Chapter 1 – Introduction to Nanomaterials
1.1 Definition of Nanomaterials
Materials at the nanometric scale are defined as a set of substances in which at least one
dimension is smaller than 100 nanometers. A nanometer (nm) corresponds to one millionth of
a millimeter, or about 100,000 times smaller than the diameter of a human hair.
Nanomaterials are of great interest because, at this scale, unique properties emerge — optical,
magnetic, electrical, mechanical, and others. These emerging properties can have a major
impact in fields such as electronics, medicine, energy, and the environment [1].
1.2 History of Nanomaterials
Nanotechnology encompasses the synthesis and application of materials with dimensions on
the order of one billionth of a meter (10⁻⁹ m).
These so-called ultrafine particles exhibit behaviors very different from those of bulk matter.
Figure 1.1 illustrates a size comparison between various living and non-living structures [2].
When particles reach the nanometric scale, their electronic, chemical, thermal, and
mechanical properties are profoundly altered.
Thanks to nanotechnology, it is now possible to design materials and devices at the atomic
and molecular level. Natural colloids and nanoparticles have been observed and studied since
the last two decades [3, 4]. However, the history of nanomaterials actually dates back to the
origins of the universe: just after the Big Bang, nanostructures formed in primitive meteorites.
Nature then developed nanostructures such as seashells, skeletons, and combustion smokes
produced by early humans.
Scientifically, the first studies date from the 19th century, notably with colloidal
gold particles synthesized by Michael Faraday in 1857.
In the 1940s, precipitated silica nanoparticles were already being produced
industrially in the United States and Germany as rubber reinforcements [1]. In
recent years, nanomaterials (NM) have attracted the attention of researchers
because of their specific physical, biological, and chemical properties.
They can be classified according to their size, chemical composition, shape, and
origin [5].
1.3 Main Differences Between Nanomaterials and Bulk Materials
Nanomaterials have particles whose size varies between 1 and 100 nm in at
least one dimension; they are invisible to the naked eye.
Examples: nanozymes, titanium dioxide nanoparticles, graphene, etc.
Bulk materials, on the other hand, have particles larger than 100 nm in all
dimensions and are visible to the naked eye (e.g., plaster, sand, cement, salts,
ores…).
Property Nanomaterials Bulk materials
Size 1–100 nm >100 nm
Specific surface area Very high Low
Chemical reactivity Strong Limited
Optical/electrical properties Variable and tunable Fixed
Defect density Low High
Observation Invisible to the naked eye Visible
Figure 1.2 illustrates the main differences between nanomaterials and bulk
materials [6].
1.4 Types and Classifications of Nanomaterials
With the rapid development of nanotechnology, a large number of nanomaterials
have been created.
They are classified according to their structure, shape, size, and chemical
composition [7].
Generally, seven main categories are distinguished:
1.4.1 Carbon-Based Nanomaterials
These nanomaterials are mainly composed of carbon and can exist in several
forms:
• Hollow tubes (nanotubes)
• Spheres (fullerenes)
• Sheets (graphene)
They include carbon fibers, graphene, fullerenes, carbon black, carbon
nanotubes (CNTs), and carbon onions (see Figure 1.3) [7].
1.4.2 Metallic and Metal Oxide Nanomaterials
Pure metals and their oxides can also be produced at the nanometric scale.
Examples:
• Metals: gold (Au), silver (Ag)
• Metal oxides: TiO₂ (titanium dioxide), ZnO (zinc oxide)
These materials are grouped under the term inorganic nanomaterials [7].
1.4.3 Organic Nanomaterials
Organic nanomaterials are mainly made up of organic substances and have non-
covalent (weak and easily breakable) bonds.
They can be chemically modified to obtain various forms: liposomes,
dendrimers, micelles, polymers (see Figure 1.4) [7].
1.4.4 Nanocomposites
A nanocomposite results from the combination of several types of
nanomaterials: nanofibers, nanoparticles, polymers, metals, ceramics, etc. These
combinations make it possible to obtain materials with improved mechanical
and chemical properties (see Figure 1.5) [7].
1.4.5 Ceramic Nanomaterials (Nanoceramics)
Nanoceramics are inorganic, non-metallic solids, heat-resistant, and smaller than
100nm[8].
Their preparation through various chemical or physical methods gives them:
•Improvedstructure
• Enhanced electro-optical, ferromagnetic, and superconductive properties
For example, hydroxyapatite (HAP) nanoceramics exhibit antimicrobial
activity depending on their porosity and surface charge [10].
Al₂O₃–ZrO₂ nanoceramics, obtained at low temperature, show homogeneous
amorphous materials of nanometric size [11].
1.4.6 Semiconductor Nanomaterials
Semiconductor nanomaterials have a small band gap energy (< 4 eV).
Examples: silicon, germanium, gallium arsenide, ZnO, etc.
Their nanometric structure alters their properties due to quantum effects and
increased surface area.
They are classified as:
1. Intrinsic semiconductors: pure compounds without doping; their
resistance decreases as temperature increases.
2. Extrinsic semiconductors: doped with other metals to enhance
conductivity (n-type and p-type) [12].
1.4.7 Polymeric Nanomaterials
Polymeric nanomaterials are solid particles made from natural or synthetic
polymers.
They are widely used in pharmaceutical and biomedical applications, especially
for:
• Controlled drug release
• Biocompatibility
• Low toxicity [13]
They are classified as:
1. Polymeric micelles: formed by self-assembly of amphiphilic copolymers.
2. Polymeric nanoparticles (10–1000 nm): used as targeted drug delivery
vectors [14–15].
3. Dendrimers: three-dimensional macromolecules (< 15 nm) with
advanced medical applications [16].
4. Polymeric nanocomposites: combination of polymers and nanofillers to
improve mechanical properties [17].
1.5 Classification of Nanomaterials
1.5.1 Dimensions and Sizes
Nanomaterials can be classified according to their electronic dimensions [19]:
Type Electron movement Example
0D Electrons confined in three axes Quantum dots
1D Free movement along one axis (x) Nanowires, nanotubes
2D Free movement along two axes (x, y) Sheets, thin films
3D Free movement in all directions Nanostructured bulk materials
The classification by Pokropivny and Skorokhod links the properties of
nanomaterials to their shape and dimensionality [19].
1.5.2 Origin of Nanomaterials
Nanomaterials are also classified according to their origin:
[Link] Natural Nanomaterials
Naturally occurring, they are formed in:
• Biological organisms (microbes, plants)
• Soils, rocks, oceans, the atmosphere, and even the human body [20–21].
[Link] Synthetic Nanomaterials
Artificially produced through physical, chemical, biological, or hybrid methods.
These techniques allow:
• Large-scale production of nanomaterials
• Precise control of size and shape
• Addition of functional molecules to the surface
However, synthetic nanomaterials may exhibit different environmental
behavior from natural nanomaterials [22].