Nanoparticle

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.

Nanoparticles are particles between 1 and 100 nanometers in size. In nanotechnology, a particle is defined as a small object that behaves as a whole unit with respect to its transport and properties. Particles are further classified according to diameter. Ultrafine particles are the same as nanoparticles and between 1 and 100 nanometers in size, fine particles are sized between 100 and 2,500 nanometers, and coarse particles cover a range between 2,500 and 10,000 nanometers. Nanoparticle research is currently an area of intense scientific interest due to a wide variety of potential applications in biomedical, optical and electronic fields. The National Nanotechnology Initiative has led to generous public funding for nanoparticle research in the United States.

Definition

IUPAC definition

Particle of any shape with dimensions in the 1 × 10⁻⁹ and 1 × 10⁻⁷ m range.

Note 1: Modified from definitions of nanoparticle and nanogel in [refs.,].

Note 2: The basis of the 100-nm limit is the fact that novel properties that
differentiate particles from the bulk material typically develop at a critical
length scale of under 100 nm.

Note 3: Because other phenomena (transparency or turbidity, ultrafiltration,
stable dispersion, etc.) that extend the upper limit are occasionally considered,
the use of the prefix nano is accepted for dimensions smaller than 500 nm,
provided reference to the definition is indicated.

Note 4: Tubes and fibers with only two dimensions below 100 nm are also
nanoparticles.

The reason for the synonymous definition of nanoparticles and ultrafine particles is that, during the 1970-80s, when the first thorough fundamental studies with "nanoparticles" were underway in the USA (by Granqvist and Buhrman) and Japan, (within an ERATO Project) 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 ). Nanoparticles may or may not exhibit size-related properties that differ significantly from those observed in fine particles or bulk materials. 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 are agglomerates of ultrafine particles, nanoparticles, or nanoclusters. Nanometer-sized single crystals, or single-domain ultrafine particles, are often referred to as nanocrystals.

Background

Although, in general, nanoparticles are considered a discovery of modern science, they actually have a long history. Nanoparticles were used by artisans as far back as the ninth century in Mesopotamia for generating a glittering effect on the surface of pots.

Even these days, pottery from the Middle Ages and Renaissance often retain a distinct gold- or copper-colored metallic glitter. This luster 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 reducing atmosphere.

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 Muslim world. As Muslims were not allowed to use gold in artistic representations, they sought a way to create a similar effect without using real gold. The solution they found was using luster.

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 that 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 composite materials. 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 heterogeneity. 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.

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.

Inert gas evaporation and inert gas deposition are free many of these defects due to the distillation (cf. purification) nature of the process and having enough time to form single crystal particles, however even their non-aggreated deposits have lognormal size distribution, which is typical with nanoparticles. The reason why modern gas evaporation techniques can produce a relatively narrow size distribution is that aggregation can be avoided. 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.

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 that 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.

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 that 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.

Properties

Silicon nanopowder

1 kg of particles of 1 mm³ has the same surface area as 1 mg of particles of 1 nm³

Nanoparticles are of great scientific interest as they are, in effect, 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, gold nanoparticles appear deep-red to black in solution. Nanoparticles of yellow gold and grey 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);. Absorption of solar radiation is much higher in materials composed of nanoparticles than it is in thin films of continuous sheets of material. In both solar PV and solar thermal applications, controlling the size, shape, and material of the particles, it is possible to control 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. What would appear ironic is that 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.

Suspensions of nanoparticles are possible since the interaction of the particle surface with the solvent is strong enough to overcome density differences, 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. In theory, this 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 cannot 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, is completely photostable and toxic.

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.

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.

Semiconductor nanoparticle (quantum dot) of lead sulfide with complete passivation by oleic acid, oleyl and hydroxyl (size ~5nm)

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.

Synthesis

There are several methods for creating nanoparticles, including attrition, pyrolysis and hydrothermal synthesis. 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 by-product gases. Traditional pyrolysis often results in aggregates and agglomerates rather than single primary particles. Ultrasonic nozzle spray pyrolysis (USP) on the other hand aids in preventing agglomerates from forming.

A thermal plasma can also deliver the energy necessary to cause vaporization 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 formed between the anode and the cathode. For example, silica sand can be vaporized with an arc plasma at atmospheric pressure, or thin aluminum wires can be vaporized by exploding wire method. 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 30–50 kW, whereas 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 (see Induction plasma technology).

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-size particles, which can be entrained in the inert gas stream and deposited on a substrate or studied in situ.

Nanoparticles can also be formed using radiation chemistry. Radiolysis from gamma rays can create strongly active free radicals in solution. This relatively simple technique uses a minimum number of chemicals. These including water, a soluble metallic salt, a radical scavenger (often a secondary alcohol), and a surfactant (organic capping agent). High gamma doses on the order of 10⁴ Gray are required. In this process, reducing radicals will drop metallic ions down to the zero-valence state. A scavenger chemical will preferentially interact with oxidizing radicals to prevent the re-oxidation of the metal. Once in the zero-valence state, metal atoms begin to coalesce into particles. A chemical surfactant surrounds the particle during formation and regulates its growth. In sufficient concentrations, the surfactant molecules stay attached to the particle. This prevents it from dissociating or forming clusters with other particles. Formation of nanoparticles using the radiolysis method allows for tailoring of particle size and shape by adjusting precursor concentrations and gamma dose.

Sol-gel

The sol-gel process is a wet-chemical technique (also known as chemical solution deposition) widely used recently in the fields of materials science and ceramic engineering. Such methods are used primarily for the fabrication of materials (typically a metal oxide) starting from a chemical solution (sol, short for solution), which acts as the precursor for an integrated network (or gel) of either discrete particles or network polymers.

Typical precursors are metal alkoxides and metal chlorides, which undergo hydrolysis and polycondensation reactions to form either a network "elastic solid" or a colloidal suspension (or dispersion) – a system composed of discrete (often amorphous) submicrometer particles dispersed to various degrees in a host fluid. Formation of a metal oxide involves connecting the metal centers with oxo (M-O-M) or hydroxo (M-OH-M) bridges, therefore generating metal-oxo or metal-hydroxo polymers in solution. Thus, the sol evolves toward the formation of a gel-like diphasic system containing both a liquid phase and solid phase whose morphologies range from discrete particles to continuous polymer networks.

In the case of the colloid, the volume fraction of particles (or particle density) may be so low that a significant amount of fluid may need to be removed initially for the gel-like properties to be recognized. This can be accomplished in a number of ways. The most simple method is to allow time for sedimentation to occur, and then pour off the remaining liquid. Centrifugation can also be used to accelerate the process of phase separation.

Removal of the remaining liquid (solvent) phase requires a drying process, which is typically accompanied by a significant amount of shrinkage and densification. The rate at which the solvent can be removed is ultimately determined by the distribution of porosity in the gel. The ultimate microstructure of the final component will clearly be strongly influenced by changes implemented during this phase of processing. Afterward, a thermal treatment, or firing process, is often necessary in order to favor further polycondensation and enhance mechanical properties and structural stability via final sintering, densification, and grain growth. One of the distinct advantages of using this methodology as opposed to the more traditional processing techniques is that densification is often achieved at a much lower temperature.

The precursor sol can be either deposited on a substrate to form a film (e.g., by dip-coating or spin-coating), cast into a suitable container with the desired shape (e.g., to obtain a monolithic ceramics, glasses, fibers, membranes, aerogels), or used to synthesize powders (e.g., microspheres, nanospheres). The sol-gel approach is a cheap and low-temperature technique that allows for the fine control of the product’s chemical composition. Even small quantities of dopants, such as organic dyes and rare earth metals, can be introduced in the sol and end up uniformly dispersed in the final product. It can be used in ceramics processing and manufacturing as an investment casting material, or as a means of producing very thin films of metal oxides for various purposes. Sol-gel derived materials have diverse applications in optics, electronics, energy, space, (bio)sensors, medicine (e.g., controlled drug release) and separation (e.g., chromatography) technology.

Colloids

The term colloid is used primarily to describe a broad range of solid–liquid (and/or liquid–liquid) mixtures, all of which containing distinct solid (and/or liquid) particles that are dispersed to various degrees in a liquid medium. The term is specific to the size of the individual particles, which are larger than atomic dimensions but small enough to exhibit Brownian motion. If the particles are large enough then their dynamic behavior in any given period of time in suspension would be governed by forces of gravity and sedimentation. But, if they are small enough to be colloids, then their irregular motion in suspension can be attributed to the collective bombardment of a myriad of thermally agitated molecules in the liquid suspending medium, as described originally by Albert Einstein in his dissertation. Einstein proved the existence of water molecules by concluding that this erratic particle behavior could adequately be described using the theory of Brownian motion, with sedimentation being a possible long-term result. This critical size range (or particle diameter) typically ranges from nanometers (10⁻⁹ m) to micrometers (10⁻⁶ m).

Morphology

Nanostars of vanadium(IV) oxide

Scientists have taken to naming their particles after the real-world shapes that they might represent. Nanospheres, nanoreefs, nanoboxes and more have appeared in the literature. These morphologies sometimes arise spontaneously as an effect of a templating or directing agent present in the synthesis such as miscellar emulsions or anodized alumina pores, or from the innate crystallographic growth patterns of the materials themselves. Some of these morphologies may serve a purpose, such as long carbon nanotubes used to bridge an electrical junction, or just a scientific curiosity like the stars shown at right.

Amorphous particles usually adopt a spherical shape (due to their microstructural isotropy), whereas the shape of anisotropic microcrystalline whiskers corresponds to their particular crystal habit. At the small end of the size range, nanoparticles are often referred to as clusters. Spheres, rods, fibers, and cups are just a few of the shapes that have been grown. The study of fine particles is called micromeritics.

Characterization

The majority of nanoparticle characterization techniques are light-based, but a non-optical nanoparticle characterization technique called Tunable Resistive Pulse Sensing (TRPS) has been developed that enables the simultaneous measurement of size, concentration and surface charge for a wide variety of nanoparticles. This technique, which applies the Coulter Principle, allows for particle-by-particle quantification of these three nanoparticle characteristics with high resolution.

Functionalization

The surface coating of nanoparticles is crucial to determining their properties. In particular, the surface coating can regulate stability, solubility, and targeting. A coating that is multivalent or polymeric confers high stability. Functionalized nanomaterial-based catalysts can be used for catalysis of many known organic reactions.

Surface coating for biological applications

Main article: Nanoparticle–biomolecule conjugate

For biological applications, the surface coating should be polar to give high aqueous solubility and prevent nanoparticle aggregation. In serum or on the cell surface, highly charged coatings promote non-specific binding, whereas polyethylene glycol linked to terminal hydroxyl or methoxy groups repel non-specific interactions. Nanoparticles can be linked to biological molecules that can act as address tags, to direct the nanoparticles to specific sites within the body, specific organelles within the cell, or to follow specifically the movement of individual protein or RNA molecules in living cells. Common address tags are monoclonal antibodies, aptamers, streptavidin or peptides. These targeting agents should ideally be covalently linked to the nanoparticle and should be present in a controlled number per nanoparticle. Multivalent nanoparticles, bearing multiple targeting groups, can cluster receptors, which can activate cellular signaling pathways, and give stronger anchoring. Monovalent nanoparticles, bearing a single binding site, avoid clustering and so are preferable for tracking the behavior of individual proteins.

Red blood cell coatings can help nanoparticles evade the immune system.

Safety

See also: Nanotoxicology, Fine particles, and Regulation of nanotechnology

Nanoparticles present possible dangers, both medically and environmentally. Most of these are due to the high surface to volume ratio, which can make the particles very reactive or catalytic. They are also able to pass through cell membranes in organisms, and their interactions with biological systems are relatively unknown. However, it is unlikely the particles would enter the cell nucleus, Golgi complex, endoplasmic reticulum or other internal cellular components due to the particle size and intercellular agglomeration. A recent study looking at the effects of ZnO nanoparticles on human immune cells has found varying levels of susceptibility to cytotoxicity. There are concerns that pharmaceutical companies, seeking regulatory approval for nano-reformulations of existing medicines, are relying on safety data produced during clinical studies of the earlier, pre-reformulation version of the medicine. This could result in regulatory bodies, such as the FDA, missing new side effects that are specific to the nano-reformulation.

Whether cosmetics and sunscreens containing nanomaterials pose health risks remains largely unknown at this stage. However considerable research has demonstrated that zinc nanoparticles are not absorbed into the bloodstream in vivo. Diesel nanoparticles have been found to damage the cardiovascular system in a mouse model.

Concern has also been raised over the health effects of respirable nanoparticles from certain combustion processes. As of 2013 the Environmental Protection Agency was investigating the safety of the following nanoparticles:

• Carbon Nanotubes: Carbon materials have a wide range of uses, ranging from composites for use in vehicles and sports equipment to integrated circuits for electronic components. The interactions between nanomaterials such as carbon nanotubes and natural organic matter strongly influence both their aggregation and deposition, which strongly affects their transport, transformation, and exposure in aquatic environments. In past research, carbon nanotubes exhibited some toxicological impacts that will be evaluated in various environmental settings in current EPA chemical safety research. EPA research will provide data, models, test methods, and best practices to discover the acute health effects of carbon nanotubes and identify methods to predict them.
• Cerium oxide: Nanoscale cerium oxide is used in electronics, biomedical supplies, energy, and fuel additives. Many applications of engineered cerium oxide nanoparticles naturally disperse themselves into the environment, which increases the risk of exposure. There is ongoing exposure to new diesel emissions using fuel additives containing CeO2 nanoparticles, and the environmental and public health impacts of this new technology are unknown. EPA’s chemical safety research is assessing the environmental, ecological, and health implications of nanotechnology-enabled diesel fuel additives.
• Titanium dioxide: Nano titanium dioxide is currently used in many products. Depending on the type of particle, it may be found in sunscreens, cosmetics, and paints and coatings. It is also being investigated for use in removing contaminants from drinking water.
• Nano Silver: Nano silver is being incorporated into textiles and other materials to eliminate bacteria and odor from clothing, food packaging, and other items where antimicrobial properties are desirable. In collaboration with the U.S. Consumer Product Safety Commission, EPA is studying certain products to see whether they transfer nano-size silver particles in real-world scenarios. EPA is researching this topic to better understand how much nano-silver children come in contact with in their environments.
• Iron: While nano-scale iron is being investigated for many uses, including “smart fluids” for uses such as optics polishing and as a better-absorbed iron nutrient supplement, one of its more prominent current uses is to remove contamination from groundwater. This use, supported by EPA research, is being piloted at a number of sites across the country.

Laser applications

The use of nanoparticles in laser dye-doped poly(methyl methacrylate) (PMMA) laser gain media was demonstrated in 2003 and it has been shown to improve conversion efficiencies and to decrease laser beam divergence. Researchers attribute the reduction in beam divergence to improved dn/dT characteristics of the organic-inorganic dye-doped nanocomposite. The optimum composition reported by these researchers is 30% w/w of SiO₂ (~ 12 nm) in dye-doped PMMA.

Medicinal applications

• Liposome
• Dendrimer
• Iron oxide nanoparticles
• Nanomedicine
• Polymer-drug conjugate
• Polymeric nanoparticle

See also

• Ceramic engineering
• Coating
• Colloid
• Colloid-facilitated transport
• Colloidal crystal
• Colloidal gold
• Eigencolloid
• Fullerenes
• Fungal-derived nanoparticles
• Gallium selenide
• Icosahedral twins
• Indium selenide
• Liposome
• Magnetic immunoassay
• Magnetic nanoparticles
• Micromeritics
• Nanobiotechnology
• Nanocrystalline silicon
• Nanogeoscience
• Nanomaterials
• Nanomedicine
• Nanoparticle Tracking Analysis
• Nanotechnology
• Photonic crystal
• Plasmon
• Platinum nanoparticles
• Quantum dot
• Silicon
• Silver Nano
• Sol-gel
• Transparent materials

Further reading

• Nanoparticles Used In Solar Energy Conversion (ScienceDaily).
• Nanoparticles: An occupational hygiene review by RJ Aitken and others. Health and Safety Executive Research Report 274/2004
• EMERGNANO: A review of completed and near completed environment, health and safety research on nanomaterials and nanotechnology by RJ Aitken and others.
• High transmission Tandem DMA for nanoparticle studies by SEADM, 2014.

External links

• Nanohedron.com images of nanoparticles
• Lectures on All Phases of Nanoparticle Science and Technology
• ENPRA – Risk Assessment of Engineered NanoParticles EC FP7 Project led by the Institute of Occupational Medicine