SYNTHESIS OF NANOMATERIALS

Unit –II Physical Methods

Ball Milling:
It is a process where a powder mixture placed in the ball mill and is subjected to
high-energy collision from the balls. It is a top-down method of nanomaterial
synthesis. It can be defined as the process of grinding a material into a very fine
powder using a cylindrical device filled with both material to be processed and the
grinding media.
Principle:
It works on the principle of impact and attrition. i.e., size reduction is done by impact
as the balls drop from near the top of the shell.
Construction and working:
● The apparatus has a rotating chamber which has both the media and the material
in it.
● As the chamber rotates the media is lifted up on the riding side and cascades
down on other
● With this motion the particles between the media and chamber walls are
reduced in size by both impact and attrition
● The desired particle is achieved by controlling the time, applied energy and the
size and density of the grinding media.
Ball milling will result in a ball curve particle size distribution with one or more
peaks.
The grinding media
● The balls which could be of different diameter occupy 30 – 50 % of the mill
volume and its size depends on the feed and mill size. The large balls tend to
break down the coarse feed materials and the smaller balls help to form fine
product by reducing void spaces between the balls.
● The grinding balls are available in stainless steel, tungsten carbide and
zirconium oxide. Sizes range from 0.1 mm to 15 mm, depending on the
material. The grinding jars are also of different sizes made up of different
materials
Process Parameters:
 ● Type of mill
● Height and volume of vial.
● Operation: Milling duration, rotation speed, kinetic shock energy, and shock
frequency.
● Number, size and type of milling balls, ball to powder mass ratio.
● - Other parameters: temperature of milling, milling atmosphere (e.g. argon) and
process control agent.

Advantages Disadvantages
● Low cost of installation ● contamination
● Low cost of grinding ● long processing time
● Capacity and fineness of the process ● no control on particle
can be adjusted just by changing the morphology
balls ● agglomerates, and residual
● Suitable for both batch and continuous strain in the crystallized
operation phase
● Suitable for open and closed circuit ● Crystal defects
grinding
● It can be applied to any material
without hardness limitation

Planetary ball mill

● Planetary ball mill is a most frequently used system in the Laboratories for
Research purposes.
● The ball mill system consists of one turn disc and two or four bowls.
● The turn disc rotates in one direction while the bowls rotate in the opposite
direction.
● The centrifugal forces, created by the rotation of the bowl around its own axis
together with the rotation of the turn disc, are applied to the powder mixture and
milling balls in the bowl
● The powder mixture is fractured and cold welded under high energy impact.
● Since the rotation directions of the bowl and turn disc are opposite, the
centrifugal forces are alternately synchronized.
 ● Thus friction resulted from the hardened milling balls and the powder mixture
being ground alternately rolling on the inner wall of the bowl and striking the
opposite wall.
● The impact energy of the milling balls in the normal direction attains a value of
up to 40 times higher than that due to gravitational acceleration.
● During the high-energy ball milling process, the powder particles are subjected
to high energetic impact. Micro structurally, the mechanical alloying process
can be divided into four stages:
 initial stage,
 intermediate stage,
 final stage, and
 Completion stage.
(a) At the initial stage of ball milling, the powder particles are flattened by the
compressive forces due to the collision of the balls. Micro-forging leads to changes in
the shapes of individual particles, or cluster of particles being impacted repeatedly by
the milling balls with high kinetic energy. However, such deformation of the powders
shows no net change in mass.
(b) At the intermediate stage of the mechanical alloying process, significant changes
occur in comparison with those in the initial stage. Cold welding is now significant.
The intimate mixture of the powder constituents decreases the diffusion distance to the
micrometre range. Fracturing and cold welding are the dominant milling processes at
this stage. Although some dissolution may take place, the chemical composition of the
alloyed powder is still not homogeneous.
(c) At the final stage of the mechanical alloying process, considerable refinement and
reduction in particle size is evident. The microstructure of the particle also appears to
be more homogenous in microscopic scale than those at the initial and intermediate
stages. True alloys may have already been formed.
(d) At the completion stage of the mechanical alloying process, the powder particles
possess an extremely deformed metastable structure. At this stage, the lamellae are no
longer resolvable by optical microscopy. Further mechanical alloying beyond this
stage cannot physically improve the dispersed distribution. Real alloy with
composition similar to the starting constituents is thus formed.
Inert gas Condensation
Inert gas condensation is one of the primitive methods for nanomaterial's synthesis
that employs inert gas like helium or argon. It is a bottoms-up method. The method of
Inert Gas Condensation can be utilized for the production of the nanoparticle and
Nano composites of different metals or inorganic materials including Co, Mn, Mo, Fe
and Zn nanoparticles. The method is also used to produce metal alloy nanoparticles
like Fe-Cu and Fe-Ni.
Principle:
Inert Gas Condensation involves the vaporization of the metal or inorganic materials
from a vaporizing source in the presence of an inert gas atmosphere followed by rapid
condensation of the vaporized atoms of the metal or inorganic material on a cold
surface to form nanoparticles.
Construction:
● The technique of inert-gas condensation (IGC) consists of evaporating,
sputtering or ablating a material inside a chamber that is evacuated to a vacuum
pressure of about 10-8 mbar and then back-filled with a low-pressure inert gas
like helium.
● The material atoms collide with the gas atoms inside the chamber, lose their
kinetic energy, and condense in the form of small particles.
● The condensed particles are collected on a cold finger and the deposit is scraped
off into a compaction unit.
● The scraping and compaction processes are carried out under ultra-high vacuum
conditions to maintain the cleanliness of the particle surfaces and to minimize
the amount of trapped gases.
● The inert gas condensation method produces equiaxed crystallites. 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 and temperature, the
evaporation/sputtering/ablation rate, and the gas composition.
● A wide class of metals and alloys can be processed by IGC technique as well as
oxides, nitrides, carbides, etc. using a corresponding gas atmosphere. Recently,
a new class of non-crystalline solids – Nano glasses - has been achieved by
condensation of Nano sized amorphous particles and their subsequent
compaction at high applied pressure of a few GPa.

Thermal-evaporation inert gas condensation

● Thermal evaporation is the most popular technique due to its easy handling and
good yield. Several pure nanocrystalline metals like Cu, Au, Pd, Ni, Fe etc., can
be synthesized with a narrow particle size distribution between 5-20 nm.
● Gas pressure and temperature can be varied to vary the particle size in thermal
evaporation technique.
● Alloys with different vapor pressures of constituent elements are difficult to
make by thermal evaporation in IGC which limits the applicability of this
technique.
Magnetron-sputtering inert gas condensation
● Magnetron sputtering is employed in inert gas condensation because elements
with different vapor pressures can be synthesized with good compositional
homogeneity.
● Also, metals with very high melting point like Mo and oxides like ZrO2 can be
synthesized by magnetron sputtering which are very difficult to synthesize in
thermal evaporation.
● Unlike traditional sputtering of thin films in which the sputtering is done at
very low pressures (in the order of 10-3 mbar), pressures of the order of 10-
1
mbar are employed in IGC to synthesize nanoparticles.
● Unlike thermal evaporation, one cannot change the gas pressure to change the
particle size in magnetron sputtering which is an obvious limitation in the
synthesis technique
Pulsed-laser-ablation inert gas condensation
● This technique consists of ablation of a material by means of Pico-second
pulsed laser irradiation in a vacuum chamber (base pressure 10-7 mbar) under a
flow of inert gas such as helium and argon.
● The ablated atoms condense into clusters or nanoparticles, which are
continuously collected on a liquid nitrogen cooled collection device.
● A wide range of Nano powders of metals, metallic alloys, semiconductors, and
metal oxides can be synthesized by this method

Advantages Disadvantages
● extensive range of materials such as ● It Is hard to work under
intermetallic compounds, ceramics metals, inert gas conditions with
alloys, semiconductors and composites can be all flasks and apparatus
synthesized via inert gas condensation and perfecltly sealed
technique. ● Ultra high vaccum
● Inert gas condensation is a very flexible one in chambers with high
terms of cluster sizes to be made, controlling pressure are needed
the size and the size distribution of the ● It is more expensive
particles over a broad range through the
process and parameter alteration such as
temperature and pressure
● Article surface cleanliness and ultrafine sizes
of the particles make it possible to overcome
the conventional restrictions of kinetics and
 phase equilibria through the combination of
high driving forces, diffusion distances and
more importantly, uncontaminated surfaces.

Thermal Evaporation Method

One of the common methods of Physical Vapor Deposition (PVD) is Thermal
Evaporation. This is a form of Thin Film Deposition, which is a vacuum technology
for applying coatings of pure materials to the surface of various objects. The coatings,
also called films, are usually in the thickness range of angstroms to microns and can
be a single material, or can be multiple materials in a layered structure.
Principle:
This method uses a resistive heat source to evaporate a solid material in a vacuum
environment to form a thin film. The material is heated in a high vacuum chamber
until vapor pressure is produced.
Construction and working:
● Thermal Evaporation involves heating a solid material inside a high vacuum
chamber, taking it to a temperature which produces some vapor pressure.
● Inside the vacuum, even a relatively low vapor pressure is sufficient to raise a
vapor cloud inside the chamber.
● This evaporated material now constitutes a vapor stream, which traverses the
chamber and hits the substrate, sticking to it as a coating or film
● Since, in most instances of Thermal Evaporation processes the material is
heated to its melting point and is liquid, it is usually located in the bottom of the
chamber, often in some sort of upright crucible.
● The vapor then rises above this bottom source, and the substrates are held
inverted in appropriate fixtures at the top of the chamber.
● The surfaces intended to be coated are thus facing down toward the heated
source material to receive their coating
● Steps may have to be taken to assure film adhesion, as well as control various
film properties as desired.
 ● Fortunately, Thermal Evaporation system design and methods can allow
adjustability of a number of parameters in order to give process engineers the
ability to achieve desired results for such variables as
 thickness
 uniformity
 adhesion strength
 stress, grain structure
 optical or electrical properties, etc
● There are two primary means of heating the source material namely
 Filament evaporation
 E-beam evaporation
● Most Thermal (Filament or E-Beam) Evaporation PVD systems include quartz
crystal deposition control, whereby real time deposition rate monitoring and
control takes most of the work out of achieving the right thickness.
Filament Evaporation:
● There are numerous different physical configurations of these resistive
evaporation filaments, including many known as "boats" - essentially thin sheet
metal pieces of suitable high temperature metals (such as tungsten) with formed
indentations or troughs into which the material is placed.
● The filament source offers the safety of low voltage, although very high current
is required, usually several hundred amps.

E-beam Evaporation
● This is certainly a more "high tech" approach to heating a material up, and
involves some dangerous high voltage (usually 10,000 volts), so E-Beam
systems always include extra safety features.
● The source itself is an E-Beam "gun", where a small and very hot filament boils
off electrons which are then accelerated by the high voltage, forming an
electron beam with considerable energy
 Advantages Disadvantages
● Versatile, can be used to coat ● Materials with Low Vapor
different kind of particles. pressure are hard to evaporate.
● Deposited films are usually very ● Film Adhesion can be
pure Problematic.
● Limited step coverage. ● Needs precise control of
● Good deposition rate Deposition rate and crucible
● Low expenses equipment's. temperature.
● Good control in composition of
film deposition.

Sources:
Books referred:
● The essentials of nano. By T. Pradeep.
● Nano crystals: Synthesis, Properties and Applications, C. N. R. Rao, P. J.
Thomas and G. U. Kulkarni
● Nanostructures & Nanomaterial: Synthesis, Properties & Applications,
Guozhong Gao, Imperial College Press
● Nanoparticles: Synthesis, Stabilization, Passivation, and Functionalization by
Ramanathan Nagarajan and T. Alan Hatton.
Online Sources:
PPT on nanomaterial synthesis.
https://icarus-alloys.eu/sites/default/files/SpringSchool/Presentations/
16.%20Spring%20School%20Presentation__Sebastiano%20Garroni.pdf
Ball milling resources:
https://www.pharmapproach.com/ball-mill/
https://www.understandingnano.com/nanomaterial-synthesis-ball-milling.html
Synthesis of nanomaterials by HEBMP by W.cao
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3124392/
High-energy ball milling technique for ZnO nanoparticles as antibacterial
material
http://www.semicore.com/news/71-thin-film-deposition-thermal-evaporation
Thermal evaporation notes
https://www.sciencedirect.com/topics/physics-and-astronomy/thermal-evaporation