INERT GAS CONDENSATION METHOD

Inert Gas Condensation Method:

The inert gas evaporationcondensation (IGC) technique, in which
nanoparticles are formed via the evaporation of a metallic source in an
inert gas, has been widely used in the synthesis of ultrafine metal
particles since the 1930s.
A similar method has been used in the manufacture of carbon black, an
ink pigment, since ancient times. The technique employed now for the
formation of nanopowders, in reality, differs from that used to produce
carbon

and

lampblack

primarily

in

the

choice

of

atmospheric

composition and pressure and in the use of a chemically reactive

source.
Thus, although the technology is old, the application to the production
of truly nanoscaled powders is relatively recent.
In its basic form, the method consists of evaporating a metallic source,
using resistive heating (although radio frequency heating or use of an
electron or laser beam as the heating source are all equally effective
methods) inside a chamber which has been previously evacuated to
about 10 power -7 torr and backfilled with inert gas to a low pressure.
The metal vapour migrates from the hot source into the cooler inert
gas by a combination of convective flow and diffusion and the
evaporated atoms collide with the gas atoms within the chamber, thus
losing kinetic energy. Ultimately, the particles are collected for
subsequent consolidation, usually by deposition on a cold surface.

Most applications of the inert gas condensation technique carry this

approach to extremes by cooling the substrate with liquid nitrogen to
enhance the deposition efficiency.
Particles collected in this manner are highly concentrated on the
deposition substrate. While the particles deposited on the substrate
have complex aggregate morphology, the structure tends to be
classified in terms of the size of the crystallites that make up these
larger structures.
The scraping and compaction processes take place within the clean
environment to ensure powder surface cleanliness (i.e., to reduce oxide
formation) and to minimise problems associated with trapped gas.

Sol-Gel methods The sol-gel process may be described as: Formation

of an oxide network through polycondensation reactions of a molecular
precursor in a liquid.
A sol is a stable dispersion of colloidal particles or polymers in a
solvent. The particles may be amorphous or crystalline. An aerosol is
particles in a gas phase, while a sol is particles in a liquid,
A gel consists of a three dimensional continuous network, which
encloses a liquid phase, In a colloidal gel, the network is built from
agglomeration of colloidal particles. In a polymer gel the particles have
a polymeric sub-structure made by aggregates of sub-colloidal
particles. Generally, the sol particles may interact by van der Waals
forces or hydrogen bonds. A gel may also be formed from linking
polymer chains. In most gel systems used for materials synthesis, the
interactions are of a covalent nature and the gel process is irreversible.
The gelation process may be reversible if other interactions are
involved.
The idea behind sol-gel synthesis is to dissolve the compound
in a
liquid in order to bring it back as a solid in a controlled
manner.
Multi component compounds may be prepared with a controlled
stoichiometry by mixing sols of different compounds.
The sol-gel method prevents the problems with co-precipitation,
which may be inhomogeneous, be a gelation reaction.
Enables mixing at an atomic level. Results in small particles,
which are easily sinterable.
The sol-gel method was developed in the 1960s mainly due to the need
of new synthesis methods in the nuclear industry. A method was
needed where dust was reduced (compared to the ceramic method)
and which needed a lower sintering temperature. In addition, it should
be possible to do the synthesis by remote control.
One of the well known examples of a sol-gel system often cited is quick
clay. Clay may form a sol (quick clay) if it is washed sufficiently to
remove the counter ions. Quick clay may be gelled if enough counter
ions are added, so that the colloidal particles aggregate.
(exfoliation/restacking may be involved)
Sol-gel synthesis may be used to prepare materials with a variety of
shapes, such as porous structures, thin fibers, dense powders and thin
films.

Approach 1: Electrochemical deposition of

nanomaterials
Electrochemical deposition is a deposition process in which metal ions
in a solution are transported by an electric field to coat the surface of a
substrate. The deposition process can be either cathodic or anodic
reaction depending on the work piece to be coated (cathode or
anode). Electrodeposition of nanostructures, eg. nanocrystallines,

nanocomposites, amorphous film or layered materials can be obtained

by controlling the electrolysis parameters. The most commonly
practiced techniques are (a) pulse current deposition to manipulate
the growth of deposits, (b) deployment of additives and surfactants to
alter the grain size of deposits and (c) nanoparticles inclusion into
deposits to form nanocomposites.
Pulse current electrodeposition of nanostructured
coating

Direct current is the most commonly deployed technique to deposit a

metal coating. Recent years have seen the use of pulsating the
current

to

achieve

nanostructure

coating.

The

pulse

regime

parameters include pulse duty, pulse cycle, frequency and its

amplitude, cathodic or anodic current, zero current at open-circuit, etc.
Pulsating the deposition current can affects the diffusion layer next to
the electrode surface which is in contact with the liquid solution. This
will influence the deposition mechanisms of metal deposits such as
altering the nucleation process and the subsequent growth of the
deposit. Pulsed current can enable the incorporation of nanoparticles
to a high content in the coating as well as producing a wider range of
alloys, deposit composition and material properties

2.

Nanoparticles in a metal coating to form

nanocomposites

Nanosized particles can be incorporated into metallic coating to form

nanocomposite coating. Two common processes involved in the
incorporation of particles into metallic coatings are (a) physical
dispersion of particles in the electrolyte and (b) electrophoresis
migration of particles to the work piece supported by surface charged
particles. The metal coating can be plain metal, eg. nickel, copper, tin,
gold, or alloys and multilayered coatings. Nanoparticles may include
metals, alloys, ceramics, metal oxides, nitrides, carbides, etc. The
inclusion of nanoparticles into a metal coating is dependent on many
electrolysis parameters such as characteristics of the nanoparticle
(particle concentration, surface charge, type, shape, size), electrolyte
composition (electrolyte concentration, additives, temperature, pH,
surfactant type and concentration), current density (direct current,
pulsed current, potentiostatic control) and flow hydrodynamics
(laminar, turbulent regimes), electrode geometry and electrodeposition
reactor, eg. rotating disk electrode, rotating cylinder electrode, parallel
plate electrodes, etc. Figures below show electrodeposited nickel

coatings containing nanoparticles of silicon carbide (SiC) and titanium

dioxide nanotubes (TiO ), for wear and corrosion resistance.
2

3.

Deployment

of

electrolyte

additives

and

surfactant technology
Electrolyte additives and surfactant technology are keys to the
development of nanostructured materials and coatings. Surfactants
can be categorised into groups such as: cationic, anionic, non-ionic or
amphoteric. Surfactants can be hydrocarbon or fluorocarbon based. In
the surface metal finishing industry, electrolyte additives are
commonly grouped by names such as brighteners (provide surface
finish as matte, semi-matte or bright appearance), surface wetters
(reduce surface tension between, reduce coating porosity or liberation
of gas bubbles) and stress relievers (relieve compressive or tensile
stress of the coating). Additives and surfactants are deployed to affect
the growth
mechanisms.

of metal deposits, via adsorption or desorption

Many metallic coatings are conventionally designed on the macroscale. By reducing the macro-scale to the nano-scale could provide
enhanced surface properties, leading to a longer lasting, lighter weight
and more protective coatings. Electrolyte additives and surfactants are
used to affect the grain size of coating. The figure shows a
polycrystalline vs. nanocrystalline coating. A nanocrystalline coating
has nm grain size, with enhanced coating performance against an
external load.

Pulsed Laser Deposition

An introduction to Pulsed Laser Deposition
The technique of PLD has been used to deposit high quality films of materials for more
than a decade.The technique uses high power laser pulses (typically ~108 Wcm-2) to
melt, evaporate and ionize material from the surface of a target.This "ablation" event
produces a transient, highly luminous plasma plume that expands rapidly away from the
target surface.The ablated material is collected on an appropriately placed substrate
upon which it condenses and the thin film grows. Applications of the technique range
from the production of superconducting and insulating circuit components to improved
wear and biocompatibility for medical applications.In spite of this widespread usage, the
fundamental processes occurring during the transfer of material from target to substrate
are not fully understood and are consequently the focus of much research.
In principle PLD is an extremely simple technique, which uses pulses of laser
energy to remove material from the surface of a target, as shown schematically on the
right. The vaporized material, containing neutrals, ions, electrons etc., is known as a
laser-produced plasma plume and expands rapidly away from the target surface
(velocities typically ~106 cms-1 in vacuum).Film growth occurs on a substrate upon
which some of the plume material recondenses.In practice, however, the situation is not
so simple, with a large number of variables affecting the properties of the film, such as
laser fluence, background gas pressure and substrate temperature.These variables
allow the film properties to be manipulated somewhat, to suit individual applications.
However, optimization can require a considerable amount of time and effort.Indeed,
much of the early research into PLD concentrated on the empirical optimization of
deposition conditions for individual materials and applications, without attempting to
understand the processes occurring as the material is transported from target to
substrate.

The PLD process can be crudely split into two sections, i.e. the plasma creation and
expansion, followed by film growth at the substrate. In the current article only data
relating to the initial stage will be presented. The temporal evolution of densities,
temperatures and velocities within laser-produced plasmas can only be determined
using fast diagnostics (~ns time-scales), due to the high luminosity and transient nature
of the plumes.
A variety of techniques, including interferometry, optical spectroscopy and Laser-Induced
Fluorescence (LIF), are used to investigate different stages of the plasma creation and
expansion.At short delay times after the ablation pulse (<100ns) Mach-Zehnder
interferometry has been used to study the free electron component within the plume
expanding into vacuum. The time-varying electron density was calculated from a series
of interferograms of the plume, captured using an Andor ICCD camera with a 2ns gate
width.A typical image is shown in the on the left.