:Fabrication and Applications

What do you mean by the term “nano”?

1 µm= 10-6 m
1 nm= 10-9 m
Similarly
1 µL= 10-6 L
1 nm= 10-9 L
And
1 µg= 10-6 g
1 ng= 10-9 g
 Nanoscience
Definition: Nanoscience is the study of structures, properties, and
application of materials on the scale of nanometers.

Importance: Nanoscience has already impacted our lives with innovations.

Scientists and engineers from several disciplines including physics,
chemistry, biology and materials science use nanoscience principles for
advanced applications in energy, medicine, information storage, computing
and elsewhere.
 Terms
Nanoscale – The size range roughly 1 to 100 nanometers, where many of the
fundamental structures of biology are formed, composite materials may take
on their distinctive characteristics, and many important physical phenomena
are found.

Nanoscience – The study of unique properties of matter at the nanoscale; an

interdisciplinary field of science combining physics, materials science, the
chemistry of complex molecules, and related disciplines.

Nanotube – Hollow, cylindrical structures, with a diameter usually less than

5 nanometers. They are often but not necessarily, composed of carbon,
and having remarkable strength and electrical properties.
 Terms

Colloid - Nanoscale or microscale particles suspended in another medium;

colloids include gels, aerosols, and emulsions.
 Terms
Carbon nanotube (CNT) - Carbon molecule with a cylindrical shape. The
structure and chemical bonds of CNTs result in unique strength, electrical,
and thermal properties.
 Terms
Nanocomposite – A material composed of two or more substances, of which at
least one has a nanoscale dimension, such as nanoparticles dispersed
throughout another solid material.
Self-assembly – A process in which a given nanostructure spontaneously
constructs itself, generally limited to very specific structures in chemical
environments precisely defined in order to promote self-assembly.
Quantum dot – A nanoscale crystal with a diameter that is typically between 2-
20 nm, having unique electrical and optical properties that are dependent
on its size.
They are finding commercial applications in new light sources, enhanced
medical imaging, and being explored as components in spintronic quantum
computers, and has a very wide range of potential scientific and industrial
applications.
Nanosensor – A device for sensing radiation, forces, chemicals, or biological
agents, in which some portion of a device operates at the nanoscale, for
example, by having receptors into which the particular molecules to be
sensed fit.

Nanoparticles Nanocubes Nanotubes Nanocrystals Nanoemulsion

Diffusion: Diffusion is the net movement of molecules or atoms from a region
of high concentration (or high chemical potential) to a region of low
concentration (or low chemical potential). This is also referred to as the
movement of a substance down a concentration gradient.
Definition: In general, a colloid is a
system consisting of one substance
(the dispersed phase: a solid, liquid,
or gas) finely divided and distributed
evenly (relatively speaking) throughout
a second substance (the dispersion
medium or continuous phase: a solid,
liquid, or gas).
Terms related to colloids:
Coagulum: An aggregate of colloidal particles having a relatively
tight, dense structure, normally formed irreversibly.

Coagulation: The process of forming coagulum.

Creaming: The separation of coagulum or flocs from the continuous

phase, where the aggregate is less dense than that phase.

Floc: An aggregate of colloidal particles that have a rather loose,

open structure (related to coagulum) may be reversible to the
dispersed state with minimal energy input.

Flocculation: The process of forming flocs.

Monodisperse: Particles in the colloidal system have approximately
same size.

Polydisperse: A broad range of particle sizes.

Sedimentation: As in creaming except that the aggregates are denser

than the liquid and settle to the bottom.
Colloid Size: The size of dispersed phase falls in the range of 1~1000nm.
However, many systems with dimensions beyond that range (emulsions,
paints, aerosols)

Colloidal stability: The stability of a colloidal system is defined by

particles remaining suspended in solution at equilibrium. Stability
is hindered by aggregation and sedimentation phenomena, which
are driven by the colloid's tendency to reduce surface energy.
Lyophilic and lyophobic sols

●Sols (lyosols) are dispersed colloidal particles in a liquid

medium (=solid/liquid dispersions)
●These sols can be
●Lyophilic : strong interactions exist between the particles and the
solvent (the particles are wetted)
–Thermodynamically stable
●Lyophobic: little or no interactions between the particles and the
solvent (partially wetted or unwetted particles)
–Thermodynamically unstable
–Can be kinetically stable or unstable
 Stability of colloids
● Solutions are thermodynamically stable if Gibbs energy of the components
before mixing is higher than after mixing (ΔG<0)
●Dispersions are thermodynamically unstable if the Gibbs energy increases by
mixing (ΔG>0)
●But if unmixing is slow enough → kinetically stable dispersions
 Stability of colloids

In an unstable system the particles may adhere to one another and form
aggregates of increasing size that may settle out under the influence of
gravitational force. An initially formed aggregate is called a floc and the process
of its formation flocculation. The floc may or may not separate out. If the
aggregate changes to a much denser form, it is said to undergo coagulation. An
aggregate usually separates out either by sedimentation (if it is more dense
than the medium) or by creaming (if it less dense than the dispersion medium).
The term’s flocculation and coagulation have often been used inter-changeably.
Usually coagulation is irreversible whereas flocculation can be reversed by the
process of deflocculation.
 Coagulation or flocculation

a)The suspended particles settle out and form a firm, dense mass (cake). The
cake can not be re-dispersed by gentle agitation.
b)The suspended particles form light, fluffy agglomerates held together by
strong van der Waals forces.
The flocculated particles settle rapidly forming a loosely adhering mass with a
large sediment height. Gentle agitation will easily resuspend the particles.
Weak flocculation requires strong adhesion and a zeta potential of almost
zero.
 Strength of inter particle forces

Encounters between particles occur as a result of

Brownian motion and stability of a suspension is
determined by the interaction between particles
during these encounters. Stability depends on the
balance of attractive and repulsive interactions. There is no repulsion
Attraction comes from van der Waals forces
between particles. Repulsion is a consequence of
interaction between similarly charged electric
double layers and/or particle-solvent affinity.
Repulsion prevents particles to get close enough
and attach.
There is repulsion
 Stability of lyophobic sols
●Lyophobic sols are thermodynamically unstable

●However there are stabilizing factors → kinetical stability can be attained

●Whether aggregation does or does not occur depend of the balance of

attractive and repulsive forces
⃗F=⃗FA+⃗FR

●For stabilization to occur, the repulsive forces must dominate

Electrostatic and steric stabilization
 DLVO Theory
• The study of colloidal stability is based on the DLVO theory, in honor of Boris
Derjaguin, Lev Landau, Evert Verwey, and Theodor Overbeek.
• what? The theory describes the force between charged surfaces interacting
through a liquid medium: it combines the effects of the van der Waals
attraction and the electrostatic repulsion due to electrical double layers.
The theory explains the aggregation of aqueous dispersions quantitatively and
describes the force between charged surfaces interacting through a liquid
medium.
•why: The DLVO theory is used to examine the dependence of colloid stability
on the various parameters that determine the shapes and the magnitudes of
interaction energies between particles.
The interactions between two colloidal particles with electrical double
layers can be visualized as two blocks connected by a spring. At large
distances of separation the spring is stretched and applies a net force
pulling the blocks together (attractive van der Waals interactions). At close
approach, the spring is compressed producing a net repulsive force pushing
the blocks apart (electrostatic repulsion). At some intermediate distance,
the forces will be in equilibrium.
Balance of attraction and repulsion (DLVO theory)
Van der Waals attraction will predominate at small and at large interparticle distances. At
intermediate distances double layer repulsion may predominate, depending on the actual
values of the forces. In order to agglomerate, two particles on a collision course must have
sufficient kinetic energy due to their velocity and mass, to “jump over” this barrier.
 Electrostatic stability of dispersions

Ionic strength: I1 < I2 < I3 < I4 < I5

Inverse Debye length: κ1 < κ2 < κ3 < κ4 < κ5

An increase in electrolyte concentration leads to a compression of the double layer (κ

increase) and so the energy barrier to coagulation decreases or disappears. If the barrier
is cleared, then the net interaction is all attractive, and as a result the particles coagulate.
This inner region is after referred to as an energy trap since the colloids can be considered
to be trapped together by van der Waals forces.
 Critical Coagulation Concentration
What concentration of salt (n0) eliminates the repulsive barrier?

If the potential energy maximum is large compared with the thermal energy, kT
of the particles, the system should be stable; otherwise, the system should
coagulate.
C. C. C. is the concentration of salt that just eliminates the repulsive barrier
The Schulze–Hardy Rule:
The critical coagulation concentration (c.c.c.) inversely depends on the sixth power
of the charge on the ions.
c.c.c (in mol/l) ~ z-6
c monovalent : c divalent : c trivalent
1 : 2-6 : 3-6 = 1 : 0.015 : 0.0014

Fast coagulation: If no barrier to particle approach (said to be non interacting),

the coagulation process is equivalent to a reaction with zero activation energy.
The rate of coagulation will be controlled by diffusion kinetics.

Slow coagulation: Some energy barrier to particle contact exists. Analogous to a

bimolecular reaction in which there is a substantial activation energy.
 Electrostatic repulsion between EDLs
∆GT = ∆GA + ∆GR
• The key element in determining the height of the energy barrier imposed by
the electrical double layer is the concentration and valence of electrolyte in the
system

• An increase in the electrolyte concentration reduces the repulsive

electrostatic interaction, reducing the energy barrier and facilitating effective
particle collisions - nanoparticles in the system tend to aggregate.

• A good approximation to the point at which the system will begin to undergo
rapid coagulation indicating a loss of stability.
Steric Stabilizer
The stabilizing polymer must
be in a good solvent environment
 Bridging Flocculation
Good adsorbent, good solvent, (very) low polymer density, (very) long
polymers. The long polymers ‘bind’ the colloids together in open flocs.

In general, a higher-molecular weight material can be expected to provide better

protection against flocculation. (longer chains imply longer loops and tails, and thicker
protective layer). However, a very high molecular weight may lead to sensitization and
bridging flocculation.
Reason: when there is more than one attachment point, it is possible that various
attaching points will encounter two (or more) different particles and ties them together
 Depletion Flocculation

✓ As two particles approach, such polymer molecules are squeezed out of

the area of closest approach, leaving “bare” surfaces.
✓ There may arise an additional attractive force caused by osmotic balance. -
---- As polymer is forced out, the concentration of polymer between
particles is less than in the bulk. Osmosis then forces solvent to flow from
between the particles out into the solution.
 Solvent Effect in Steric Stabilization
✓ If the solvent becomes a better solvent for the monomer units acting as
anchors, the chains may be more weakly adsorbed.---- decrease stability.
✓ If the solvent is changed from a “good” to a “poor” solvent for the loops
and tails, the thickness of the protective layer will be reduced (polymer
chains collapse on the particle surface). ----reduced stability.
The solubility of polymer in a given solvent is a function of temperature.

In a “good” solvent, polymer chains extend in open and random-coil

configuration, given optimum protective layer thickness.
The θ point: The temperature at which the solvent changes from “good” to
“poor” properties.
Critical flocculation temperature: the temperature at which the colloidal
stability changes from good to bad.
 Synthesis of Nanomaterials
1. Top-down
Attrition/Milling: Generally, mechanical milling is meant as grinding or reducing
powders of pure metals or intermetallic compounds. Conventional milling in a
ball mill provides low mechanical energy, which adequately disintegrates large
particles into small particles (10-1000 nm). However, their crystalline structure
does not change. When milling in a high-energy ball mill the impact energy is
1000-fold higher, so it induces rapid changes of phases and chemical reactions
just at ambient temperature.
Severe plastic deformation (SPD) processing: Severe plastic deformation (SPD) is
a generic term describing a group of metalworking techniques involving very
large strains typically involving a complex stress state or high shear, resulting in
a high defect density and equiaxed "ultrafine" grain (UFG) size (d < 500 nm) or
nanocrystalline (NC) structure (d < 100 nm)
 2. Bottom – up:
Via
- Pyrolysis
- Inert gas condensation
- Solvothermal Reaction
- Sol-gel Fabrication
- Structured Media

Phase Classification:
I. Gas (Vapor) Phase Fabrication: Pyrolysis, Inert Gas
Condensation, ….
II. Liquid Phase Fabrication: Solvothermal Reaction, Sol-gel,
Micellar Structured Media
Example: Aerosol Spray Methods (e.g., Spray Pyrolysis)
Mechanism:
(i) precursor vaporization
(ii) nucleation, and
(iii) growth stage

Effectiveness: simple process, low cost, continuous operation, high yield

Gas/Vapor phase synthesis
Gas-phase synthesis is a class of bottom-up method for
producing nanoparticles (NPs) from individual atoms or
molecules.
It is a bottom-up process in which individual atoms, ions, and
molecules condense together to form NPs.
Spray pyrolysis
 Specific example of spray pyrolysis
GaN nanoparticles synthesis
Ga(NO3)3 + H2O
and LiCl
 Inert Gas Condensation(IGC)

The inert gas condensation technique consists of evaporating a metal (by

resistive heating, radio-frequency heating, sputtering, electron beam heating,
laser/plasma heating, or ion sputtering) inside a chamber that was evacuated to
a very high vacuum of about 10–4 Pa and then backfilled with a low pressure
inert gas, typically a few hundred Pascals of helium. The evaporated atoms
collide with the gas atoms inside the chamber, lose their kinetic energy, and
condense in the form of small, discrete crystals of loose powder. The crystal size
of the powder is typically a few nanometers and the size distribution is narrow.

The crystal size is dependent upon the inert-gas pressure, the evaporation rate,
and the gas composition. Extremely fine particles can be produced by decreasing
either the gas pressure in the chamber or the evaporation rate and by using light
gases such as He rather than heavy inert gases such as Xe.
Inert Gas Condensation(IGC)

Indium antimonide (InSb)

 Liquid phase synthesis methods
• Solvothermal Methods
(e.g. hydrothermal)
• Sol-Gel Methods
• Synthesis in Structure Media
(e.g., microemulsion)
General Mechanism:
 Solvothermal/Hydrothermal process
Precursors are dissolved in hot solvents (e.g., n-butyl alcohol)
- Solvent other than water can provide milder and friendlier reaction conditions
If the solvent is water then the process is referred to as hydrothermal method.
A “solvothermal reaction can be defined as a chemical reaction (or a
transformation) between precursor(s) in a solvent (in a close system) at a
temperature higher than the boiling temperature of this solvent and under high
pressure”

→ Autogeneous pressure or imposed pressure.

→ Subcritical or supercritical domain.
→Homogeneous or heterogeneous system.
Hydrothermal/solvothermal Hydrothermal synthesis: H2O, temperatures above
100˚C.
Other solvents: NH3, HF, HBr, Cl2, HCl, CO2, SO2, H2S, CS2, C2H5OH, CH3NH2,
CH3OH, HCOOH.
NH3 is a common solvent (ammonothermal)) and carbon dioxide is becoming
important.

1. Hydrothermal crystallization of large crystals and gem stones (Iron oxide

nanocrystals).
2. Hydrothermal synthesis of e.g. powder samples of oxides (e.g. zeolites)
3. Hydrothermal leaching (e.g. for treatment of ores).
Synthesis usually in closed vessels, so temperature-pressure-volume
considerations are crucial.

Starting materials (solution, slurry, gel, sol) placed in a sealed autoclave Heated
to the desired reaction temperature. Reaction and formation of product (usually
by dissolution/precipitation) Formation of barium titanate at (150-250˚C)

Ba(OH)2(aq) + TiO2 BaTiO3(s) + H2O

•Isothermal: Mainly for powder synthesis

•Temperature gradient: Generally formation of larger crystals
 Sol-Gel method
The sol-gel process is a more chemical method (wet chemical method) for the synthesis
of various nanostructures, especially metal oxide nanoparticles. In this method, the
molecular precursor (usually metal alkoxide) is dissolved in water or alcohol and
converted to gel by heating and stirring by hydrolysis/alcoholysis.
Sol-Gel method
Sol-Gel method
Micro-emulsions are stable transparent dispersions of water and oil (mixture of various
hydrocarbons and olefins) and surfactant. They are prepared by simple mixing of the
components and do not require specific preparation conditions.