NANOMATERIALS

Lecture #4
Surface Science

Introduction

To understand and apply nanomaterials, besides knowledge on materials

science, a basic understanding of physics and chemistry is necessary.
Many applications are connected to biology and medicine; knowledge in
these fields are also of advantage.

Introduction

The surface forms a sharp interface between a particle and the

surrounding atmosphere or between a precipitated phase and the
parent phase.
In mathematics, the surface of a body, for example, a sphere or a
polyhedron, is clearly defined.
In a sphere, the ratio surface over volume is indirectly proportional to the
diameter, which is different in the case of a real, physically existing
material.
One has to distinguish between free surfaces in the case of particulate
materials and grain boundaries in bulk material.
As nanoparticles become small, they have large surfaces.
What is a surface of a real solid?
The answer must not be restricted to the geometrical surface.

A solid and its behavior can give the surface-influenced volume.

A simplified model assumes a layer with a thickness at the surface.
The thickness is found experimentally in the range between 0.5 and 1 nm.

Nanoparticles
Some birds and mammals apply magnetic nanoparticles for
navigation, a sense called magnetoception.
In plants, the phenomenon of self-cleaning of leafs caused
by nanoparticles at the surface, called the Lotus effect is
well known and technically exploited for self cleaning
windows or porcelain ware for sanitary use.
The Sumerians already produced a red pigment to decorate
pottery. This pigment consisted of gold nanoparticles
embedded in a glass matrix stabilized with tin oxide.
In science, especially chemistry, suspensions of
nanoparticles have been well known since the nineteenth
century; however, at that time, this science was called
colloid chemistry.

The Lotus Effect

The leaves of the Lotus plant are always clean
because the lotus leaf cannot be moistened, it
is hydrophobic
Each drop of water flows immediately off the
leaf, picking up any dust, which is hydrophilic.
The Lotus effect is caused by an apparent
increase of the contact angle between water
and a solid surface.

The Lotus Effect

Equilibrium of surface
stresses at a contact
between a solid and
a liquid.
Due to the corrugated surface,
one has the impression of a
huge contact angle . However,
looking at the points of contact
of the individual particles, it is
obvious that there is nothing
special there, still at the
standard values.

The Lotus Effect

The contact angle, for a water/solid interface, at a maximum of
110 is a result of the equilibrium of the surface stresses.

where:
sg - the surface stresses at the interface between the solid and
the gas phase
s1 - the surface stress between the solid and the liquid phase
1g - the one between liquid and the gas pas phase
- the contact angle
The surface stress is described by a vector in the tangential plane
of the particle. However, for these simplified considerations, it is
correct to work with the absolute values of these vectors.

The Lotus Leaf

The lotus plant (Nelumbo nucifera) is a native Asian plant which has the distinct property of
being able to maintain its leaves particularly clean even if its natural habitat is muddy.
The leaves of the lotus plant have the outstanding characteristic of totally repelling water
because they are superhydrophobic.
The water droplets roll off the leaf surface and drag dirt away from it.
This self-cleaning effect renders the lotus leaf clean and resistant to dirt. The same effect
is found in other leaves such as those of nasturtium (Tropaeolum) and some Cannas, and in
some animals such as the water strider.
The surface properties of the lotus leaf were first investigated by Wilhelm Barthlott.
In 1997, he published an important paper where he described for the first time the Lotus
effect (a term that he later copyrighted) responsible for the self-cleaning properties of the
lotus leaves.
Barthlott showed that the self-cleaning properties of the lotus plant are produced by a
combination of the microstructure of the leaves and the epidermal cells on their rough
surfaces, which are covered with wax crystals.
The crystals provide a water-repellent layer, which is enhanced by the roughness of the
surface, making it a superhydrophobic surface, with a contact angle of about 150.
The water droplets on the surface tend to minimise the contact between the surface and
the drop, forming a nearly spherical droplet.

The Lotus Leaf

The consequence is that water droplets roll off the leaf surface and,
in doing so, drag dirt away from it. This effect, self-cleaning,
renders the lotus leaf clean and resistant to dirt.
Contaminants on the surface (generally larger than the cellular
structure of the leaves) rest on the tips of the rough surface and
when a water droplet rolls over the contaminant, the droplet
removes the particle from the surface of the leaf.

The Lotus Leaf

The Lotus effect has been an inspiration for several innovative materials, mainly
involving self-cleaning properties to reduce the amount of cleaning needed, with an
obvious environmental benefit

Particles of Equal Size

pn = cn
where:
pn - probability of touching particles
n - number of particles
c - volume concentration c
In producing bulk nanocomposites, the central problem is to obtain a perfect distribution of
the particulate phase in the matrix.
Processes based on mechanical blending or synthesizing the two phases separately and
mixing during the step of particle formation, never lead to homogeneous products on the
nanometer scale.
Provided there are no preferences and the process of blending is random, the probability
that two or more particles are touching each other and form a cluster is very high.
Usually, in such a mixture, one wants to obtain a relatively high concentration of active
particles, carrying the physical property of interest.
It is impossible to obtain the intended perfect distribution of two phases by blending.
Except for properties related to grain boundaries, the special properties of nanomaterials are
of single isolated particles that are altered or even lost in the case of interacting particles.
Most of the basic considerations are related to isolated nanoparticles as the unavoidable
interaction of two or more particles.

Surface Science

Regardless of whether we consider a bulk material or a nanoscale material, its physical and
chemical properties depend on many of its surface properties.
Surfaces perform numerous functions:

keep things in or out

allow the flow of a material or energy across an interface
can initiate or terminate a chemical reaction, as in the case of catalysts

The branch of science that deals with the chemical, physical and biological properties of surfaces is
called surface science.
Interface, rather than surface, is often used, to emphasise the fact that it is a boundary between
two phases: the material and the surrounding environment (liquid, solid or gas).
If a bulk material is subdivided into an ensemble of individual nanomaterials, the total volume
remains the same, but the collective surface area is greatly increased.
The consequence is that the surface-to-volume ratio of the material compared to that of the
parent bulk material is increased.

Granular and Caster Sugar

Caster sugar is finer, stickier (more surface absorption)
and dissolves faster in water.
How would the total surface area increase if a cube of
1m3 were progressively cut into smaller and smaller
cubes, until it is composed of 1nm3 cubes?

Surface Atoms

In surface science, the chemical groups that are at the material interface
determine its properties.
Properties like catalytic reactivity, electrical resistivity, adhesion, gas
storage and chemical reactivity depend on the nature of the interface.
Nanomaterials have a significant proportion of atoms existing at the
surface, which has a profound effect on reactions that occur at the surface
such as:
catalysis reactions
detection reactions
reactions that, to be initiated, require the physical adsorption of certain
species at the materials surface

In a nanomaterial, a larger fraction of the atoms is at the surface

influences some physical properties such as the melting point.
Given the same material, its melting point will be lower if it is nano-sized.
Surface atoms are more easily removed than bulk atoms, so the total
energy needed to overcome the intermolecular forces that hold the atom
fixed is less, thus the melting point is lower.

Shape also Matters

Given the same
volume, the extent of
the surface area
depends on the shape
of the material.
Example: a sphere and
a cube having the same
volume
The cube has a larger
surface area than the
sphere.
In nanoscience, not
only the size of a
nanomaterial is
important, but also its
shape.

The ratio between the height (h) and the

diameter (d) determines whether a shape is like
a wire or a disc: shape influences surface area.

Surface of Nanoparticles
The first and most important consequence of the small
particle size is the huge surface area.
The ratio surface/volume is inversely proportional to the
diameter of the particle.
The ratio is also applicable to the particle diameter.

Surface of Nanoparticles

Assuming spherical particles with the diameter d:

The surface area a of one particle: a = d2
The volume v of this particle: v = /6 d3
The surface/volume ratio: R=a/v = 6/d
This ratio is inversely proportional to the particle size. The surface A per
mol, a quantity important in thermodynamics:

n the number of particles per mol, M the molecular weight, and the
density of the particles

Surface of Nanoparticles

Theoretical dependency of the specific surface area of the particle diameter.

(Due to the agglomeration of the particles, experimentally the values are not observed.)

Agglomeration of particles increases with decreasing particle diameter, as the influence of the Van
der Waals forces increases too.
(Van der Waals forces are weak interactions between molecules or small particles having their
origin in quantum dynamics. These forces are neither covalent nor based on electrostatic or dipolar
interaction.)
Experimentally, the largest values are measured with activated charcoal in the range of 2000 m2 g1
and finely dispersed amorphous silica with values up to 600 m2 g1.

Physical Surface of Particles

Assuming a sphere with the diameter d and a layer with the thickness , which is
influenced by the surface. In this case the volume of this shell is:

Now a dimensionless volume ratio R* is defined as:

This ratio approaches one if d 2.

Surface of Nanoparticles

The figure depicts the ratio of the

surface-influenced volume over the
total volume of the particle.
The shape of the particles was
assumed to be spherical.
For a 5-nm particle, 49% or 78% of the
volume belongs to the surfaceinfluenced volume.
For smaller particles, the relative
amount of material influenced by
surface phenomena is significantly
larger.
In the first approximation the magnetic
moment at saturation and the
susceptibility depend primarily on the
part of the particles, which is not
influenced by the surface; hence,
magnetic nanoparticles exhibit only
low values for these parameters.

Surface Energy

The considerations valid for

free nanoparticles may be
adapted for nanocrystalline
bulk materials.
The term free surface
should be grain boundaries.
The atoms located in the
grain boundaries are highly
mobile, and sometimes
called liquid-like.
Surfaces and grain
boundaries are connected to
surface energy.
The surface energy is
proportional to the surface,
then, as the surface of the
particle, the geometrical
value is used.

Surface Energy
Atoms and molecules that exist at the surface or at an
interface are different from the same atoms or
molecules that exist in the interior of a material.
Atoms and molecules at the interface have enhanced
reactivity and a greater tendency to agglomerate:
surface atoms and molecules are unstable, they have
high surface energy.
Example of high surface energy is to coat some ping
pong balls with Velcro (putting the two sides on
different balls). If you place the balls in a plastic bag
and shake, the balls will stick together. If normal balls
are used, no attachment occurs.

Surface Energy
Nanomaterials have a very large fraction of their atoms and
molecules on their surface.
Fundamental chemical principle is that systems of high energy will
strive to attain a state of lower energy, by whatever means
possible.
So how is it possible to have nanomaterials?
Nanomaterials are abundant in nature (proteins, DNA, etc.).
Nanomaterials are inherently unstable, therefore, there are various
methods that nanomaterials adopt to minimise their inherent high
surface energy.

One of the ways of reducing the surface energy in nanoparticles is

agglomeration.
Surface energy is an additive quantity.
The surface of 10 identical nanoparticles is equal to the sum of the
surface energy of each individual nanoparticle. If these were to
agglomerate, and become one large particle, the overall surface
energy would be reduced.

Surface Energy
If a generic surface energy value is associated with each
lateral surface of cube A, than its total surface energy is 6.
The same applies to cube B.
Therefore, the total surface energy of both cubes, A and B,
separated, is 2 x 6 = 12.
The total surface energy of the parallelepiped C, on the
other hand, is 10.

Surface Energy
Nanoparticles have a strong intrinsic tendency
to agglomerate.
To avoid this, surfactants can be used.
When nanoparticles are used in research and
industry they are often immobilised on a solid
support or mixed within a matrix.
Even in commercial products that claim to
contain nanoparticles (such as sunscreens)
microscope images show that they are actually
present in the form of agglomerates of >100nm
dimensions.

Surface Energy of Particles

One particle with a geometrical surface a = d2 and a specific surface energy has a surface
energy of: usurface = a
With respect to thermodynamic considerations, the surface energy per mol is needed. The
number of particles per mol, N=M/v and the volume of one particle is v=/6 d3
The surface energy per mol:

The surface energy per mol is indirectly proportional to the particle diameter.
Please note: Quantities related to one particle are printed in lower case letters and quantities
valid for one mol in capital letters.
It is important to realize that the surface energy per mol is inversely proportional to the
particle diameter; this means that the surface energy increases drastically when the particle
size gets very small.

Surface Energy
A model to explain the origin of surface energy
starts with an infinitely extended solid.
The production of a particle by dividing this large
chunk of material into small particles is assumed.
The bonds between neighboring atoms are
separated.
(Within this introductory text, the word atom is
used equally for atoms, ions and molecules.) Now,
between each two atoms in the lattice, the
energy of bonding, u is needed to break the
bonds.

Surface Energy
Creating new surfaces, for example, by
breaking a larger part into smaller
pieces requires the energy u for each
bond to be broken.

Forces acting between atoms at lattice positions.

Because of the reduced number of neighbors, the
atoms at the surface are pulled in the direction to
the interior of the particle.
This does not lead to a pressure comparable with
a hydrostatic pressure, rather, it leads to a stress in
the surface, the surface stress.
For the estimation of thermal effects, for example,
during coagulation of two particles, the sum value
of the surface energy of both particles, is the ruling
one.

Surface Energy

To break a larger part of material into smaller pieces, each bond between two
neighboring atoms must be broken.
After breaking, two new surfaces emerge.
On both sides, for each atom at the new surface, half of the binding energy is
stored at the surface.
In the interior of a particle, the atoms are in a mechanical equilibrium of binding
forces, fixing them at their lattice positions.
Atoms at the surface have lost bonds at the outside. Because of the reduced
number of neighbors, at each atom at the surface, a force acts perpendicular to
the surface.
At a plane surface (to be mathematically exact: the surface of a plane infinite halfspace), against any intuition, this does not lead to a hydrostatic pressure in the
material, rather to a stress in the surface plane.
The surface stress deforming the surface results in the surface stretching. In a
spherical particle of limited size, the situation is different.
Caused by the curvature, in connection with the surface stress, a hydrostatic
pressure, comparable with one stemming from a gas or a liquid at the outside, in
the particle comes into action. This allows modeling of the surfaces of particles as
a skin made of elastic material, then the rubber skin model of the surface was
developed.

Origin of Surface Energy

Breaking a chunk of material into two parts forms two surfaces, with n
broken bonds.
The binding energy u per atom is split to both sides: ubreak = n(u/2)
The specific energy to break the bonds: o= N* (u/2)
where N* is the number of broken bonds per square meter. Due to the
uncompensated bonds at the surface, a force f perpendicular to the
surface emerges.
If a is the area occupied by one atom, the resulting surface stress: = f/a
The stress leads to a surface stretch s, assumed constant in any direction
of the tangent plane of the particle, of the surface, (To be mathematically
exact, and s are vectors in the tangential plane of the surface. For
reasons of simplicity, they are replaced by their absolute values. In the
context of these considerations, this does not make any difference.)
leading to the contribution S to the surface energy: = o + s
The contribution 0 exists only in the case of solids; for liquids 0 = 0 is
valid.
The pressure p caused by surface stress is given by: p = 4 /d

Surface Energy

The surface energy of these materials depends on the direction; hence, to minimize surface
energy, the materials crystallize in rods or platelets.
Surface-active substances can influence the surface energy, which is used for the production
of one- or two-dimensional particles such as needles or plates.
In the case of small particles, the surface energy dominates its behavior. Whenever
possible, particles that are touching each other will coagulate with a temperature flash.

Temperature Flash Caused by Particle

Coagulation

Temperature Flash Caused by Particle

Coagulation

The temperature flash makes coagulation possible at all, as the increased temperature
increases the mobility of the atoms.
Decrease of the temperature flash with increasing particle size explains the occurrence of
odd-shaped particles in the size range above 3 or 4nm.
The process of coagulation can be observed in the electron microscope
One of the two particles is in an orientation where lattice fringes are visible. These particles
are moving around on the surface of the carbon specimen carrier.
This movement changes the relative orientation of the particle lattice to the electron beam
and; therefore, the lattice fringes.
When, by chance, the particles touch each other, the particles rotate until their orientation is
equal.
When coagulation starts; the larger particle swallows the smaller one. This process needs a
significant thermal mobility of the atoms, to some extent, the necessary thermal energy is
provided from the reduction of the surface.
The temperature flash occurring due to coagulation has a severe influence on the particle
formation during synthesis.
Lastly, the consequence is that, using a random process; it is nearly impossible to obtain very
small particles.

Surface Energy
For particles smaller than 2nm, the surface energy is comparable to
the energy of formation. The free enthalpy of the monoclinic
tetragonal transformation is significantly smaller than the surface
energy.
Look only at the surface change during the phase transformation.
The small difference of the surface caused by the volume change
of roughly 4% during phase transformation leads to a change of
the surface energy, which is comparable to the free enthalpy of
transformation.
The particle size influences the phase transformation significantly.
For the isolated particles, the hydrostatic pressure caused by
surface stress in the particles. (The surface-induced hydrostatic
pressure is also why free water drops are spherical.)
This hydrostatic pressure p is a function of the curvature and the
surface stress; and most importantly, in the case of a spherical
particle, it is inversely proportional to the particle diameter.

Surface Energy

For the surface stress, a value of 1 N m 1 J m2 was selected. As values for

the surface energy and surface stress are poorly known for ceramic materials,
this value is often selected.
The hydrostatic pressure in a spherical particle with a diameter of 5 nm and a
surface energy of 1 N m1 is 4 108 Pa 4 103 bar. This is a very high value.
Hence, phase transformations connected to a volume change, which are
pressure sensitive, depending on the external pressure, are significantly
influenced.
Therefore, particle size influences phase transformations.

Surface Energy

The hydrostatic pressure, caused by the surface stress deforms the particle.
For metallic nanoparticles, particle contraction is so small which can be determined only by high-precision
X-ray lattice constant measurements.
For ceramic particles, reduction is generally superimposed by phenomena leading to lattice expansion.
For metals, the lattice expands with decreasing particle size. This phenomenon is explained by a change
in the lattice structure at the surface with decreasing particle size.
The cations at the surface of an oxide are terminated by oxygen ions or other anions, such as (OH).
Therefore, the surface of an oxide is covered with ions, all bearing negative electrical charges. These
negative charges repel each other; hence, the lattice expands.

Quantum Confinement

Quantum confinement causes the energy of the band gap to increase

At very small dimensions when the energy levels are quantified, the band
overlap present in metals disappears and is actually transformed into a
band gap.
This is why some metals become semiconductors as their size is
decreased.

Quantum Confinement
The increase in band gap energy due to quantum
confinement means that more energy will be needed
in order to be absorbed by the band gap of the
material.
Higher energy means shorter wavelength (blue shift).
The same applies to the wavelength of the fluorescent
light emitted from the nano-sized material, which will
be higher, so the same blue shift will occur.
Thus, a method of tuning the optical absorption and
emission properties of a nano-sized semiconductor
over a range of wavelengths by controlling its
crystallite size is provided.

Hypothetical Nanomotors Driven by

Surface Energy

There are experiments applying energy exchange during coagulation or the dependency
of the surface energy of anisotropic materials on the orientation for technical use.
A prominent example is the proposal of Regan et al. for a nanomotor based on
coagulation processes [8,9]. The basic idea of a motor based on coagulation is
relatively simple. It applies the migration of metallic atoms in an electric field at the
surface of carbon nanotubes [10]. Because of its low melting point, this device is
realized with indium as the metal to be transported. This led to the idea of a relaxation
oscillator.
On a carbon nanotube, which is connected to a direct current, DC source, two droplets
of indium are placed in close proximity. After switching the electrical current on, indium
is transported by electromigration from one droplet to the next. As a result, on the
carbon nanotube, one droplet shrinks and the other grows. When this process comes to
the point where the two droplets touch each other, they coagulate. The coagulation
process concentrates the material of both drops in the larger drop.
After coagulation, the continuing material transport leads again to the formation of the
smaller second droplet, which is nucleated at a discontinuity at the surface of the
nanotube. If there are no evaporation losses, this setup oscillates as long as it is
connected to a DC source.

Hypothetical Nanomotors Driven by

Surface Energy
The carbon nanotube, the droplets and, most
importantly, the growth of the smaller particle
at the expense of the larger one can be seen
easily in the series of electron.
The arrangement after coagulation shows that
the process may start again. The time for
complete coagulation was estimated to be in
the range of 200ps.

REFERENCES
Nanotechnologies: Principles, Applications,
Implications and Hands-on Activities by European
Commission 2012
Principles of Nanotechnology by G. Ali Mansoori
Nanoparticles, Nanocomposites, Nanomaterials:
An Introduction for Beginners by Dieter Vollath
2013
Nanotechnology: A Gentle Introduction to the
Next Big Idea by Mark A. Ratnell 2003

Seatwork