LECTURE 2
This topic is mapped with CO3 and CO4 of the course
Properties of nanomaterials
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 impediment to dislocation motion (dislocation 'pileup
mechanism- the usually accepted mechanism!). But when grain size reduces to tens of
nanometres (< 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. They are even reporting in literature of decreasing strength with decreasing grain
size at very small grain sizes (< 5 nm).
Giant Magnetoresistance
Giant magnetoresistance is the dramatic decrease in the electrical resistance on the
application of magnetic field, in an otherwise antiferromagnetic hybrid. Giant
magnetoresistance is seen in a hybrid consisting of a non-magnetic- nano-film placed
between ferromagnetic layers. In the absence of external magnetic fields the magnetic
layers are anti-ferromagnetically coupled. The resistance of this state is very high. On
application of a magnetic field, the spin vectors in the ferromagnetic layer tends to align in
parallel leading to a drastic reduction in resistivity.
Superparamagnetic
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.
Figure 1: hysteresis curve for different magnetic materials
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
super hydrophobicity; 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 super
hydrophobicity can lead to the development of non-wetting clothes, self-cleaning windows,
non bio-fouling surfaces etc.
Figure 2: Modelling super hydrophobicity surface
Super surface activity
With decreasing dimension of the particles, the number of surface atoms increases
drastically (calculation shown later in an example). 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.
Targeted drug delivery
Nanoparticles can be loaded with specific sensor and drug molecule(s). The drug can be
transported to the required site through blood stream. On detection of the affected
tissue/cells/area by the functionalized surface group the drug is released locally on desired
target (targeted drug delivery).
Figure 3: target drug delivery system [3]
Achieving superhydrophobic/antibiofouling surfaces
Nanoscale surface roughness enhances material properties like hydrophilicity or
hydrophobicity, which is otherwise unattainable (by exploring different materials). The
phenomenon of super hydrophobicity relies on achieving Cassie Baxter state (allowing
support of water droplet on nano-roughness, without actually wetting the entire surface).
Correspondingly, these water-repelling surfaces do not allow fungal/algae growth on their
surfaces by rejecting water deposition on their surface.
Figure 4: water bounces off from water repellent surface [4]
Rapid catalysis
Surface activity of nanoparticles enhances multifold (few orders of magnitude) because of
two reasons: (i) the surface area available to react increases as we go down in size, and (ii)
the unsatisfied bonds lead to instability of nanoparticle itself. Hence the synergistic
combination of enhanced surface with high energetic associated with nanoparticles
enhances their catalytic activity dramatically.
Functionalization
Functionalization is the addition of one (or more) functional groups on the surface of a
material (or particles). Usually this surface modification is achieved by chemical synthesis
methods to impart certain properties to the surface (e.g enhance affinity of surface for a
particular species or make the surface water repellent). It is easier to functionalize
nanoparticles as they possess higher surface activity. Functionalized nanoparticles find
applications in rapid catalysis, targeted drug delivery, sensors etc.
Nano porous membrane filters
Membrane filters sieve out harmful bacteria and are permeable only to the molecules which
can pass through the nano-porous membrane. These are utilized in the filtering of water to
get bacteria-free water.
Non-wetting clothing
Non-wetting clothes have been developed by coating nanoparticles on the fabric. If you spill
coffee on your trousers made of such a material, it will just flow away without leaving a
stain. This layer of nanoparticles is transparent and is invisible to eye!
Scratch resistant lenses
Nanometre sized alumina particles can be used as a feedstock for thermal spraying or spark
plasma sintering to form fully dense pellets of transparent ceramic. These optical
components being made of a ceramic provides for superior strength, hardness and thermal
shock resistance as compared to their glass/plastic counterparts. Wear resistant optical
components can be utilized in aerospace applications.
Figure 5: scratch resistant coating on glasses [5]
Spin Valves
Spin valves essentially utilizes the giant magnetoresistance (GMR) effect. An applied
magnetic field can be used to switch the material showing GMR effect from a high
resistance state to a low resistance state. This makes these devices behave as ‘spin valves’
or micro-switches. Spin valves have been used in the fabrication of spin valve transistors
(using silicon emitter and collector), which can be used in the detection of magnetic fields.
Properties of Nanomaterials
1. Large Surface Area-to-Volume Ratio
• As particle size decreases to the nanoscale, a large fraction of atoms are on the surface.
• Effect: Increased reactivity, catalytic efficiency, and surface energy.
2. Quantum Size Effects
• Electrons are confined in very small dimensions, altering the material’s electronic and optical properties.
• Effect: Changes in color, fluorescence, and conductivity compared to bulk material.
3. Enhanced Mechanical Strength
• Many nanomaterials have higher hardness and tensile strength due to fewer defects and grain boundary
strengthening.
Example: Carbon nanotubes have tensile strength ~100× greater than steel.
4. Optical Properties
• Nanoparticles interact differently with light because of surface plasmon resonance (SPR).
• Effect: Unique colors in gold/silver nanoparticles; UV blocking in nano-TiO₂.
5. Thermal Properties
• Nanomaterials can have higher or lower thermal conductivity than their bulk form.
• Example: Carbon nanotubes conduct heat extremely well, while nanostructured ceramics may have
reduced conductivity.
6. Electrical Properties
• Quantum confinement and high surface scattering can change conductivity.
• Effect: Some nanowires show metallic behavior, while others become semiconducting
7. Magnetic Properties
• Below a critical size, magnetic nanoparticles can exhibit superparamagnetism.
• Effect: Magnetic response only in an external field, useful in medical imaging (MRI contrast agents).
8. Chemical Reactivity
• Increased surface atoms and defects lead to higher chemical reactivity.
• Example: Nanocatalysts in fuel cells, pollution control.
9. Reduced Defects
• Small size often means fewer internal dislocations and voids.
• Effect: Improves strength and durability.
10. Tailorability
• Properties can be tuned by controlling size, shape, and surface functionalization.
• Example: Drug delivery nanoparticles modified for targeted release.
Unusual behaviour of nanomaterials
Surface to volume ratio
The surface area to volume ratio for a material or substance made of nanoparticles has a
significant effect on the properties of the material. Firstly, materials made up of
nanoparticles have a relative larger surface area when compared to the same volume of
material made up of bigger particles.
For example, let us consider a sphere of radius r .
The surface area of the sphere will be 4πr 2
The volume of the sphere = 4/3πr 3
Therefore the surface area to the volume ratio will be 4πr 2 /(4/3πr 3 ) = 3/r
It means that the surface area to volume ratio increases as the radius of the sphere
decreases and vice versa. It also means that when a given volume of material is made up of
smaller particles, the surface area of the material increases. Therefore, as particle size
decreases, a greater proportion of the particles are found at the surface of the material. For
example, a particle of size 3 nm has 50% of its particles on the surface; at 10 nm, 20% of its
particles are on the surface; and at 30 nm, 5% of its particles are on the surface. Therefore,
materials made of nanoparticles have a much greater surface area per unit volume ratio
compared with the materials made up of bigger particles. This leads to nanoparticles being
more chemically reactive. As chemical reactions occur between particles that are on the
surface, a given mass of nanomaterial will be much more reactive than the same mass of
material made up of large particles. This means that materials that are inert in their bulk
form are reactive when produced in their nanoparticle form.
Electron/Quantum confinement
Electron confinement or quantum confinement is another process that occurs in
nanoparticles. We know that when atoms are isolated, then their energy levels are discrete
but when they are in packed form and in large numbers (in solid form), the energy levels
split and form bands (band means group of levels). Nanoparticles represents intermediate
stage.
As we have discussed the problem of particle in a box that when the dimensions of such box
is of the order of the de Broglie wavelength of electrons or mean free path of the electrons,
then the energy levels of the electrons change. This process is called electron confinement
or quantum confinement. This process results from the electrons and holes being squeezed
into a dimension that approaches a critical quantum measurement known as excit or Bohr
radius. It can affect the electrical, magnetic and optical properties of nanoparticles.
Figure 6 : change in the energy level from continuous to discrete state [6]
Types of nano materials
Figure 7 : differentiate nano-materials on the basis of dimensional [7]
Quantum well / 2 D dimensional nanomaterials
A quantum well is a potential well with only discrete energy values.
The classic model used to demonstrate a quantum well is to confine particles, which were
initially free to move in three dimensions, to two dimensions, by forcing them to occupy a
planar region. The effects of quantum confinement take place when the quantum well
thickness becomes comparable to the de Broglie wavelength of the carriers
(generally electrons and holes), leading to energy levels called "energy sub bands", i.e., the
carriers can only have discrete energy values.
If one dimension is reduced to the nano-range while the other two dimensions remain large,
then we obtain a structure known as quantum well. This reduction in dimension produces
confinement of the electrons that also refers to the number of degrees of freedom in the
electron momentum.
Figure 8: squeezing one length into nano-meter [8]
Example thin films
Figure 9: quantum well- thin film [9]
Quantum wire/ 1 Dimensional nanomaterials
If two dimensions are reduced (confined) and one remains large, the resulting structure is
referred to as a quantum wire.
Figure 10: squeezing 2 dimensions into nano sizes [10]
For example. Carbon nanotubes
Figure 11: carbon nanotube [11]
Quantum dot
The last case is the reduction or the confinement in all three dimensions is called a quantum
dot.
Figure 12 squeezing all three dimensions in nano sizes [12]
For example, fullerenes
Figure 13: fullerenes [13]
Summary
• Nanomaterials can be used to produce giant magnets
• Nano materials behave like super hydrophobicity.
• They behave like super paramagnetic.
• They can use a target medicines to many deceases.
• They help in making water resistant surfaces, non-wetting cloths.
• If one dimension is reduced to the nano-range while the other two dimensions remain large,
then we obtain a structure known as quantum well.
• If two dimensions are reduced (confined) and one remains large, the resulting structure is
referred to as a quantum wire.
• The confinement in all three dimensions is called a quantum dot.
Practice questions
1. Differentiate nanomaterials on the basis of confinement of dimensions.
2. Enlist some properties of nano materials.
3. What you under by quantum confinement. How it effects properties of nano materials?
4. How surface to volume ratio increases with decrease in size?
Image reference
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bandwidth/
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bandwidth/
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delivery/
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earch&go=Go&ns0=1&ns6=1&ns12=1&ns14=1&ns100=1&ns106=1#/media/File:Quantum_
dot_schema.jpg
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References
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Video link
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Books
Sahni V., Goswami D. (2008) Nano Computing, McGraw Hill Education Asia Ltd., ISBN:
978007024892
Beiser A., Ghatak A, Garg S.C., Applied Physics, Edition 1st, (2013), Tata McGraw-Hill, Noida.