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Unit 3 – The Chemistry of Engineering

Materials

Engineered Nanomaterials


LEARNING OBJECTIVES

•
Determine the basic concepts in nanotechnology and learn the formation

of nanomaterials.
• Describe the properties and application of nanomaterials in different
fields.




1.0 Introduction to Nanotechnology and Nanomaterials
Nanomaterials has attractive properties and amazing technological possibilities,
which can be any one of the four basic types - metals, ceramics, polymers or composites. But
difficulties with nanomaterials arise from the fact that, in contrast to conventional materials,
a profound knowledge of materials science is not sufficient. Nanomaterials lie at the
intersection of materials science, physics, chemistry, and for many of the most interesting
applications – also of biology and medicine.
The first – and broadest – definition of nanomaterials states that, these are materials
where the sizes of the individual building blocks are less than 100 nm (a very small scale), at
least in one dimension (nm; equivalent to the diameter of approximately 500 atoms). Usually
nanomaterials are developed to show innovative characteristics compared to the same
material without the nanoscale features which includes, increased strength, chemical
reactivity or conductivity.

2.0 NANOTECHNOLOGY AND CONVENTIONAL TECHNOLOGY
The main difference between nanotechnology and conventional technologies is that
the “bottom-up” approach is favored in nanotechnology, whereas conventional technologies
generally use the “top-down” approach. On examining these technologies more closely, the
expression “top-down” means starting from large pieces of material and producing the
expected structure by mechanical or chemical methods This situation is shown schematically
in Figure 1. As long as the structures are within a range of sizes that are accessible by either

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mechanical tools or photolithographic processes, then top-down processes have an

unmatched flexibility in their application.



block or sheet of metal structured part








Figure 1. Conventional goods are produced via top-down processes, starting from bulk
materials. The intended product is obtained by the application of mechanical and/or
chemical processes (Vollath, 2013).

The condition is different in “bottom-up” processes where atoms or molecules are
used as the building blocks to produce nanoparticles, nanotubes, or nanorods, or thin films
or layered structures. Given their dimensionality, these features are also referred to as zero-
, one-, or two-dimensional nanostructures (see Figure 2). Figure 2 also reveals the building
of particles, layers, nanotubes, or nanorods from atoms (ions) or molecules. Although such
processes provide exceptional freedom among the resultant products, the number of
possible structures to be obtained is comparatively small. In order to obtain ordered
structures, bottom-up processes must be supplemented by the self-organization of
individual particles.

product dimensiona
lity
particles zero

atoms

nanotubes one
or rods

molecules
layers two

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Figure 2. The bottom-up process starting with atoms and molecules as the building blocks
that produced particles, nanotubes or nanorods and these products are also characterized
by their dimensionality (Vollath, 2013) .

Nanotubes and nanorods are usually referred to as one-dimensional nanoparticles,
nanoparticles and fullerenes, in contrast, are generally denominated as zero-dimensional
structures. Consequently, nanoplates, in particular graphenes, could be considered as two-
dimensional nanoparticles. A typical example of nanorods (in this case ZnO) is shown in
Figure 3. These rods are over 5 mm long (most are about 15 mm long), with diameters
ranging from 120 to 140 nm, and are clearly separated. For nanoplates, an example (in this
case gold nanoplates) is shown in Figure 4a. The size of these platelets is approximately 400
nm in the plane and their thickness ranges from 25 to 60 nm. As can be seen from the
hexagonal shape of the platelets, the nanoplates have a single orientation with the direction
perpendicular to the plane.

(Reproduced by permission of Springer.)
Figure 3. Secondary electron micrograph of ZnO nanorods. These nanorods have lengths of
about 15 mm and diameters ranging from 120 to 140 nm. (Vollath, 2013).

(Reproduced with permission by The American Institute of Physics.)

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Figure 4. (a) Electron micrograph of the gold platelets; these are about 400 nm wide, with
thickness ranging from 25 to 60 nm. (b) Electron diffraction pattern of a gold platelet as
shown in (a) (Vollath, 2013).

The hexagonal symmetry of the diffraction pattern indicates that the direction of the
platelets was perpendicular to the faces of the platelet; in other words, the electron beam
was exactly parallel to the direction.

3.0 FORMATION OF NANOMATERIALS
Formation of Rods and Plates
In the formation of nanorods and nanoplates, the influence of surface energy is to be
considered. For nonspherical nanostructures, this is especially important in the case of
anisotropic (noncubic) structures. But for surface-active molecules it is possible to grow rods
or plates even from isotropic materials. In this context, it should be noted that even from
gold, the existence of cubic material, nanorods, and nanoplates is well known (see Figure 4).
The second possibility of obtaining nanorods and nanotubes is related to layered
structures, where the crystal structure is built from layers held together with van der Waals
forces rather than by electrostatic attraction. The general arrangement of a particle
crystallized in such a layered structure is shown schematically in Figure 5a, where the layers
are independent. At the circumference of each layer, the bonds are not saturated (these
“dangling bonds” are indicated in Figure 5b). Based on this explanation, it is clear that all
compounds that crystallize in layered structures show a tendency to form nanotubes. Typical
examples are boron nitride (BN), WS2, MoS2, WSe2, MoSe2, and, most importantly, carbon.

Figure 5. Layout of a particle that crystallizes in a layered structure. (a) Particle set-up.
(b) One layer of a particle as depicted in (a). The bindings at the circumference of the layer
are not saturated (Vollath, 2013).

The dangling bonds (short lines) need additional energy; thus, there is a strong
tendency to saturate these dangling bonds.
The use of compounds that crystallize in only one dimension is the third possibility
of obtaining nanotubes. In concept, this is the most promising way to obtain long fibers, but

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unfortunately the importance of this route is negligible as the numbers of compounds

coming into question is small.
Imogolite is the most important compound in this context with an ideal composition
of Al2SiO3(OH)4. The ratio of silicon over aluminum is fairly flexible and can be used to adjust
the tube diameter. Imogolite tubes with the ideal composition are very narrow, with internal
diameters of 1 nm and external diameters of 2 nm. The structure of imogolite (see Figure 6)
is characterized by aluminum, silicon, oxygen, and OH- ions arranged in rings. This structure
allows the addition of organic molecules (to “functionalize”) at the surface.

Figure 6. Arrangement of ions in imogolite (Vollath, 2013).

Attachment of organic compounds at the outer layer consisting of oxygen ions is a

possibility where tube diameter can be adjusted by altering the aluminum/silicon ratio.

Formation of Carbon Nanotubes

Discussions about graphite and fullerenes as special modification of carbon is
essential in order to understand carbon nanotubes. The modifications of a substance differ
in the ways in which the atoms are arranged and bond with each other, and so different
modifications will have different physical and chemical properties. For example, graphite
crystallizes in a layered hexagonal structure (Figure 7) in which each carbon atom is bound
covalently to its three neighbors.

Figure 7. Structure of graphite. Each layer consists of interconnected hexagons with one
carbon atom at each vertex (Vollath, 2013).

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Consequently, only three of the four valences of the carbon atom are saturated. The
fourth electron of the atoms remains unbound and becomes delocalized across the
hexagonal atomic sheets of carbon. Electrons in graphite are mobile which shows electrical
conductivity within the layers; perpendicularly to the layers, graphite is an insulator. Within
the layers are strong covalent bonds, whereas in between the layers are weak van der Waals
bonds and, accordingly, it is possible to cleave pieces of monocrystalline graphite. These
single layers of graphite are known as graphene, and because of its structure and bonding
graphene is often denominated as an infinitely extended, two-dimensional aromatic
compound.
The bonding is shown in Figure 8a, representing one elementary hexagon and its first
row of neighbors clearly shows the interplay between single and double bonds.
In boron nitride (BN), one observes single bonds only, as nitrogen as well as boron
are both in their three valency state. Hence, there are no free electrons, with the consequence
that bulk BN is an isolator. (BN nanotubes, however, are wide-band semiconductors.) In
correlation to Figure 8a, Figure 8b displays the elementary hexagon of BN and its first
neighbors.


a) b)





Figure 8. (a) Structure elements of graphene and (b) boron nitride (BN). In contrast to
graphene, BN has only single bonds (Vollath, 2013).

In the sense that graphene is a two-dimensional aromatic compound, fullerenes,
which also exist in the case of BN, are three-dimensional aromatics. Fullerenes consist of a
combination of hexagons and pentagons; Figure 9 illustrates one pentagon surrounded by
five hexagons. The arrangement leaves gaps between the hexagons, the closure of these (as
indicated by an arrow in Figure 9) leads to the formation of a three-dimensional structure.
This is the basic structural element of fullerenes. Spherical shapes are formed by combining
a larger number of these structures.
The most common fullerene, and the first to be identified consists of 60 carbon atoms
(this is written as C60), with the molecular structure comprising 12 pentagons and 20
hexagons. The fullerene with the least number of carbon which is identified
(experimentally) is C20 while the smallest stable fullerene is C36. These fullerenes are most
stable, where each pentagon is surrounded by hexagons only. In addition to C60, the most
important other fullerenes are C70, C76, C78, and C84. The appearances of C60 and C70 are shown

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in Figure 10a and b. It is possible to attach metal atoms or other molecules at the surface of
fullerene even if it is quite stable, this reaction is of major importance in view of the
applications of fullerenes. Fullerenes also appear quite often in many layers; these
aggregates are known as “nested fullerenes” or “onion molecules.”

Figure 9. Five hexagons surrounding a pentagon. Closing the gaps between the hexagons
leads to a three-dimensional structure – the basic element of fullerenes (Vollath, 2013).

a) b)

Figure 10. Two different fullerenes. The hexagons and pentagons – the constitutive
elements of fullerenes – can be seen easily in both models. (a) C60 fullerene. (b) C70 fullerene
(Vollath, 2013).

It may be easily conceived that single graphite layers (graphene) reduce the energy
stored in the dangling bonds by forming tubes. There are, however, alternative possibilities
for these planes to form coils and this determines the properties of the carbon nanotubes.
Nanotubes are formed by wrapping graphene layers of limited size to form a tube.
After rolling the graphene sheet to form a tube, a nanotube with a diameter of 1.35 nm has
the appearance (armchair type) illustrated in Figure 11.

Figure 11. Armchair-type carbon nanotube. The diameter is calculated as 1.35 nm (Vollath,
2013)

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The formation of nanotubes is not limited to single graphene layers and, as for
fullerenes, both “multiwall” and “single-wall” nanotubes may be observed. The multiwall
nanotubes consist of a series of coiled graphene layers and can be described perfectly using
electron microscopy (see Figure 12).

Figure 12. Example of a multiwall carbon nanotube. The outer diameter of this multiwall
nanotube is 1.25 nm (Vollath, 2013).

4.0 PROPERTIES AND APPLICATIONS OF NANOMATERIALS

Nanocarbons
Nanocarbons which are a class of recently discovered materials have innovative and
exceptional properties and are currently being used in some cutting-edge technologies and
will certainly play an important role in future high-tech applications. Three nanocarbons that
belong to this class are fullerenes, carbon nanotubes, and graphene.

Fullerenes
The material composed of C60 molecules is known as buckminsterfullerene, (or
buckyball for short) (Figure 10), named in honor of R. Buckminster Fuller, who invented the
geodesic dome; each C60 is simply a molecular replica of such a dome. The term fullerene is
used to denote the class of materials that are composed of this type of molecule.
In the solid state, the C60 units form a crystalline structure and pack together in a face-
centered cubic array. This material is called fullerite, and Table 1 lists some of its properties.
A few fullerene compounds have been developed which have uncommon chemical,
physical and biological characteristics and does have the potential to be used in a of new
applications. Some of these compounds involve atoms or groups of atoms that are enclosed
within the cage of carbon atoms (and are termed endohedral fullerenes). For other
compounds, atoms, ions, or clusters of atoms are attached to the outside of the fullerene shell
(exohedral fullerenes). Uses and potential applications of fullerenes include antioxidants in
personal care products, biopharmaceuticals, catalysts, organic solar cells, long-life batteries,
high- temperature superconductors, and molecular magnets.

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Table 1. Properties of Carbon Nanomaterials (Callister & Rethwisch, 2014).

Material
Property C60 (Fullerite) Carbon Graphene
Nanotubes (In-Plane)
(Singled
Walled)
-
Density (&') ) 1.69 1.33-1.40 -
Modulus of elasticity (GPa) - 1000 1000
Strength (MPa) - 13,000 - 53,000 130,000
9
Thermal Conductivity Ž' ∙ 𝐾• 0.4 ~2000 3000 - 5000

Coefficient, Thermal Expansion - - ~-6

(1035 𝐾 3( )
Electrical Resistivity (Ω ∙ 𝑚) 1014 10-6 10-8

Carbon Nanotubes
Carbon nanotubes are another molecular form of carbon which has recently been
discovered that has some unique and technologically promising properties. Its structure
consists of a single sheet of graphite (i.e., graphene) that is rolled into a tube; the term single-
walled carbon nanotube (abbreviated SWCNT) is used to denote this structure. Each
nanotube is a single molecule composed of millions of atoms; the length of this molecule is
much greater (on the order of thousands of times greater) than its diameter. Multiple-walled
carbon nanotubes (MWCNTs) consisting of concentric cylinders also exist (see Figure 12).
Nanotubes are extremely strong and stiff and relatively ductile. Additionally,
nanotubes have relatively low densities. Table 1 shows several properties of single-walled
nanotubes. On the basis of their exceedingly high strengths, carbon nanotubes have the
potential to be used in structural applications. On the other hand, most current applications
are limited to the use of bulk nanotubes—collections of unorganized tube segments. Thus,
bulk nanotube materials will most likely never achieve strengths comparable to individual
tubes. Bulk nanotubes are currently being used as reinforcements in polymer-matrix
nanocomposites to improve not only mechanical strength, but also thermal and electrical
properties.
Carbon nanotubes also have unique and structure-sensitive electrical characteristics.
Depending on the orientation of the hexagonal units in the graphene plane (i.e., tube wall)
with the tube axis, the nanotube may behave electrically as either a metal or a
semiconductor. As a metal, they have the potential for use as wiring for small-scale circuits.
In the semiconducting state they may be used for transistors and diodes. Furthermore,
nanotubes are excellent electric field emitters. As such, they can be used for flat-screen
displays (e.g., television screens and computer monitors).

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Other potential applications are varied and numerous, and include the following:
• More efficient solar cells
• Better capacitors to replace batteries
• Heat removal applications
• Cancer treatments (target and destroy cancer cells)
• Biomaterial applications (e.g., artificial skin, monitor and evaluate engineered
tissues)
• Body armor
• Municipal water-treatment plants (more efficient removal of pollutants and
contaminants)

Graphene
Graphene as the newest member of the nanocarbons, is a single-atomic-layer of
graphite, composed of hexagonally sp2 bonded carbon atoms (see graphite in Figure 7).
These bonds are extremely strong, yet flexible, which allows the sheets to bend. The first
graphene material was produced by peeling apart a piece of graphite, layer by layer using
plastic adhesive tape until only a single layer of carbon remained (micromechanical
exfoliation, or the adhesive-tape method). Although pristine graphene is still produced using
this technique (which is very expensive), other processes have been developed that yield
high-quality graphene at much lower costs.
Two characteristics of graphene make it an exceptional material. First is the perfect
order found in its sheets where no atomic defects such as vacancies exist; also these sheets
are extremely pure and only carbon atoms are present. The second characteristic relates to
the nature of the unbonded electrons: at room temperature, they move much faster than
conducting electrons in ordinary metals and semiconducting materials.
In terms of its properties (some are listed in Table 1), graphene could be labeled the
ultimate material. Furthermore, it is transparent, chemically inert, and has a modulus of
elasticity comparable to the other nanocarbons (~1 TPa).
Given this set of properties, the technological potential for graphene is enormous, and
it is expected to modernize many industries to include electronics, energy, transportation,
medicine/biotechnology, and aeronautics. However, before this revolution can begin to be
realized, economical and reliable methods for the mass production of graphene must be
developed.
The following is a short list of some of the potential applications for graphene: touch-
screens, conductive ink for electronic printing, transparent conductors, transistors, heat
sinks (electronics); polymer solar cells, catalysts in fuel cells, battery electrodes,
supercapacitors (energy); artificial muscle, enzyme and DNA biosensors, photoimaging
(medicine/biotechnology); chemical sensors (for explosives); and nanocomposites for
aircraft structural components (aeronautics).

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