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.

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

[1] https://www.sciencedirect.com/science/article/pii/B9780128137413000388

[2] https://blog.iglcoatings.com/how-liquid-works-with-hydrophobic-
hydrophilic-surfaces/
 [3] https://www.slideshare.net/JigyashaBhatt/targeted-drug-delivery-system-
94064136

[4] https://www.livescience.com/49515-water-repellent-material.html

[5] https://www.allaboutvision.com/lenses/coatings.htm

[6] https://www.sciencedirect.com/topics/engineering/quantum-confinement-
effect

[7] https://www.edn.com/thick-and-thin-quantum-wells-dramatically-affect-
cyan-led-bandwidth/

[8] https://www.edn.com/thick-and-thin-quantum-wells-dramatically-affect-
cyan-led-bandwidth/

[9] https://www.pharmaceutical-business-review.com/products/oral-thin-films-
drug-delivery/

[10] https://commons.wikimedia.org/wiki/File:Quantum_wire.jpg

[11] https://www.youtube.com/watch?v=wsWD5dJv2OE

[12]https://commons.wikimedia.org/w/index.php?search=quantum+dot&title=S
pecial%3ASearch&go=Go&ns0=1&ns6=1&ns12=1&ns14=1&ns100=1&ns106
=1#/media/File:Quantum_dot_schema.jpg

[13]https://www.indiamart.com/proddetail/carbon-fullerenes-13710958673.html

References

1. https://www.hindawi.com/journals/bmri/2014/498420/
2. https://link.springer.com/chapter/10.1007/978-3-319-09171-6_8
3. https://www.circuitstoday.com/nanomaterials
4. https://maken.wikiwijs.nl/bestanden/427519/Lesson_7_APPENDIX-
2_Article2.pdf
5. https://www.sciencedirect.com/science/article/pii/S1878535217300990

Video link

1. https://www.youtube.com/watch?v=RvtlBh_-_Rw
2. https://www.youtube.com/channel/UCa1LT1sfzVGP6grvbfcqUjQ
3. https://www.youtube.com/watch?v=5lvjo0rm-F0
4. https://www.youtube.com/watch?v=WElm-VglY7s
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.