Nanomaterials

Nanoparticles
The word ‘ nano’ is to a Greek prefix
meaning dw arf or something very
small and depicts one billionth
(𝟏𝟎 −𝟗 ).

Nanomaterials may be classified as

those materials w hich have at least
one of their dimensions in the
nanometric range , below which there
is significant variation in the property
of interest compared to
microcrys talline materials .

Par ticles with size ranging from

𝟏 𝒏𝒎 − 𝟏𝟎𝟎 𝒏𝒎
✓ Carbon black is a nanostructured material that is used in car tyres to
increase the life of the tyre and impart black colour. This material was
discovered in the 1900s.

✓ Steel (an alloy of iron and carbon). In year 2006, scientist found the
presence of carbon nanotubes in an ancient Damascus sabre. This
finding has surprised scientists. People now believe that the high
strength of these steels may be due to the presence of these carbon
nanotubes, which are known for their exceptionally large Young’s
modulus.

Prepared by Dr. Yeap Swee Pin

Fullence

A fullerene is an allotrope of
carbon whose molecule consists
of carbon atoms connected by single and
double bonds so as to form a closed or
partially closed mesh, with fused rings of
five to seven atoms.
 Carbon nanotubes
Carbon nanotubes are cylindrical fullerenes. These tubes of carbon are usually
only a few nanometres wide, but they can range from less than a micrometer to
several millimeters in length. They often have closed ends, but can be open-
ended as well.

Carbon nanotubes (CNTs) were first observed by Iijima in 1991 and are
characterized by their nanosized hollow tube -shaped structures.
Single-walled carbon nanotubes (SWCNTs) consist of single
graphene layer with diameter varying between 0.4 and 2 nm and
usually occurs as hexagonal-packed bundles. Multi-walled
carbon nanotubes (MWCNTs) comprises of two or several
cylinder, each made up of graphene sheets. The diameter varies
from 1 to 3 nm Both SWCNTs and MWCNTs are popular
nanomaterials for commercial applications and widely used in
fuel cell designs, photovoltaics, and biomedicine
CNTs exhibit excellent chemical and physical properties such as
high tensile strength, ultra-light weight, special electronic structures
and high chemical and thermal stability.

The main applications of carbon nanotube include biomolecule, drug,

and drug delivery to the targeted org ans, biosensor diagnostic and
analysis [10] .

Carbon nanotubes are utilized in energy storage, device modelling,

automotive parts, boat hulls, sporting goods, water filters, thin -film
electronics, coatings, actuators, and electromagnetic shields.
Nanoparticles NOT necessary in
spherical shape!

Nanotubes Nanowires Nanoflowers

Nanostars
Nanorings

Nano prisms Nanoro Nanohelix

d
2.3 Effect of grain size on magnetic properties

b. Electrical Properties
Nanomaterials can hold considerably more
energy than conventional coarse-grained materials
because of their large grain boundary (surface)
area.
Provide 3 example
of nanoparticles
used in battery.

1.
Fig. The energy density (storage capacity)
of conventional batteries is usually quite
2. low, requiring frequent recharging.
Nanocrystalline materials are good
3. candidates for separator plates in
batteries because they can hold
considerably more energy than
conventional ones.
2.3 Effect of grain size on thermal properties

c. Thermal Properties

Concept:
Smaller particle size
phonon is a quantum of energy

Increase grain boundaries area

Better/Poorer phonon
scattering?

High/Low thermal conductivity?

So we can use nanoparticles as

insulator or thermal conductor?
2.3 Effect of grain size on optical properties

d. Optical Properties
Different sizes of nano-gold Bulk gold

Vs.

Do you notice something?

Smaller nanospheres : Absorb light and have peaks near 520 nm,
Larger nanospheres : increased scattering and have peaks at longer wavelengths

Special
case

Unaggregated aggregated
Define Magnetophoresis:

Define Cooperative Magnetophoresis:

Define Non-cooperative Magnetophoresis:

Cooperative Magnetophoresis Non-Cooperative Magnetophoresis

Fast/slow? Fast/slow?
radius

radius
Synthesize methods

Bottom up & top down methods

Top Down approach

-Concept
The top-down approach often uses
the traditional workshop or
microfabrication methods where
externally controlled tools are used
to cut, mill, and shape materials
into the desired shape and order.
Anything also can be cut & milled into
Nanosize!

M.E.H.A

1. Mechanical
Alloying/Milli
ng
2. Equal
channel
angular
pressing
3. High Nanopowder
Pressure
Torsion
4. Accumulativ
e roll bonding
 TopDown approach: Mechanical
Alloying/Milling
Mechanical alloying or milling is usually carried out in high-energy
mills such as:
√ Vibratory mills √ Planetary mills √
Attritor mills.
Vibratory mills Planetary mills Attritor mills

The vibratory mill has one vial,
containing the sample and
grinding balls and vibrates in
all three directions.
Because of the amplitude
(about 50 mm) and speed
(about 1200 rpm), the ball
velocities are high (in the order
of 5 m/s) and consequently
the force of the ball’s impact is
unusually high.
The vials rotate around their
own axes while the support disk
rotate in opposite direction.
Such an opposite rotation
Consist of a stationary
causes the centrifugal forces drum with a rotating
alternately act in opposite
impeller, particle
directions. breakdown due to the
Due to this, the balls run down
impact between balls,
and lifted off alternately and between balls and the
apply strong impact on the container wall, and
sample. between balls, the agitator
shaft and impellers.
 TopDown approach: Equal channel
angular pressing
How it works?
✓ The ECAP consists of a die and a
plunger.

✓ The internal channel of the die is

bent through an abrupt angle, φ,
equal to 90°.

✓ The sample is PRESSED through

the die by using the plunger.

✓ Shear deformation occurs as

the sample passes.

✓ The process is repeated until the

grain size is reduced.
 TopDown approach: High
Pressure Torsion

HPT HPDT

Normally used to produce disc-type nanostructured

 TopDown approach: Accumulative
roll bonding

❖ Rolling is the most advantageous metal working process

for continuous production of plates, sheets and bars.

❖ However, the total reduction applied to the materials is

substantially limited because of the decrease in the cross-
sectional dimension of the materials with increasing
reduction.
 The Top-Down Method to synthesis
Nanoparticles

M.E.H.A

1.Mechanical
Alloying/Milling
2.Equal channel
angular
pressing
3.High Pressure
Torsion
4.Accumulative
roll bonding
Bottom up approach

-Concept
Starts from precursor, the BottomUp method helps
to synthesis nanoparticles.
Interesting to note that the precursor can be
liquid or gaseous materials!

C.S.S.P.C

1. Chemistry
method (Wet)
2. Sol-gel
method.
3. Spray
conversion
method.
4. Physical Vapor
deposition
(PVD). Nanoparticles
5. Chemical
Vapor
deposition
(CVD).
 BottomUp approach: Co-precipitation
method
How it works? Adding in
precipitator as
reducing agent
Chemical (eg. NaOH, KOH, Purified the This
Well-mix these
precursors are ammonia, sodium precipitated precipitated
precursors (by
prepared! (in borohydrite and solid solid is your
stirring).
chloride, sulfate,
etc.) nanoparticles!
oxalates forms)

Example: It will precipitate

all the precursors
simultaneously.

FeCl2
+

FeCl3 Fe2+ + 2 Fe3+ + 8OH- → Fe3O4 + 4H2O

BottomUp approach: Sol-Gel
method
What is a Sol-gel
R-OMe or Me salt
process?

+H2O Stabilizer Sol-gel process

consists in the
Nano-dispersed chemical
Sol transformation of a
- H2 O liquid (the sol) into a
gel state and with
subsequent post-
Gel
treatment and
transition into solid
- H2 O
- Solvent (ROH oxide material.

Xerogel
- H2 O

Dense gel
BottomUp approach: Spray conversion
method
✓ This route involves the atomization of chemical precursors into aerosol
droplets.
✓ The aerosol droplets is then dispersed throughout a gas medium.
✓ The aerosols are then transported into a heated reactor where the
solution is evaporated to form ultrafine particles or thin films.

UCSI
 BottomUp approach: Physical Vapour
Deposition (PVD)

1. PVD is a process whereby material in

solid/liquid phase are first converted to vapour
phase.

How How How? Via physical processes such as

evaporation, sputtering or laser ablation.

2. The generated vapour atoms will travel

through a space and reach to the wafer.

3. The vapour atoms will deposited onto the

wafer to form a coating layer.

4. This coating layer is the nanoparticles.

 BottomUp approach: Chemical Vapour
Deposition (CVD)

Chemical vapour deposition (CVD) is a process where one or more gaseous

adsorption species react or decompose on a hot surface to form stable solid
products. The main steps that occur in the CVD process can be summarized as
follows:
1. Transport of reacting gaseous species to the surface
2. Adsorption of the species on the surface
3. Heterogeneous surface reaction catalysed by the surface
4. Surface diffusion of the species to growth sites
5. Nucleation and growth of the film
6. By-products from the chemical reaction being removed.
UCSI
 Summary of PVD and CVD

Whether it is via CVD or via PVD, the end result is basically the
same as they both create a very thin layer of material depending on
the desired thickness. CVD and PVD are very broad techniques
with a number of more specific techniques under them. The actual
processes may be different but the goal is the same. Some
techniques may be better in certain applications than others
because of cost, ease, and a variety of other reasons; thus they are
preferred in that area.

1.PVD uses physical processes only while CVD

primarily uses chemical processes

2.PVD typically uses a pure source material while

CVD uses a mixed source material
 Reactor for synthesis of Nanoparticles
1. Batch Reactors A batch reactor is a vessel that has no input or
output during the time reaction proceeds. The
reactants are loaded into the reactor at the
beginning of the operation and the reaction is
allowed continuing for a predetermined time, and
finally, the products are discharged.
Example: Synthesis of Au nanoparticles in batch reactors.

The preparation of gold nanoparticles was performed by NaBH4

reduction method .Briefly, 10 mg of HAuCl4 was dissolved in 100 ml
of deionized water (≈ 0.25 mM), and shaken properly to mix the
solution. And, 0.1 M solution of reducing agent (NaBH4) was
prepared by dissolving 1.891 g of NaBH4 in 500 ml of deionized
water. Then, 100 ml of HAuCl4 (0.25 mM) were taken in 250 ml batch
reactor with stirring at 750 rpm and the reducing agent solution was
added with continuous stirring. The color of HAuCl4 solution changed
from pale yellow to dark red over several minutes indicating
production of Au nanoparticles. Stirring process was continued for
another 10 minutes for complete homogenization.
 2. Continous Reactors In continuous reactors, feeding and product
takeoff are both continuous, but not necessarily
at a constant rate. Both input and output lines
are opened during reaction. Not the total mass
Example: Continuous synthesis of
inside the vessel or the density of the stream is
CNTs.
constant with time, and the system may
The apparatus used for the production of CNTs operate at steady state or at unsteady state.
was developed by Iyuke,34 presented An ideal model for continuous reactors is
schematically in Fig. 1. The equipment consisted continuous stirred tank reactor (CSTR) and
of a vertical silica plug flow reactor (1) immersed
in a furnace (2) with a sensitive temperature Plug-Flow reactor (PFR).
regulator, and a system of rotameters, pressure
controllers and valves that controlled the flow of
hydrogen, nitrogen, argon and acetylene gases
into the reactor. The upper end of the reactor
was connected to a condenser (3) which led to
two delivery cyclones (4 and 5) where the CNTs
produced were collected. The ferrocene catalyst
was dissolved in xylene at specific quantities and
pumped (8) at regular intervals into a ferrocene
vaporiser (6) placed on a heater with a sensitive
temperature regulator. This catalyst vaporiser
was connected to the swirled mixer (7) which in
turn led into the reactor.
3. Micro-Reactors Micro-reactors are reactors with the small
dimensions, which do not exceed 1 mm. They are
miniaturized chemical reaction systems, which
contain micro-channels, in which fluid flows
continuously and chemical reactions take place.

POWDERIZATION to EASE TRANSPORTATION
Some companies sell their
nanoparticles in liquid
suspension form. HOWEVER…
- Only small quantity can be
sold.
- Large bottle will be needed
if the customer request for
large quantity.
- Not easy to be handled
when come to large bottle.
- Occupy large space when
come to transportation.
Prepared by Dr. Yeap Swee Pin UCSI
Last but not least,
Thus, most companies prefer
to sell the nanoparticles in
powder form.
- Easily pack into bottle or
plastic.
- Compact and thus occupy
only little space when
come to transportation.
Powderization
 Powderization

Chemical processes:
- Conventional drying
(by heating)
- Advanced drying (by
solvent evaporation)
- Advanced drying (by
lyophilisation process)
- Compress into
compact powder form
Further reading:
https://www.sciencedirect.com /science /article /pii /S2666351120
300036

Credits： Appreciates Dr Yeap Swee Pin for contributing partial

notes.