavelengths (colours) of light, merely by controlling their size. Recently, quantum dots have found applications in composites, solar cells (Gratzel cells) and fluorescent biological labels (for example to trace a biological molecule) which use both the small particle size and tuneable energy levels. Recent advances in chemistry have resulted in the preparation of monolayer-protected, high-quality, monodispersed, crystalline quantum dots as small as 2nm in diameter, which can be conveniently treated and processed as a typical chemical reagent.

Nanoparticles

Nanoparticles are often defined as particles of less than 100nm in diameter. We classify nanoparticles to be particles less than 100nm in diameter that exhibit new or enhanced size-dependent properties compared with larger particles of the same material. Nanoparticles exist widely in the natural world: for example as the products of photochemical and volcanic activity, and created by plants and algae. They have also been created for thousands of years as products of combustion and food cooking, and more recently from vehicle exhausts. Deliberately manufactured nanoparticles, such as metal oxides, are by comparison in the minority.

Nanoparticles are of interest because of the new properties (such as chemical reactivity and optical behaviour) that they exhibit compared with larger particles of the same materials. For example, titanium dioxide and zinc oxide become transparent at the nanoscale, however are able to absorb and reflect UV light, and have found application in sunscreens. Nanoparticles have a range of potential applications: in the short-term in new cosmetics, textiles and paints; in the longer term, in methods of targeted drug delivery where they could be to used deliver drugs to a specific site in the body. Nanoparticles can also be arranged into layers on surfaces, providing a large surface area and hence enhanced activity, relevant to a range of potential applications such as catalysts.


Manufactured nanoparticles are typically not products in their own right, but generally serve as raw materials, ingredients or additives in existing products. Nanoparticles are currently in a small number of consumer products such as cosmetics and their enhanced or novel properties may have implications for their toxicity. For most applications, nanoparticles will be fixed (for example, attached to a surface or within in a composite) although in others they will be free or suspended in fluid. Whether they are fixed or free will have a significant affect on their potential health, safety and environmental impacts.