Definition of nanomaterial

On 18 October, the European Commission agreed the wording of a definition. Perhaps that is a useful opening sentence for this article, since the current opening sentence is terribly weak. "nanomaterials are a natural, incidental or manufactured material containing particles, in an unbound state or as an aggregate or as an agglomerate and where, for 50% or more of the particles in the number size distribution, one or more external dimensions is in the size range 1 nm 100 nm.". In nanotechnology, a particle is defined as a small object that behaves as a whole unit in terms of its transport and properties. Particles are further classified according to size [1] : in terms of diameter, coarse particles cover a range between 10,000 and 2,500 nanometers. Fine particles are sized between 2,500 and 100 nanometers. Ultrafine particles or nanoparticles are sized between 100 and 1 nanometers. The reason for this double name of the same object is that, during the 1970-80's, when the first thorough fundamental studies were running with "nanoparticles" in the USA (by Granqvist and Buhrman)[2] and Japan, (within an ERATO Project)[3] they were called "ultrafine particles" (UFP). However, during the 1990s before the National Nanotechnology Initiative was launched in the USA, the new name, "nanoparticle" had become fashionable (see, for example the same senior author's paper 20 years later addressing the same issue, lognormal distribution of sizes [4]). Nanoparticles may or may not exhibit size-related properties that differ significantly from those observed in fine particles or bulk materials.[5][6] Although the size of most molecules would fit into the above outline, individual molecules are usually not referred to as nanoparticles. Nanoclusters have at least one dimension between 1 and 10 nanometers and a narrow size distribution. Nanopowders[7] are agglomerates of ultrafine particles, nanoparticles, or nanoclusters. Nanometersized single crystals, or single-domain ultrafine particles, are often referred to as nanocrystals. Nanoparticle research is currently an area of intense scientific interest due to a wide variety of potential applications in biomedical, optical and electronic fields.

TEM (a, b, and c) images of prepared mesoporous silica nanoparticles with mean outer diameter: (a) 20nm, (b) 45nm, and (c) 80nm. SEM (d) image corresponding to (b). The insets are a high magnification of mesoporous silica particle.[8]

The National Nanotechnology Initiative has led to generous public funding for nanoparticle research in the United States.

Background
Although nanoparticles are generally considered a discovery of modern science, they actually have a very long history. Nanoparticles were used by artisans as far back as the 9th century in Mesopotamiafor generating a glittering effect on the surface of pots[citation needed]. Even these days, pottery from the Middle Ages and Renaissance often retain a distinct gold or copper colored metallic glitter. This so calledluster is caused by a metallic film that was applied to the transparent surface of a glazing. The luster can still be visible if the film has resisted atmospheric oxidation and other weathering. The luster originated within the film itself, which contained silver and copper nanoparticles dispersed homogeneously in the glassy matrix of the ceramic glaze. These nanoparticles were created by the artisans by adding copper and silver salts and oxides together with vinegar,ochre and clay, on the surface of previously-glazed pottery. The object was then placed into a kiln and heated to about 600 C in a reducingatmosphere. In the heat the glaze would soften, causing the copper and silver ions to migrate into the outer layers of the glaze. There the reducing atmosphere reduced the ions back to metals, which then came together forming the nanoparticles that give the colour and optical effects.

Luster technique showed that ancient craftsmen had a rather sophisticated empirical knowledge of materials. The technique originated in the Islamic world. As Muslims were not allowed to use gold in artistic representations, they had to find a way to create a similar effect without using real gold. The solution they found was using luster.[9] Michael Faraday provided the first description, in scientific terms, of the optical properties of nanometer-scale metals in his classic 1857 paper. In a subsequent paper, the author (Turner) points out that: "It is well known that when thin leaves of gold or silver are mounted upon glass and heated to a temperature which is well below a red heat (~500 C), a remarkable change of properties takes place, whereby the continuity of the metallic film is destroyed. The result is that white light is now freely transmitted, reflection is correspondingly diminished, while the electrical resistivity is enormously increased

Uniformity
The chemical processing and synthesis of high performance technological components for the private, industrial and military sectors requires the use of high purity ceramics, polymers, glass-ceramics and material composites. In condensed bodies formed from fine powders, the irregular particle sizes and shapes in a typical powder often lead to non-uniform packing morphologies that result in packing density variations in the powder compact. Uncontrolled agglomeration of powders due to attractive van der Waals forces can also give rise to in microstructural in homogeneities. Differential stresses that develop as a result of non-uniform drying shrinkage are directly related to the rate at which the solvent can be removed, and thus highly dependent upon the distribution of porosity. Such stresses have been associated with a plastic-to-brittle transition in consolidated bodies, and can yield to crack propagation in the unfired body if not relieved. [13] [14] [15] In addition, any fluctuations in packing density in the compact as it is prepared for the kiln are often amplified during the sintering process, yielding inhomogeneous densification. Some pores and other structural defects associated with density variations have been shown to play a detrimental role in the sintering process by growing and thus limiting end-point densities. Differential stresses arising from inhomogeneous densification have also been shown to result in the propagation of internal cracks, thus becoming the strength-controlling flaws. [16][17] [18] Inert gas evaporation and inert gas deposition [2][3] are free many of these defects due to the distillation (c.f. purification) nature of the process and having enough time to form single crystal particles, however even their nonaggreated deposits have lognormal size distribution, which is typical with nanoparticles.[3] The reason why modern gas evaporation techniques can produce a relatively narrow size distribution is that aggregation can be avoided.
[3]

However, even in this case, random residence times in the growth zone, due to the combination of drift and

diffusion, result in a size distribution appearing lognormal.[4] It would therefore appear desirable to process a material in such a way that it is physically uniform with regard to the distribution of components and porosity, rather than using particle size distributions which will maximize the green

density. The containment of a uniformly dispersed assembly of strongly interacting particles in suspension requires total control over interparticle forces. Monodisperse nanoparticles and colloids provide this potential. [19] Monodisperse powders of colloidal silica, for example, may therefore be stabilized sufficiently to ensure a high degree of order in the colloidal crystal or polycrystalline colloidal solid which results from aggregation. The degree of order appears to be limited by the time and space allowed for longer-range correlations to be established. Such defective polycrystalline colloidal structures would appear to be the basic elements of submicrometer colloidal materials science, and, therefore, provide the first step in developing a more rigorous understanding of the mechanisms involved in microstructural evolution in high performance materials and components. [20] [21]

Properties

Silicon nanopowder

Nanoparticles are of great scientific interest as they are effectively a bridge between bulk materials and atomic or molecular structures. A bulk material should have constant physical properties regardless of its size, but at the nano-scale size-dependent properties are often observed. Thus, the properties of materials change as their size approaches the nanoscale and as the percentage of atoms at the surface of a material becomes significant. For bulk materials larger than one micrometer (or micron), the percentage of atoms at the surface is insignificant in relation to the number of atoms in the bulk of the material. The interesting and sometimes unexpected properties of nanoparticles are therefore largely due to the large surface area of the material, which dominates the contributions made by the small bulk of the material. Nanoparticles often possess unexpected optical properties as they are small enough to confine their electrons and produce quantum effects. For example goldnanoparticles appear deep red to black in solution. Nanoparticles of usually yellow gold and gray silicon are red in color. Gold nanoparticles melt at much lower temperatures (~300 C for 2.5 nm size) than the gold slabs (1064 C);.[22] And absorption of solar radiation in photovoltaic cells is much higher in

materials composed of nanoparticles than it is in thin films of continuous sheets of material. I.E. the smaller the particles, the greater the solar absorption. Other size-dependent property changes include quantum confinement in semiconductor particles, surface plasmon resonance in some metal particles and superparamagnetism in magnetic materials. Ironically, the changes in physical properties are not always desirable. Ferromagnetic materials smaller than 10 nm can switch their magnetisation direction using room temperature thermal energy, thus making them unsuitable for memory storage.[23] Suspensions of nanoparticles are possible since the interaction of the particle surface with the solvent is strong enough to overcome densitydifferences, which otherwise usually result in a material either sinking or floating in a liquid. The high surface area to volume ratio of nanoparticles provides a tremendous driving force for diffusion, especially at elevated temperatures.Sintering can take place at lower temperatures, over shorter time scales than for larger particles. This theoretically does not affect the density of the final product, though flow difficulties and the tendency of nanoparticles to agglomerate complicates matters. Moreover, nanoparticles have been found to impart some extra properties to various day to day products. For example the presence of titanium dioxide nanoparticles imparts what we call the self-cleaning effect, and the size being nano-range, the particles can not be observed. Zinc oxide particles have been found to have superior UV blocking properties compared to its bulk substitute. This is one of the reasons why it is often used in the preparation of sunscreen lotions,[24] and is completely photostable.[25] Clay nanoparticles when incorporated into polymer matrices increase reinforcement, leading to stronger plastics, verifiable by a higher glass transition temperature and other mechanical property tests. These nanoparticles are hard, and impart their properties to the polymer (plastic). Nanoparticles have also been attached to textile fibers in order to create smart and functional clothing.[26] Metal, dielectric, and semiconductor nanoparticles have been formed, as well as hybrid structures (e.g., core-shell nanoparticles). Nanoparticles made of semiconducting material may also be labeled quantum dots if they are small enough (typically sub 10 nm) that quantization of electronic energy levels occurs. Such nanoscale particles are used in biomedical applications as drug carriers or imaging agents. Semi-solid and soft nanoparticles have been manufactured. A prototype nanoparticle of semi-solid nature is the liposome. Various types of liposome nanoparticles are currently used clinically as delivery systems for anticancer drugs and vaccines. Nanoparticles with one half hydrophilic and the other half hydrophobic are termed Janus particles and are particularly effective for stabilizing emulsions. They can self-assemble at water/oil interfaces and act as solid surfactants. There are several methods for creating nanoparticles, including both attrition and pyrolysis. In attrition, macro or micro scale particles are ground in a ball mill, a planetary ball mill, or other size reducing mechanism. The resulting particles are air classified to recover nanoparticles. In pyrolysis, a vaporous precursor (liquid or gas) is forced through an orifice

Synthesis

There are several methods for creating nanoparticles, including both attrition and pyrolysis. In attrition, macro or micro scale particles are ground in a ball mill, a planetary ball mill, or other size reducing mechanism. The resulting particles are air classified to recover nanoparticles. In pyrolysis, a vaporous precursor (liquid or gas) is forced through an orifice at high pressure and burned. The resulting solid (a version of soot) is air classified to recover oxide particles from byproduct gases. Pyrolysis often results in aggregates and agglomerates rather than single primary particles. A thermal plasma can also deliver the energy necessary to cause evaporation of small micrometer size particles. The thermal plasma temperatures are in the order of 10,000 K, so that solid powder easily evaporates. Nanoparticles are formed upon cooling while exiting the plasma region. The main types of the thermal plasma torches used to produce nanoparticles are dc plasma jet, dc arc plasma and radio frequency (RF) induction plasmas. In the arc plasma reactors, the energy necessary for evaporation and reaction is provided by an electric arc which is formed between the anode and the cathode. For example, silica sand can be vaporized with an arc plasma at atmospheric pressure. The resulting mixture of plasma gas and silica vapour can be rapidly cooled by quenching with oxygen, thus ensuring the quality of the fumed silica produced. In RF induction plasma torches, energy coupling to the plasma is accomplished through the electromagnetic field generated by the induction coil. The plasma gas does not come in contact with electrodes, thus eliminating possible sources of contamination and allowing the operation of such plasma torches with a wide range of gases including inert, reducing, oxidizing and other corrosive atmospheres. The working frequency is typically between 200 kHz and 40 MHz. Laboratory units run at power levels in the order of 3050 kW while the large scale industrial units have been tested at power levels up to 1 MW. As the residence time of the injected feed droplets in the plasma is very short it is important that the droplet sizes are small enough in order to obtain complete evaporation. The RF plasma method has been used to synthesize different nanoparticle materials, for example synthesis of various ceramic nanoparticles such as oxides, carbours/carbides and nitrides of Ti and Si . Inert-gas condensation is frequently used to make nanoparticles from metals with low melting points. The metal is vaporized in a vacuum chamber and then supercooled with an inert gas stream. The supercooled metal vapor condenses into nanometer-sized particles, which can be entrained in the inert gas stream and deposited on a substrate or studied in situ.