Properties of Nanomaterials

Size-dependent properties
At the nanometer scale, properties become size-dependent.

For example,

(1) Chemical properties – reactivity, catalysis

(2) Thermal properties – melting temperature

(3) Magnetic properties – superparamagnetic effect

(4) Mechanical properties – adhesion

(5) Optical properties – absorption and scattering of light

(6) Electrical properties – tunneling current

New properties enable new applications

 Size effect of Nanomaterials
Surface Effects

 As a particle decreases in size, a greater proportion

of atoms are found at the surface compared to those
inside. For example, a particle of

 Size-30 nm-> 5% of its atoms on its surface

 Size-10 nm->20% of its atoms on its surface
 Size-3 nm-> 50% of its atoms on its surface

 Nanoparticals are more reactive than large particles

(Catalyst)
Super surface activity: Catalytic property

With decreasing dimension of the particles, the

number of surface atoms increases drastically.
This leads to a significant energy contribution
to the system from the unsatisfied bonds of the
surface atoms. Hence, the surface becomes
extremely 'active' due to the high available
surface energy. This effect finds applications
in: adsorption of toxic gases, catalysis, etc.
Thermal property - Melting point
Melting temperature directly related to the bond
energy
 Mechanical Properties
Materials structures

Most materials are made up of

ordered crystals that meet at
disordered boundaries; the crystals in
nanomaterials are only 100–10,000
atoms across.

Amorphous or “glassy” materials are

totally disordered; the only
characteristic dimension is that of the
atoms or molecules that make them
up. They are an extreme from of
1
0 nanomaterial.
Mechanical Properties
 In a crystalline material, atoms are well organized in a specific
orientation. Crystalline materials have less number of dislocation
or faults and large numbers of boundaries.
 While in amorphous materials, atoms are randomly organized and
does not show any orientation of atoms/molecules.
 Besides this, amorphous materials have comparatively large grain
size with less number of boundaries. Thus, large numbers of
dislocations or faults are present in amorphous materials.
 According to hall patch effect, when a stress is applied the
dislocation propagate and cause deformation but grain boundaries
hindered the propagation of dislocations.
 So, nanomaterials due to small size (high number of boundaries)
hinder the propagation of dislocations. Therefore, it would be good
in mechanical strength.
 And, the deformation in crystalline nanomaterials is found less as
compared to the amorphous nanomaterials.
Mechanical Properties Bulk: More Room for Deformation
in bulk polycrystalline materials
Hall Petch Model (no longer valid)
The Hall-Petch model treats grain
boundaries as barriers to dislocation
motion, and thus dislocations pile up d = micrometer
scale grain size
against the boundary. Upon reaching a
critical stress, the dislocations will cross
over to the next grain and induce yielding.

Hall Petch Model says the smaller the

grain size the stronger the material.

The model is no longer valid as you go to

single crystal materials.
A“new” aspects about nano are:
Inverse Hall-Petch effect

 It is well established that decreasing the grain size results

in an increased hardness and strength as grain boundaries
pose an hindrance to dislocation motion.
 But, when grain size reduces to tens of nanometers (< 15
nm) the grain is not able to support a dislocation pile-up.
Hence the trend of increasing hardness/strength with a
decrease in grain size is broken in the nanocrystalline
materials.
 Nanoparticles
Nano-materials: Grain size few nm

Nanoparticles increase grain boundaries

Influence on mechanical properties: Increased

hardness, yield strength, elastic modulus, toughness

5
Comparison of Young modulus
Material Young modulus (GPa)
Rubber 0.1
Al 70
Fe 200
SiC 440
Fe nanoparticles (100 nm) 800
C nanotubes 1000
Diamond 1200

Young's modulus measures the resistance of a material

to elastic (recoverable) deformation under load. A stiff material has a high
Young's modulus and changes its shape only slightly under elastic loads
(e.g. diamond). A flexible material has a low Young's modulus and changes
its shape considerably (e.g. rubbers).

7
Magnetic properties
 Magnetic properties
Magnetic Materials are those materials in which a state of
magnetization can be induced.

Such materials when magnetized create a magnetic field in

the surrounding space.

Classification Of M a gne tic M a te ria ls

Paramagnetic
Diamagnetic
Ferromagnetic
Ferrimagnetic
Antiferromagnetic
P a r a m a g n e ti c : It is a substance or body which very
weakly attracted by a magnet, but not retaining any
permanent magnetism.

Al, Pt, Ca, O2

F e r r o m a g n e ti c : A type of material that is highly

attracted to magnets and can become permanently
magnetized is called as ferromagnetic. (when external field
is removed they do not lost the magnetism even then same
momentum are not applied in opposite direction).

Fe, Co, Ni, Cr, Mn

Superparamagnetism
Ferromagnetic materials consist of magnetic domains within
which the spins are parallel.

When the particle size is reduced to very small sizes (typically

less than 20 nm) the entire particle becomes a single domain.

On further reduction in size (about less than 5 nm) the spins get
thermally disordered in the absence of magnetic fields.
When an external magnetic field is applied the spins are able to
align in the direction of applied magnetic field, making them
behave as super paramagnets (i.e., in the absence of external
field the particle is paramagnetic and in the presence of a field
all the spins are aligned in parallel, leading to a large increase
in magnetization).
This is an interesting example in which a ferromagnetic
material in bulk behaves like a paramagnet when particle
size is made very small.
Nanoparticles exhibit the phenomenon of
“superparamagnetism”, i.e, on application of an external
magnetic field, they become magnetized up to their
saturation magnetization, and on removal of the magnetic
field, they no longer exhibit any residual magnetic
interaction.
This property is size-dependent and generally arises
when the size of nanoparticles is as low as 10–20 nm.
This superparamagnetism, unique to nanoparticles, is
very important for their use as drug delivery vehicles
because these nanoparticles can literally drag drug
molecules to their target site in the body under the
influence of an applied magnet field.

.
The term ‘quantum confinement’ is mainly
deals with energy of confined electrons
(electrons or electron-hole). The energy levels
of electrons will not remain continuous as in
the case of bulk materials compare to the
nanocrystal. Moreover, obtains the confined
electron wave functions, they become a
discrete set of energy levels as shown in the
figure 1. Such kinds of effects appear when the
dimensions of the potential approach nearly to
de Broglie wavelength of electrons and
resulting in the changes or discreteing levels of
energy. The effects are defined as quantum
confinement and consequently, for nano-
crystals are often called quantum dots (QDs)
Conductive/Electrical properties
Quantum confinement
In small nanocrystals, the electronic energy
levels are not continuous as in the bulk but are
discrete (finite density of states), because of the
confinement of the electronic wavefunction to
the physical dimensions of the particles. This
phenomenon is called quantum confinement and
therefore nanocrystals are also referred to as
quantum dots (QDs).
Metals behave like semiconductor in nanosize as compared to conductor.
 Optical properties of Nanomaterials
SCATTERING EFFECT:
The colors arises from the fact that different particle
sizes scatter different wavelengths.
Maximum scattering occurs for wavelengths
twice as large as the cluster size.

Therefore if the cluster is about 200 nm, than

maximum scattering is observed at 400nm, which
lies in the visible light range
 Optical Properties Example – Zinc
Oxide (ZnO)
Large ZnO particles
◦ Block UV light
◦ Scatter visible light
◦ Appear white Nanoscale ZnO
Nanosized ZnO particles sunscreen is clear
“Traditional” ZnO
◦ Block UV light sunscreen is white

◦ So small compared to the

wavelength of visible light that
they don’t scatter it
◦ Appear clear
Zinc oxide nanoparticles
Sources: http://www.apt powders.com/images/zno/im_zinc_oxide_particles.jpg
http://www.abc.net.au/science/news/stories/s1165709.htm
http://www.4girls.gov/body/sunscreen.jpg 29
localized surface plasmon resonance Effect: differentiate the optical
properties of metal nanoparticles in general from their bulk counterpart.

Due to this effect, when light hits a metal surface (of any size) some of
the light wave propagates along the metal surface giving rise to a
surface plasmon – a group of surface conduction electrons that
propagate in a direction parallel to the metal/dielectric (or
metal/vacuum) interface.

When a plasmon is generated in a conventional bulk metal, electrons

can move freely in the material and no effect is registered. In the case
of nanoparticles, the surface plasmon is localized in space, so it
oscillates back and forth in a synchronised way in a small space, and the
effect is called Localised Surface Plasmon Resonance (LSPR).

Figure 10. Transmission electron micrographs and UV—Vis spectra of

gold nanoparticle colloids with various geometries: (top) spheres,
(middle) decahedra and (bottom) rods. (Image credit: Reprinted from:
Borja Sepúlveda et al., "LSPR-based Nanobiosensors", Nano Today
(2009), 4 (3), 244- 251, with permission from Elsevier).
When the frequency of this oscillation is the same as
the frequency of the light that it generated it (i.e., the
incident light), the plasmon is said to be in resonance
with the incident light.

One of the consequences of the LSPR effect in metal

nanoparticles is that they have very strong visible
absorption due to the resonant coherent oscillation of the
plasmons.

As a result, colloids of metal nanoparticles such as gold or

silver can display colours which are not found in their
bulk form, like red, purple or orange, depending on the
nanoparticles’ shape, size and surrounding media.
Super-hydrophobicity
As the surface roughness is increased from micron-scale to
nano-scale, the actual contact area of the surface decreases
(assuming the apparent contact to be constant). The tip of
each asperity supports part of the water droplet.
This shifts hydrophobicity to higher level of
superhydrophobicity; wherein, contact angles of greater than
165 can be obtained.
The normal (maximum) contact angle obtained in the case of
hydrophobicity is about 120 (with the best available
substrate of least surface energy).
The phenomenon of superhydrophobicity can lead to the
development of non-wetting clothes, self-cleaning windows,
non bio-fouling surfaces etc.
 Lotus Leaf: Water does not stick to the surface of lotus leaf (small
droplets 'bead up') and cleans the surface-dirt as it rolls off.
Microscopically, the lotus leaf surface has fine distribution of
micro-protrusions (~ 10 µm long, ~ 10 µm high and spread ~ 15
µm apart), which enhance the surface roughness and decrease
contact area by a few orders of magnitude.
 Further, these micro-protrusion and the base surface have nano-
hairs (~ 80- 150 nm diameter) spread over the entire surface of
Lotus leaf, making the surface superhydrophobic.
 It is to be noted that the wetting angle (purely arising from the
chemical nature of the surface and as characterized by the surface
energy) can reach a maximum of 120.
 Contact angles >165 are observed on a lotus leaf and this increase
of 45 arises from the hierarchical structure of the lotus leaf (i.e.
from micro-protrusions and nanohairs on the surface of a lotus
leaf).
Lotus leaf- a hierarchical
structure

Protrusions
Hairs on
protrusion

Hairs on the
base
Examples of Nano structures in nature

Gecko: Gecko is known for its super sticky feet, as it can stick even to a
glass surface (works on almost any surface!). In spite of the strong
adhesion provided by the gecko's feet the animal can move around
with ease.

Gecko's foot contains rows of setae (~106 setae on each foot, ~ 5 m

diameter), each of which is tipped with few hundred fine hair-like
structures called spatulae.

These fine spatulae increase the surface area of contact and the adhesion
is through van der Waal's forces. The setae can be detached by
increasing the angle it makes to the surface and low forces are
required for this process. It spite of having this 'sticky' property
gecko feet are self cleaning.
Nacre:

The sea-shell (or nacre) has tablets or plies of calcium carbonate

sandwiched by a very fine protein layer. This protein layer acts as
glue to hold the layers (similar to cement) in a brick-cement
structure.

Correspondingly, the fracture toughness of the nacre exceeds 1000

times the toughness of calcium carbonate (a very brittle material).

Hence rearrangement and gluing by protein nano-layer can

drastically enhance the fracture toughness while retaining its
hardness.
Thank You
 MECHANICAL PROPERTIES
Classic Mechanical Properties

 Tensile test
Determination of mechanical properties

Stress: σ = F/S

Strain: ε = Δl / l0

Tensile strength = Stress/strain

3
 Tensile Test curve
Stress, σ (Mpa)

Max stress : tensile strength Necking

Max elasticity: Yield strength Fracture

Strain, ε (%)
Elastic Plastic
deformation deformation

Young modulus (Modulus of elasticity): Ratio of stress to the strain in the linearly
elastic region
 Mechanical properties
Yield strength: maximum stress before permanent strain

Tensile strength: maximum stress

Ductility: measure of deformation (Lf – Lo)/ Lo

Toughness: ability to absorbe energy: area under curve

Hardness

Resistance to plastic deformation

Measure of depth or size of indentation

4
Mechanical properties of nanomaterials compared
to coarse grain materials

Higher Young modulus and tensile strength (to

4 times higher)

Lower plastic deformation

More brittle

6
 Elongation nanostructured materials

Elongation decreased

Lower density of mobile dislocations

Short distance of dislocation movement

Strength and Hardness with grain size

 Strength and Hardness of nanostructured material

increases with decreasing size

 Grain boundaries deformation

surface area of nanocrystals