Nanoparticle

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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.
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A nanoparticle or ultrafine particle is usually defined as a particle of matter that is between 1 and
100 nanometres (nm) in diameter.[1][2] The term is sometimes used for larger particles, up to
500 nm,[citation needed] or fibers and tubes that are less than 100 nm in only two directions.[3] At
the lowest range, metal particles smaller than 1 nm are usually called atom clusters instead.
Nanoparticles are usually distinguished from microparticles (1-1000 µm), "fine particles" (sized
between 100 and 2500 nm), and "coarse particles" (ranging from 2500 to 10,000 nm), because their
smaller size drives very different physical or chemical properties, like colloidal properties and
ultrafast optical effects[4] or electric properties.
Being more subject to the brownian motion, they usually do not sediment, like colloidal particles
that conversely are usually understood to range from 1 to 1000 nm.
Being much smaller than the wavelengths of visible light (400-700 nm), nanoparticles cannot be
seen with ordinary optical microscopes, requiring the use of electron microscopes or microscopes
with laser. For the same reason, dispersions of nanoparticles in transparent media can be
transparent,[5] whereas suspensions of larger particles usually scatter some or all visible light
incident on them. Nanoparticles also easily pass through common filters, such as common ceramic
candles,[6] so that separation from liquids requires special nanofiltration techniques.
The properties of nanoparticles often differ markedly from those of larger particles of the same
substance. Since the typical diameter of an atom is between 0.15 and 0.6 nm, a large fraction of the
nanoparticle's material lies within a few atomic diameters of its surface. Therefore, the properties of
that surface layer may dominate over those of the bulk material. This effect is particularly strong for
nanoparticles dispersed in a medium of different composition since the interactions between the two
materials at their interface also becomes significant.[7]

Idealized model of a crystalline nanoparticle of platinum, about 2 nm in diameter, showing

individual atoms.
Nanoparticles occur widely in nature and are objects of study in many sciences such as chemistry,
physics, geology and biology. Being at the transition between bulk materials and atomic or
molecular structures, they often exhibit phenomena that are not observed at either scale. They are an
important component of atmospheric pollution, and key ingredients in many industrialized products
such as paints, plastics, metals, ceramics, and magnetic products. The production of nanoparticles
with specific properties is a branch of nanotechnology.
In general, the small size of nanoparticles leads to a lower concentration of point defects compared
to their bulk counterparts,[8] but they do support a variety of dislocations that can be visualized
using high-resolution electron microscopes.[9] However, nanoparticles exhibit different dislocation
mechanics, which, together with their unique surface structures, results in mechanical properties
that are different from the bulk material.[10][11][12]
Non-spherical nanonparticles (e.g., prisms, cubes, rods etc.) exhibit shape-dependent and size-
dependent (both chemical and physical) properties (anisotropy).[13][14] Non-spherical
nanoparticles of gold (Au), silver (Ag), and platinum (Pt) due to their fascinating optical properties
are finding diverse applications. Non-spherical geometries of nanoprisms give rise to high effective
cross-sections and deeper colors of the colloidal solutions.[15] The possibility of shifting the
resonance wavelengths by tuning the particle geometry allows using them in the fields of molecular
labeling, biomolecular assays, trace metal detection, or nanotechnical applications. Anisotropic
nanoparticles display a specific absorption behavior and stochastic particle orientation under
unpolarized light, showing a distinct resonance mode for each excitable axis. [15]

Contents
• 1 Definitions
• 1.1 IUPAC
• 1.2 ISO
• 1.3 Common usage
• 1.4 Related concepts
• 2 History
• 2.1 Natural occurrence
• 2.2 Pre-industrial technology
• 2.3 19th century
• 2.4 20th century
• 3 Morphology and structure
• 3.1 Variations
• 4 Nucleation
• 4.1 Impact of Nucleation
• 4.2 Burst Nucleation
• 4.3 Ostwald Ripening
• 4.4 Two Step Mechanism – Autocatalysis Model
• 4.5 Modeling Nucleation in Nanoparticles
• 4.6 Measuring the Rate of Nucleation
• 5 Properties
• 5.1 Controlling Properties
• 5.2 Large surface-area-to-volume ratio
• 5.3 Interfacial layer
• 5.4 Solvent affinity
• 5.5 Coatings
• 5.6 Diffusion across the surface
• 5.7 Ferromagnetic and ferroelectric effects
• 5.8 Mechanical Properties
• 5.9 Melting point depression
• 5.10 Quantum mechanics effects
• 5.11 Regular packing
 • 6 Production
• 6.1 Mechanical
• 6.2 Breakdown of biopolymers
• 6.3 Pyrolysis
• 6.4 Condensation from plasma
• 6.5 Inert gas condensation
• 6.6 Radiolysis method
• 6.7 Wet chemistry
• 6.8 Ion implantation
• 6.9 Functionalization
• 6.10 Uniformity requirements
• 7 Characterization
• 8 Health and safety
• 9 Regulation
• 10 Applications
• 10.1 Polymer reinforcement
• 10.2 Liquid properties tuner
• 10.3 Photocatalysis
• 10.4 Road paving
• 10.5 Biomedical
• 10.6 Sunscreens
• 10.7 Compounds by industrial area
• 11 See also
• 12 References
• 13 Further reading
• 14 External links

Definitions
IUPAC
In its 2012 proposed terminology for biologically related polymers, the IUPAC defined a
nanoparticle as "a particle of any shape with dimensions in the 1 × 10−9 and 1 × 10−7 m range".[2]
This definition evolved from one given by IUPAC in 1997.[16][17]
In another 2012 publication, the IUPAC extends the term to include tubes and fibers with only two
dimensions below 100 nm.[3]

ISO
According to the International Standards Organization (ISO) technical specification 80004, a
nanoparticle is an object with all three external dimensions in the nanoscale, whose longest and
shortest axes do not differ significantly, with a significant difference typically being a factor of at
least 3.[18]
Common usage
"Nanoscale" is usually understood to be the range from 1 to 100 nm because the novel properties
that differentiate particles from the bulk material typically develop at that range of sizes.
For some properties, like transparency or turbidity, ultrafiltration, stable dispersion, etc., substantial
changes characteristic of nanoparticles are observed for particles as large as 500 nm. Therefore, the
term is sometimes extended to that size range.[citation needed]

Related concepts
Nanoclusters are agglomerates of nanoparticles with at least one dimension between 1 and 10
nanometers and a narrow size distribution. Nanopowders[19] are agglomerates of ultrafine particles,
nanoparticles, or nanoclusters. Nanometer-sized single crystals, or single-domain ultrafine particles,
are often referred to as nanocrystals.
The terms colloid and nanoparticle are not interchangeable. A colloid is a mixture which has
particles of one phase dispersed or suspended within an other phase. The term applies only if the
particles are larger than atomic dimensions but small enough to exhibit Brownian motion, with the
critical size range (or particle diameter) typically ranging from nanometers (10−9 m) to micrometers
(10−6 m).[20] Colloids can contain particles too large to be nanoparticles, and nanoparticles can
exist in non-colloidal form, for examples as a powder or in a solid matrix.

History
Natural occurrence
Nanoparticles are naturally produced by many cosmological,[21] geological,[21][22]
meteorological, and biological processes. A significant fraction (by number, if not by mass) of
interplanetary dust, that is still falling on the Earth at the rate of thousands of tons per year, is in the
nanoparticle range;[23][24] and the same is true of atmospheric dust particles. Many viruses have
diameters in the nanoparticle range.

Pre-industrial technology
Nanoparticles were used by artisans since prehistory, albeit without knowledge of their nature. They
were used by glassmakers and potters in Classical Antiquity, as exemplified by the Roman
Lycurgus cup of dichroic glass (4th century CE) and the lusterware pottery of Mesopotamia (9th
century CE).[25][26][27] The latter is characterized by silver and copper nanoparticles dispersed in
the glassy glaze.

19th century
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."[28][29][30]
20th century
During the 1970s and 80s, when the first thorough fundamental studies with nanoparticles were
underway in the United States (by Granqvist and Buhrman)[31] and Japan (within an ERATO
Project),[32] researchers used the term ultrafine particles. However, during the 1990s, before the
National Nanotechnology Initiative was launched in the United States, the term nanoparticle had
become more common (for example, see the same senior author's paper 20 years later addressing
the same issue, lognormal distribution of sizes[33]).

Morphology and structure

Nanostars of vanadium(IV) oxide

Nanoparticles occur in a great variety of shapes, which have been given many informal names such
as nanospheres,[34] nanorods, nanochains,[35] nanostars, nanoflowers, nanoreefs,[36]
nanowhiskers, nanofibers, and nanoboxes.[37]
The shapes of nanoparticles may be determined by the intrinsic crystal habit of the material, or by
the influence of the environment around their creation, such as the inhibition of crystal growth on
certain faces by coating additives, the shape of emulsion droplets and micelles in the precursor
preparation, or the shape of pores in a surrounding solid matrix.[38] Some applications of
nanoparticles may require specific shapes, as well as specific sizes or size ranges.
Amorphous particles typically adopt a spherical shape (due to their microstructural isotropy).
The study of fine particles is called micromeritics.

Variations
Semi-solid and soft nanoparticles have been produced. 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.
The breakdown of biopolymers into their nanoscale building blocks is considered a potential route
to produce nanoparticles with enhanced biocompatibility and biodegradability. The most common
example is the production of nanocellulose from wood pulp.[39] Other examples are nanolignin,
nanchitin, or nanostarches.[40]
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 Pickering stabilizers.
Hydrogel nanoparticles made of N-isopropylacrylamide hydrogel core shell can be dyed with
affinity baits, internally.[41] These affinity baits allow the nanoparticles to isolate and remove
undesirable proteins while enhancing the target analytes.[41]

Nucleation
Impact of Nucleation
Nucleation lays the foundation for the nanoparticle synthesis. Initial nuclei play a vital role on the
size and shape of the nanoparticles that will ultimately form by acting as templating nuclei for the
nanoparticle itself. Long-term stability is also determined by the initial nucleation procedures.[42]
Homogeneous nucleation occurs when nuclei form uniformly throughout the parent phase and is
less common. Heterogeneous nucleation, however, forms on areas such as container surfaces,
impurities, and other defects.[43] Crystals may form simultaneously if nucleation is fast, creating a
more monodisperse product. However, slow nucleation rates can cause formation of a polydisperse
population of crystals with various sizes. Controlling nucleation allows for the control of size,
dispersity, and phase of nanoparticles.
The process of nucleation and growth within nanoparticles can be described by burst nucleation,
Ostwald ripening or the two-step mechanism-autocatalysis model.[44]

Burst Nucleation
The original theory of nucleation in nanoparticle synthesis believed that the changes in particle size
could be described by burst nucleation alone. There are three portions to the LaMer[clarification
needed] mechanism: 1. Rapid increase in the concentration of free monomers in solution, 2. Burst
nucleation of the monomer characterized by explosive growth of particles, 3. Growth of particles
controlled by diffusion of the monomer.[45] This model describes that the growth on the nucleus is
spontaneous but limited by diffusion of the precursor to the nuclei surface. The LaMer mechanism
alone does not explain certain kinetic and thermodynamic of nucleation such as gold sol formation.
[46]

Ostwald Ripening
Ostwald ripening is a process typically avoided in nanoparticle synthesis as it is known to
negatively impact the functionality of nanoparticles. In this process, large particles grow at the
expense of the smaller particles due to diffusion of disperse phase molecules through the continuous
phase.[47]

Two Step Mechanism – Autocatalysis Model

In later years, another theory of nucleation in nanoparticles was introduced by Watzky and Finke.
This theory suggested that constant slow nucleation occurs far from supersaturation followed by
autocatalytic growth where dispersity of nanoparticles is largely determined. Discovered by Watzky
and Finke, this model provides a firmer mechanistic basis for the design of nanoparticles with a
focus on size, shape, and dispersity control.[48] [49]

Modeling Nucleation in Nanoparticles

Recent work has begun to look at modeling the early stages of nucleation as well as the rates
associated with nucleation through multiscale computational modeling. This includes exploration
into an improved kinetic rate equation model as well as density function studies using the phase-
field crystal model.[50]

Measuring the Rate of Nucleation

The classical nucleation theory explains that the nucleation rate will correspond to the driving force
One method for measuring the nucleation rate is through the induction time method. This process
uses the stochastic nature of nucleation and determines the rate of nucleation by analysis of the time
between constant supersaturation and when crystals are first detected.[51] Another method includes
the probability distribution model, analogous to the methods used to study supercooled liquids,
where the probability of finding at least one nucleus at a given time is derived.

Properties
The properties of a material in nanoparticle form are unusually different from those of the bulk one
even when divided into micrometer-size particles.[52][53][54] Many of them arise from spatial
confinement of sub-atomic particles (i.e. electrons, protons, photons) and electric fields around
these particles. The large surface to volume ratio is also significant factor at this scale.[14]

Controlling Properties
The properties of a nanoparticle are heavily influenced by the initial nucleation stages of the
synthesis process. Nucleation, for example, is vital to the size of the nanoparticle. A critical radius
must be met in initial stages of solid formation, or the particles will redissolve into the liquid phase.
[55] The final shape of a nanoparticle is also controlled by nucleation. Possible final morphologies
created by nucleation can include spherical, cubic, needle-like, worm-like, and more particles.[56]
Nucleation can be controlled predominately by time and temperature as well as the supersaturation
of the liquid phase and the environment of the synthesis overall.[57]
The properties of a material in nanoparticle form are unusually different from those of the bulk one
even when divided into micrometer-size particles.[52][53][54] Many of them arise from spatial
confinement of sub-atomic particles (i.e. electrons, protons, photons) and electric fields around
these particles. The large surface to volume ratio is also significant factor at this scale.[14]
Large surface-area-to-volume ratio

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

A bulk materials (>100 nm in size) are expected to have constant physical properties (such as
thermal and electrical conductivity, stiffness, density, and viscosity) regardless of its size, for
nanoparticle, however, this is different: the volume of the surface layer (few atomic diameters-wide)
becomes a significant fraction of the particle's volume; whereas that fraction is insignificant for
particles with diameter of one micrometer or more.[citation needed] In other words, the surface
area/volume ratio impacts certain properties of the nanoparticles more prominently than in bulk
particles.[14]

Interfacial layer
See also: Nanoparticle interfacial layer
For nanoparticles dispersed in a medium of different composition, the interfacial layer — formed by
ions and molecules from the medium that are within a few atomic diameters of the surface of each
particle — can mask or change its chemical and physical properties. Indeed, that layer can be
considered an integral part of each nanoparticle.[7]

Solvent affinity
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.

Coatings

Semiconductor nanoparticle (quantum dot) of lead sulfide with complete passivation by oleic acid,
oleyl amine and hydroxyl ligands (size ~5nm)
Nanoparticles often develop or receive coatings of other substances, distinct from both the particle's
material and of the surrounding medium. Even when only a single molecule thick, these coatings
can radically change the particles' properties, such as and chemical reactivity, catalytic activity, and
stability in suspension.

Diffusion across the surface

The high surface area of a material in nanoparticle form allows heat, molecules, and ions to diffuse
into or out of the particles at very large rates. The small particle diameter, on the other hand, allows
the whole material to reach homogeneous equilibrium with respect to diffusion in a very short time.
Thus many processes that depend on diffusion, such as sintering can take place at lower
temperatures and over shorter time scales inducing catalysis.

Ferromagnetic and ferroelectric effects

The small size of nanoparticles affects their magnetic and electric properties. The ferromagnetic
materials in the micrometer range is a good example: widely used in magnetic recording media, for
the stability of their magnetization state, those particles smaller than 10 nm are unstable and can
change their state (flip) as the result of thermal energy at ordinary temperatures, thus making them
unsuitable for that application.[58]

Mechanical Properties
The reduced vacancy concentration in nanocrystals can negatively affect the motion of dislocations,
since dislocation climb requires vacancy migration. In addition, there exists a very high internal
pressure due to the surface stress present in small nanoparticles with high radii of curvature.[59]
This causes a lattice strain that is inversely proportional to the size of the particle,[60] also well
known to impede dislocation motion, in the same way as it does in the work hardening of materials.
[61] For example, gold nanoparticles are significantly harder than the bulk material.[62]
Furthermore, the high surface-to-volume ratio in nanoparticles makes dislocations more likely to
interact with the particle surface. In particular, this affects the nature of the dislocation source and
allows the dislocations to escape the particle before they can multiply, reducing the dislocation
density and thus the extent of plastic deformation.[63][64]
There are unique challenges associated with the measurement of mechanical properties on the
nanoscale, as conventional means such as the universal testing machine cannot be employed. As a
result, new techniques such as nanoindentation have been developed that complement existing
electron microscope and scanning probe methods.[65] Atomic force microscopy (AFM) can be used
to perform nanoindentation to measure hardness, elastic modulus, and adhesion between
nanoparticle and substrate.[66] The particle deformation can be measured by the deflection of the
cantilever tip over the sample. The resulting force-displacement curves can be used to calculate
elastic modulus.[67] However, it is unclear whether particle size and indentation depth affect the
measured elastic modulus of nanoparticles by AFM.[67]
Adhesion and friction forces are important considerations in nanofabrication, lubrication, device
design, colloidal stabilization, and drug delivery.[66] The capillary force is the main contributor to
the adhesive force under ambient conditions.[68] The adhesion and friction force can be obtained
from the cantilever deflection if the AFM tip is regarded as a nanoparticle. However, this method is
limited by tip material and geometric shape.[69] The colloidal probe technique overcomes these
issues by attaching a nanoparticle to the AFM tip, allowing control oversize, shape, and material.
[70] While the colloidal probe technique is an effective method for measuring adhesion force, it
remains difficult to attach a single nanoparticle smaller than 1 micron onto the AFM force sensor.
[70]
Another technique is in situ TEM, which provides real-time, high resolution imaging of
nanostructure response to a stimulus. For example, an in situ force probe holder in TEM was used
to compress twinned nanoparticles and characterize yield strength.[71] In general, the measurement
of the mechanical properties of nanoparticles is influenced by many factors including uniform
dispersion of nanoparticles, precise application of load, minimum particle deformation, calibration,
and calculation model.[66]
Like bulk materials, the properties of nanoparticles are materials dependent. For spherical polymer
nanoparticles, glass transition temperature and crystallinity may affect deformation and change the
elastic modulus when compared to the bulk material.[66] However, size-dependent behavior of
elastic moduli could not be generalized across polymers.[66] As for crystalline metal nanoparticles,
dislocations were found to influence the mechanical properties of nanoparticles, contradicting the
conventional view that dislocations are absent in crystalline nanoparticles.[66]

Melting point depression

A material may have lower melting point in nanoparticle form than in the bulk form. For example,
2.5 nm gold nanoparticles melt at about 300 °C, whereas bulk gold melts at 1064 °C.[72]

Quantum mechanics effects

Quantum mechanics effects become noticeable for nanoscale objects.[73] They include quantum
confinement in semiconductor particles, localized surface plasmons[73] in some metal particles,
and superparamagnetism in magnetic materials. Quantum dots are nanoparticles of semiconducting
material that are small enough (typically sub 10 nm or less) to have quantized electronic energy
levels.
Quantum effects are responsible for the deep-red to black color of gold or silicon nanopowders and
nanoparticle suspensions.[72] Absorption of solar radiation is much higher in materials composed
of nanoparticles than in thin films of continuous sheets of material. In both solar PV and solar
thermal applications, by controlling the size, shape, and material of the particles, it is possible to
control solar absorption.[74][75][76][77]
Core-shell nanoparticles can support simultaneously both electric and magnetic resonances,
demonstrating entirely new properties when compared with bare metallic nanoparticles if the
resonances are properly engineered.[78][79][80] The formation of the core-shell structure from two
different metals enables an energy exchange between the core and the shell, typically found in
upconverting nanoparticles and downconverting nanoparticles, and causes a shift in the emission
wavelength spectrum.[81]
By introducing a dielectric layer, plasmonic core (metal)-shell (dielectric) nanoparticles enhance
light absorption by increasing scattering. Recently, the metal core-dielectric shell nanoparticle has
demonstrated a zero backward scattering with enhanced forward scattering on a silicon substrate
when surface plasmon is located in front of a solar cell.[82]
Regular packing
Nanoparticles of sufficiently uniform size may spontaneously settle into regular arrangements,
forming a colloidal crystal. These arrangements may exhibit original physical properties, such as
observed in photonic crystals.[83][84]

Production
Artificial nanoparticles can be created from any solid or liquid material, including metals,
dielectrics, and semiconductors. They may be internally homogeneous or heterogenous, e.g. with a
Core–shell structure.[78][79][80]
There are several methods for creating nanoparticles, including gas condensation, attrition, chemical
precipitation,[85] ion implantation, pyrolysis and hydrothermal synthesis and biosynthesis.[86]

Mechanical
Friable macro- or micro-scale solid particles can be ground in a ball mill, a planetary ball mill, or
other size-reducing mechanism until enough of them are in the nanoscale size range. The resulting
powder can be air classified to extract the nanoparticles.[87][88][89]

Breakdown of biopolymers
Biopolymers like cellulose, lignin, chitin, or starch may be broken down into their individual
nanoscale building blocks, obtaining anisotropic fiber- or needle-like nanoparticles. The
biopolymers are disintegrated mechanically in combination with chemical oxidation or enzymatic
treatment to promote breakup, or hydrolysed using acid.

Pyrolysis
Another method to create nanoparticles is to turn a suitable precursor substance, such as a gas (e.g.
methane) or aerosol, into solid particles by combustion or pyrolysis. This is a generalization of the
burning of hydrocarbons or other organic vapors to generate soot.
Traditional pyrolysis often results in aggregates and agglomerates rather than single primary
particles. This inconvenience can be avoided by ultrasonic nozzle spray pyrolysis, in which the
precursor liquid is forced through an orifice at high pressure.

Condensation from plasma

Nanoparticles of refractory materials, such as silica and other oxides, carbides, and nitrides, can be
created by vaporizing the solid with a thermal plasma, which can reach temperatures of 10,000
kelvin, and then condensing the vapor by expansion or quenching in a suitable gas or liquid. The
plasma can be produced by dc jet, electric arc, or radio frequency (RF) induction. Metal wires can
be vaporized by the exploding wire method.
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.

Inert gas condensation

Inert-gas condensation is frequently used to produce metallic nanoparticles. The metal is evaporated
in a vacuum chamber containing a reduced atmosphere of an inert gas.[90] Condensation of the
supersaturated metal vapor results in creation of nanometer-size particles, which can be entrained in
the inert gas stream and deposited on a substrate or studied in situ. Early studies were based on
thermal evaporation.[90] Using magnetron sputtering to create the metal vapor allows to achieve
higher yields.[91] The method can easily be generalized to alloy nanoparticles by choosing
appropriate metallic targets. The use of sequential growth schemes, where the particles travel
through a second metallic vapor, results in growth of core-shell (CS) structures.[92][93][94]

Radiolysis method

a) Transmission electron microscopy (TEM) image of Hf nanoparticles grown by magnetron-

sputtering inert-gas condensation (inset: size distribution)[95] and b) energy dispersive x-ray (EDX)
mapping of Ni and Ni@Cu core@shell nanoparticles.[93]
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.[96]

Wet chemistry
Nanoparticles of certain materials can be created by "wet" chemical processes, in which solutions of
suitable compounds are mixed or otherwise treated to form an insoluble precipitate of the desired
material. The size of the particles of the latter is adjusted by choosing the concentration of the
reagents and the temperature of the solutions, and through the addition of suitable inert agents that
affect the viscosity and diffusion rate of the liquid. With different parameters, the same general
process may yield other nanoscale structures of the same material, such as aerogels and other
porous networks.[97]
The nanoparticles formed by this method are then separated from the solvent and soluble
byproducts of the reaction by a combination of evaporation, sedimentation, centrifugation, washing,
and filtration. Alternatively, if the particles are meant to be deposited on the surface of some solid
substrate, the starting solutions can be by coated on that surface by dipping or spin-coating, and the
reaction can be carried out in place.
The suspension of nanoparticles that result from this process is an example of colloid. Typical
instances of this method are the production of metal oxide or hydroxide nanoparticles by hydrolysis
of metal alkoxides and chlorides.[98][5]
Besides being cheap and convenient, the wet chemical approach allows fine control of the particle's
chemical composition. Even small quantities of dopants, such as organic dyes and rare earth metals,
can be introduced in the reagent solutions end up uniformly dispersed in the final product.[99][100]

Ion implantation
Ion implantation may be used to treat the surfaces of dielectric materials such as sapphire and silica
to make composites with near-surface dispersions of metal or oxide nanoparticles.[citation needed]

Functionalization
Many properties of nanoparticles, notably stability, solubility, and chemical or biological activity,
can be radically altered by coating them with various substances — a process called
functionalization. Functionalized nanomaterial-based catalysts can be used for catalysis of many
known organic reactions.
For example, suspensions of graphene particles can be stabilized by functionalization with gallic
acid groups.[101]
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.[102][103]
Nanoparticles can be linked to biological molecules that can act as address tags, directing them to
specific sites within the body[104] specific organelles within the cell,[105] or causing them to
follow specifically the movement of individual protein or RNA molecules in living cells.[106]
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,[107][108][109] avoid clustering and so are
preferable for tracking the behavior of individual proteins.
It has been shown that catalytic activity and sintering rates of a functionalized nanoparticle catalyst
is correlated to nanoparticles' number density[110]
Coatings that mimic those of red blood cells can help nanoparticles evade the immune system.[111]
Uniformity requirements
The chemical processing and synthesis of high-performance technological components for the
private, industrial, and military sectors requires the use of high-purity ceramics (oxide ceramics,
such as aluminium oxide or copper(II) oxide), polymers, glass-ceramics, and composite materials,
as metal carbides (SiC), nitrides (Aluminum nitrides, Silicon nitride), metals (Al, Cu), non-metals
(graphite, carbon nanotubes) and layered (Al + Aluminium carbonate, Cu + C). 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
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.[112][113][114]
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.[115][116][117]
Inert gas evaporation and inert gas deposition[31][32] 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.[32] The reason why modern gas evaporation techniques can produce a
relatively narrow size distribution is that aggregation can be avoided.[32] 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.[33]
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.[118]

Characterization
Main article: Characterization of nanoparticles
Nanoparticles have different analytical requirements than conventional chemicals, for which
chemical composition and concentration are sufficient metrics. Nanoparticles have other physical
properties that must be measured for a complete description, such as size, shape, surface properties,
crystallinity, and dispersion state. Additionally, sampling and laboratory procedures can perturb
their dispersion state or bias the distribution of other properties.[119][120] In environmental
contexts, an additional challenge is that many methods cannot detect low concentrations of
nanoparticles that may still have an adverse effect.[119] For some applications, nanoparticles may
be characterized in complex matrices such as water, soil, food, polymers, inks, complex mixtures of
organic liquids such as in cosmetics, or blood.[121][122]
There are several overall categories of methods used to characterize nanoparticles. Microscopy
methods generate images of individual nanoparticles to characterize their shape, size, and location.
Electron microscopy and scanning probe microscopy are the dominant methods. Because
nanoparticles have a size below the diffraction limit of visible light, conventional optical
microscopy is not useful. Electron microscopes can be coupled to spectroscopic methods that can
perform elemental analysis. Microscopy methods are destructive and can be prone to undesirable
artifacts from sample preparation, or from probe tip geometry in the case of scanning probe
microscopy. Additionally, microscopy is based on single-particle measurements, meaning that large
numbers of individual particles must be characterized to estimate their bulk properties.[119][121]
Spectroscopy, which measures the particles' interaction with electromagnetic radiation as a function
of wavelength, is useful for some classes of nanoparticles to characterize concentration, size, and
shape. X-ray, ultraviolet–visible, infrared, and nuclear magnetic resonance spectroscopy can be
used with nanoparticles."Structural, functional and magnetic ordering modifications in graphene
oxide and graphite by 100 MeV gold ion irradiation". Vacuum. 182: 109700. 2020-12-01.
doi:10.1016/j.vacuum.2020.109700</ref>[119][121] Light scattering methods using laser light, X-
rays, or neutron scattering are used to determine particle size, with each method suitable for
different size ranges and particle compositions.[119][121] Some miscellaneous methods are
electrophoresis for surface charge, the Brunauer–Emmett–Teller method for surface area, and X-ray
diffraction for crystal structure,[119] as well as mass spectrometry for particle mass, and particle
counters for particle number.[121] Chromatography, centrifugation, and filtration techniques can be
used to separate nanoparticles by size or other physical properties before or during characterization.
[119]

Health and safety

See also: Health and safety hazards of nanomaterials, Particulates, and Nanotoxicology
Nanoparticles present possible dangers, both medically and environmentally.[123][124][125][126]
Most of these are due to the high surface to volume ratio, which can make the particles very
reactive or catalytic.[127] They are also thought to aggregate on phospholipid bilayers[128] and
pass through cell membranes in organisms, and their interactions with biological systems are
relatively unknown.[129][130] 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.[131] A recent study looking at the effects of ZnO nanoparticles on
human immune cells has found varying levels of susceptibility to cytotoxicity.[132] 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.[133] However considerable
research has demonstrated that zinc nanoparticles are not absorbed into the bloodstream in vivo.
[134]
Concern has also been raised over the health effects of respirable nanoparticles from certain
combustion processes.[135][136] Preclinical investigations have demonstrated that some inhaled or
injected noble metal nano-architectures avoid persistence in organisms.[137][138] As of 2013 the
U.S. Environmental Protection Agency was investigating the safety of the following nanoparticles:
[139]
• 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.[139]
• 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.[139]
• 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.[139]
• Nano Silver: Nano silver is being incorporated into textiles, clothing, food packaging, and
other materials to eliminate bacteria. EPA and the U.S. Consumer Product Safety
Commission are 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.[139]
• 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 United States.
[139]

Regulation
As of 2016, the U.S. Environmental Protection Agency had conditionally registered, for a period of
four years, only two nanomaterial pesticides as ingredients. The EPA differentiates nanoscale
ingredients from non-nanoscale forms of the ingredient, but there is little scientific data about
potential variation in toxicity. Testing protocols still need to be developed.[140]

Applications
As the most prevalent morphology of nanomaterials used in consumer products, nanoparticles have
an enormous range of potential and actual applications. Table below summarizes the most common
nanoparticles used in various product types available on the global markets.
Scientific research on nanoparticles is intense as they have many potential applications in pre-
clinical[141][142] and clinical medicine, physics,[143][144][145] optics,[146][147][148] and
electronics.[79][75][73][76] The U.S. National Nanotechnology Initiative offers government
funding focused on nanoparticle research.|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.[149] 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. Nanoparticles are being investigated as potential drug delivery
system.[150] Drugs, growth factors or other biomolecules can be conjugated to nano particles to aid
targeted delivery.[151] This nanoparticle-assisted delivery allows for spatial and temporal controls
of the loaded drugs to achieve the most desirable biological outcome. Nanoparticles are also studied
for possible applications as dietary supplements for delivery of biologically active substances, for
example mineral elements.[152]

Polymer reinforcement
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.[153]

Liquid properties tuner

The inclusion of nanoparticles in a solid or liquid medium can substantially change its mechanical
properties, such as elasticity, plasticity, viscosity, compressibility.[154][155]

Photocatalysis
Being smaller than the wavelengths of visible light, nanoparticles can be dispersed in transparent
media without affecting its transparency at those wavelengths. This property is exploited in many
applications, such as photocatalysis.[citation needed]

Road paving
Asphalt modification through nanoparticles can be considered as an interesting low-cost technique
in asphalt pavement engineering providing novel perspectives in making asphalt materials more
durable.[156]

Biomedical
Nanoscale particles are used in biomedical applications as drug carriers or imaging contrast agents
in microscopy. Anisotropic nanoparticles are a good candidate in biomolecular detection.[14]
Moreover, nanoparticles for nucleic acid delivery offer an unprecedented opportunity to overcome
some drawbacks related to the delivery, owing to their tunability with diverse physico-chemical
properties, they can readily be functionalized with any type of biomolecules/moieties for selective
targeting.[157]
Sunscreens
Titanium dioxide nanoparticles imparts what is known as the self-cleaning effect, which lend useful
water-repellant and antibacterial properties to paints and other products. Zinc oxide nanoparticles
have been found to have superior UV blocking properties and are widely used in the preparation of
sunscreen lotions,[158] being completely photostable[159] though toxic.[160][161][162][163][164]
[165]

Compounds by industrial area

Various nanoparticle chemical compounds which are commonly used in the consumer products by
industrial sectors[citation needed]
Industrial
No. Nanoparticles
sectors
silver, silicon dioxide, potassium, calcium, iron, zinc, phosphorus, boron, zinc
1 agriculture
oxide and molybdenum
tungsten, disulfidesilicon dioxide, clay, titanium dioxide, diamond, copper,
cobalt oxide, zinc oxide, boron nitride, zirconium dioxide, tungsten, γ-
2 automotive
aluminium oxide, boron, palladium, platinum, cerium(IV) oxide, carnauba,
aluminium oxide, silver, calcium carbonate and calcium sulfonate
titanium, dioxidesilicon dioxide, silver, clay, aluminium oxide, calcium
3 construction carbonate calcium silicate hydrate, carbon, aluminium phosphate cerium(IV)
oxide and calcium hydroxide
silver, titanium dioxide, gold, carbon, zinc oxide, silicon dioxide, clay, sodium
4 cosmetics
silicate, kojic acid and hydroxycarboxylic acid
5 electronics silver, aluminum, silicon dioxide and palladium
6 environment silver, titanium dioxide, carbonmanganese oxide, clay, gold and selenium
silver, clay, titanium dioxide, gold, zinc oxide, silicon dioxide, calcium,
7 food
copper, zinc, platinum, manganese, palladium and carbon
home
8 silver, zinc oxide, silicon dioxide, diamond and titanium dioxide
appliance
silver, gold, hydroxyapatite, clay, titanium dioxide, silicon dioxide, zirconium
9 medicine[166]
dioxide, carbon, diamond, aluminium oxide and ytterbium trifluoride
tungsten, disulfidezinc oxide, silicon dioxide, diamond, clay, boron, boron
10 petroleum nitride, silver, titanium dioxide, tungsten, γ-aluminium oxide, carbon,
molybdenum disulfide and γ-aluminium oxide
11 printing toner, deposited by a printer onto paper or other substrate
titanium, palladium, tungsten disulfide, silicon dioxide, clay, graphite,
renewable zirconium(IV) oxide-yttria stabilized, carbon, gd-doped-cerium(IV) oxide,
12
energies nickel cobalt oxide, nickel(II) oxide, rhodium, sm-doped-cerium(IV) oxide,
barium strontium titanate and silver
sports and
13 silver, titanium dioxide, gold, clay and carbon
fitness
silver, carbon, titanium dioxide, copper sulfide, clay, gold, polyethylene
14 textile
terephthalate and silicon dioxide