Nano-Particulate Technology:

Synthesis

Feynmans Vision in 1959

There is plenty of room at the bottom
Microtechnology is a frontier to be pushed
back, like HP, HV, LT
Ordinary machines could build small
machines, which could build smaller
machines,. to atomic level

22 years later, first journal publication of

article on molecular nanotechnology
(Drexler, 1981)

Excerpts from The Hindu interview with Prof. Pradeep,

Dept of Chemistry, IIT Madras; March 28, 2007
What is nano technology?
The term nano technology refers to a broad range of technologies, all of which
involve the utilisation of the properties of nano scale objects. Nano scale refers to
the size regime of nanometers or 10 to the power of -9 meters. The properties of
materials in this size regime are unique. Nano technologies became possible as a
result of our capability to manipulate matter with atomic precision. At the scale of
nanometer, all disciplines converge. Therefore, nano technology is a fusion
technology.
At this length scale, new properties and new phenomena come about. Materials
start behaving differently. An example is reactive gold. Till now we knew only
about noble metal gold, which does not change with time. Now we have highly
reactive gold. In addition, we know of fluorescent and magnetic gold. This
example suggests that numerous other materials with completely different
properties could be made. This possibility is a result of the capability to
manipulate matter at this length scale the length scale of atoms.

Excerpts from The Hindu interview with Prof. Pradeep,

Dept of Chemistry, IIT Madras; March 28, 2007

Why is it necessary to know about nano

technology?
Well, look at nature. Leaves make complex molecules called
carbohydrates starting from a single carbon molecule,
carbon-dioxide, present in air. These molecules make life
possible for all of us. Every molecular assembly in nature is
by this atom-by-atom approach. From amoeba to elephant is
made this way. These synthetic routes are the most energy
efficient, green and sustainable. The motion of a muscle
fibre, or a flagellum is the result of nano technologies.
Therefore, ultimately an understanding of these will help us
to do things better, with improved efficiency in much more
eco-friendly, sustainable manner. Of course when you look
at properties at this length scale, one may find new things.
That drives the other side of scientific enquiry curiosity.

Nano-Engineered Products
Semiconductor nano-crystallites for use in
microelectronics
Ceramics for use in demanding environments
Polymers with enhanced functional properties
Transparent coatings with UV/ IR absorption properties,
abrasion resistance
Static dissipative/ conductive films
Enhanced heat-transfer fluids
Catalysis
Topical personal care (e.g., sunscreen) &
pharmaceutical applications
Ultrafine polishing of e.g., rigid mememory disks, optical
lenses, etc.

Functional Polymer Fillers

To improve viscoplastic properties
By addition of inorganic fillers
Glass fiber, talcum, kaolin
20-60% dosage
Disadvantage: incresed density of the composite
materials

Late 80s: Toyota developed nano-clays

(bentonite) for automotive applications
Functional polymers are very versatile, even tiny
amounts can have dramatic impact

Other Applications
Nanowire & Nanotube arrays for EMI Shielding

Superior thermal, electrical, mechanical properties

SWNT, MWNT
Metallic or semiconducting
Carbon nanotubes provide special advantage in shielding

Chemical Gas Sensing

Low-power sensor arrays with high sensitivity, selectivity
e.g., humidity sensors, solid-state resistive sensors, combustible gas
sensors, etc.

Ceramic MEMS
2D & 3D microcomponents & microelectromechanical devices for harsh
environments

Energy Conversion:
Photo-voltaics, radiation detection, electroluminescent devices, etc.

Electronics & Related Fields:

Scanning probe, scanning microscopy standards
Storage & memory media
Flat panel displays, etc.

Other Applications, contd

Marine Anti-Fouling:
Nanoparticles held in coating lattice, not leached out by marine
environment
Slowly release ions to provide long-term protection
Assure longevity of antimicrobial activity

Textile Fibers:
Nanoparticles in nylon, PP for antimicrobial character in extreme
environments, after extensive thermal cycling
Nanosized ZnO and CuO in synthetic fibers with minimal effects on
color & clarity

Permanent Coatings:
For long-term antimicrobial protection in many coating formulations
Healthcare, insdustrial, food processing, general paints & coatings

Catalysts:
Allows thinner active layers, less usage of precious metals
High, stable solids dispersions
Key application: automotive catalytic converters

Other Applications, contd

Fuel Cells:
Rare-earth metal oxides , nanoceria
As components in electrodes
As low-temperature electrolytes in solid xide fuel cells
(SOFC)

Sunscreen:
To protect human screen from harmful UV rays
Nanomaterials are effective sun blockers

Semiconductor Polishing:
CMP slurries with fumed silica, collidal silica
Ceria, alumina dispersions in nano-sizes
High planarity, efficient removal, unique surface
chemistry

Nano-Particles
Fundamental building blocks of nanotechnology
Starting point for bottom-up approaches
for preparing nano-structured materials &
devices
Their synthesis is an important research
component

Nano-Particle Synthesis Methods

Colloidal processes
Bognolo, 2003

Liquid-phase synthesis
Grieve et al., 2000

Gas-phase synthesis
Kruis et al., 1998

Vapor-phase synthesis
Swihart, 2003

Sono-fragmentation
Gopi, 2007! (Ph.D. thesis)

Colloidal Process
Nanoparticles produced directly to required
specifications, assembled to perform a specific
task
Involves use of surface-active agents
e.g., CdS 50 nm particles by mixing two solutions
containing inverted micelles of sodium bis(2-ethyl
hexyl) sulfosuccinate in heptane
e.g., antiferromagnetic nanoparticles of Fe2O3 by
decomposition of Fe(CO)5 in a mixture of decaline
and oleyl sarcosine

Coordinating ligands used to produce

nanoclusters
Surfactants play a major role

Vapor-Phase Synthesis

Vapor phase mixture rendered thermodynamically unstable relative to formation of

desired solid material

supersaturated vapor
chemical supersaturation
particles nucleate homogeneously if

Once nucleation occurs, remaining supersaturation relieved by

Weak dependence on particle size

At high temperatures, particles coalesce (sinter) rather than coagulate

By removing source of supersaturation, or

By slowing the kinetics

Coagulation rate proportional to square of number concentration

Condensation, or
Reaction of vapor-phase molecules on resulting particles

This initiates particle growth phase

Rapid quenching after nucleation prevents particle growth

Degree of supersaturation is sufficient

Reaction/ condensation kinetics permit

Spherical particles produced

At low temperatures, loose agglomerates with open structures formed

At intermediate temperatures, partially-sintered, non-spherical particles form
Control of coagulation & coalescence critical
Nanoparticles in gas phase always agglomerate

Loosely agglomerated particles can be re-dispersed with reasonable effort

Hard (partially sintered) agglomerates cannot be fully redispersed

Liquid-Phase Synthesis
Used widely for preparation of quantum
dots (semiconductor nanoparticles)
Sol-Gel method used to synthesize
glass, ceramic, and glasss-ceramic
nanoparticles
Dispersion can be stabilized indefinitely by
capping particles with appropriate ligands

Sol-Gel Method
Aqueous or alcohol-based
Involves use of molecular precursors, mainly alkoxides
Alternatively, metal formates

Mixture stirred until gel forms

Gel is dried @ 100 C for 24 hours over a water bath,
then ground to a powder
Powder heated gradually (5 C/min), calcined in air @
500 1200 C for 2 hours
Allows mixing of precursors at molecular level
better control

High purity
Low sintering temperature
High degree of homogeneity
Particularly suited to production of nano-sized multicomponent ceramic powders

Gas-Phase Synthesis
Supersaturation achieved by vaporizing material
into a background gas, then cooling the gas
Methods using solid precursors

Inert Gas Condensation

Pulsed Laser Ablation
Spark Discharge Generation
Ion Sputtering

Methods using liquid or vapor precursors

Chemical Vapor Synthesis

Spray Pyrolysis
Laser Pyrolysis/ Photochemical Synthesis
Thermal Plasma Synthesis
Flame Synthesis
Flame Spray Pyrolysis
Low-Temperature Reactive Synthesis

Inert Gas Condensation

Suited for production of metal (e.g., Bi)
nanoparticles
Reasonable evaporation rates at attainable
temperatures

Procedure:
Heat solid to evaporate it into a BG gas
Mix vapor with a cold inert gas to reduce temperature
Include reactive gas (e.g., O2) in cold gas stream to
prepare compounds (e.g., oxides)

Cntrolled sintering after particle formation used

to prepare composite nanoparticles (e.g., PbS/
Ag, Si/In, Ge/In, Al/In, Al/Pb)

Pulsed Laser Ablation

Use pulsed laser to vaporize a plume of material
Tightly confined, spatially & temporally

Can generally only produce small amounts of

nanoparticles
But can vaporize materials that cannot be easily
evaporated
e.g., synthesis of Si, MgO, titania, hydrogenatedsilicon nanoparticles

Strong dependence of particle formation

dynamics on BG gas

Spark Discharge Generation

Charge electrodes made of metal to be vaporized in
presence of inert BG gas until breakdown voltage is
reached
Arc formed across electrodes vaporizes small amount of metal
e.g., Ni

Produces very small amounts of nanoparticles

but in a reproducible manner

Reactive BG gas (e.g., O2) can be used to make

compounds (e.g., oxide)
BG gas can be pulsed between electrodes as arc is
initiated
Pulsed arc molecular beam deposition system

Ion Sputtering
Sputter solid with beam of inert gas ions
e.g., magnetron sputtering of metal targets

Low pressure (appr 1 mTorr) required

Further processing of nanoparticles in aerosol
form difficult

Chemical Vapor Synthesis

Vapor phase precursors brought into a hot-wall reactor under nucleating

condition
Vapor phase nucleation of particles favored over film deposition on surfaces
CVC reactor (Chemical Vapor Condensation) versus CVD

Very flexible, can produce wide range of materials

Can take advantage of huge database of precursor chemistries developed
for CVD processes
Precursors can be S, L or G under ambient conditions
but delivered to reactor as vapor (using bubbler, sublimator, etc)

Examples:
Oxide-coated Si nanoparticles for high-density nonvolatile memory devices
W nanoparticles by decomposition of tungsten hexacarbonyl
Cu and CuxOy nanoparticles from copper lacetonate

Allows formation of doped or multi-component nanoparticles by use of

multiple precursors
nanocrystalline europium doped yttria from organometallic yttrium & europium
precursors
erbium in Si nanoparticles
zirconia doped with alumina
one material encapsulated within another (e.g., metal in metal halide)
Can prevent agglomeration

Spray Pyrolysis
Use of a nebulizer to inject very small
droplets of precursor solution
Also known as aerosol decomposition
synthesis, droplet-to-particle conversion
Reaction takes place in solution in the
droplets, followed by solvent evaporation
e.g.: preparation of TiO2 and Cu
nanoparticles

Laser Pyrolysis/ Photothermal

Synthesis
Precursors heated by absorption of laser
energy
Allows highly localized heating & rapid
cooling
Infrared (CO2) laser used
Energy absorbed by precursors, or by inert
photosensitizer (SF6)

e.g.: Si from silane, MOS2, SiC

Pulsed laser shortens reaction time, allows
preparation of even smaller particles

Thermal Plasma Synthesis

Inject precursors into a thermal plasma
Precursors generally decomposed fully
into atoms
Which then react or condense to form
particles
When cooled by mixing with cool gas, or
expansion through a nozzle

Used for production of SiC and TiC for

nanophase hard coatings

Flame Synthesis
Particle synthesis within a flame
Heat produced in-situ by combustion reactions
Most commercially successful approach
Millions of metric tons per year of carbon black and metal oxides
produced

Complex process, difficult to control

Primarily useful for making oxides
Recent advances:
g-Fe2O3 nanoparticles
Titania, silica sintered agglomerates

Application of DC electric field to flame can influence

particle size

Flame Spray Pyrolysis

Directly spray liquid precursor into
flame
Allows use of low-vapor-pressure
precursors
Applied to synthesis of silica particles
from hexamethyldisiloxane

Low-Temperature Reactive
Synthesis
React vapor phase precursors directly w/o
external addition of heat
and w/o significant production of heat

e.g.: ZnSe nanoparticles from

dimethylzinc-trimethylamine and hydrogen
selenide
by mixing in a counter-flow jet reactor at RT
heat of reaction sufficient to allow particle
crystallization

Advances in Instrumentation for

Nano-Particle Synthesis
Need to analyze processes with short time-scales, in small
regions of a reactor, in complex mixtures
FTIR spectroscopy (in emission & transmission modes)
to simultaneously characterize

gas temperature,
gas concentrations,
particle temperature, and
particle concentration during synthesis

Localized thermophoretic sampling and in-situ light

scattering measurements of
particle concentration,
size, and
morphology

Particle mass spectrometry and TEM imaging of

extracted samples

Advances in Modeling for NanoParticle Synthesis

Compute particle nucleation rates based on
detailed chemical reaction kinetics
in cases where nucleation does not occur by simple
condensation of a supersaturated vapor

Model multi-dimensional particle size

distributions
where both particle volume and surface area are
explicitly treated

Model simultaneous coagulation and phase

segregation in multi-component particles
containing mutually immiscible phases

Sonochemical Nano-Synthesis
Sonochemistry: molecules undergo a chemical reaction
due to application of powerful ultrasound (20 kHz 10
MHz)
Acoustic cavitation can break chemical bonds
Hot Spot theory: As bubble implodes, very high temperatures (
5,000 25,000 K) are realized for a few nanoseconds; this is
followed by very rapid cooling (1011 K/s)
High cooling rate hinders product crystallization, hence
amorphous nanoparticles are formed

Superior process for:

Preparation of amorphous products (cold quenching)
Insertion of nano-materials into mesoporous materials
By acoustic streaming

Deposition of nanoparticles on ceramic and polymeric surfaces

Formation of proteinacious micro- and nano-spheres
Sonochemical spherization

Very small particles

Sonochemical Nano-Synthesis:
Examples
S-2, Se-2, Te-2

used in non-linear optic detectors, photorefractive devices,

photovoltaic solar cells, optical storage media

Gold, Co, Fe, Pg, Ni, Au/Pd, Fe/Co

Nanophased oxides (titania, silica, ZnO, ZrO2, MnOx

More uniform dispersion, higher surface area, better thermal

stability, phase purity of nanocrystalline titania reported

MgO coating on LiMn2O4

Magnetic Fe2O3 particles embedded in MgB2 bulk
Nanotubes of C, hydrocarbon, TiO2, MeTe2
Nanorods of Bi2S3, Sb2S3, Eu2O3, WS2, WO2, CdS, ZnS,
PbS, Fe3O4
Nanowires of Se

Sono-Processing of Nanocomposites
Power ultrasound can assist in synthesis,
blending, dispersion & erosion-testing of nanocomposites
dispersed phase having at least one dimensin < 100
nm

High-intensity ultrasound used with melt

processing for polymer-clay nano-composites
e.g., PP/PS-clay & PMMA/clay nano-composites
prepared by ultrasonic-assisted melt mixing
clay aggregates more finely dispersed
Superior overall homogeneity of composite, improved
performance

Sono- Fragmentation
(Size Reduction)
Bubble

Particles

Sono- Fragmentation
(Size Reduction)
Bubble
Bubble Collapse
due to Implosion

Particle Fragments
due to
Particles

a) Violent Bubble
collapse
b) Inter-particle
attrition

Sono- Fragmentation
(Size Reduction)
Bubble
Bubble Collapse
due to Implosion

Particle Fragments
due to
Particles

a) Violent Bubble
collapse
b) Inter-particle
attrition

Fragmented Particle

Feed Sample

Distilled
Water

Micron sized
feed particles

Sonication
20 kHz, 1000 W,
Probe type
Sonication/
58 kHz, 500 W, Tank

Distilled
Water

Micron sized
feed particles

Sono-Processed Sample
20 kHz, 1000 W,
Probe type
Sonication/
58 kHz, 500 W, Tank

Distilled
Water

Micron sized
feed particles

Micron sized
particles

Sub-Micron
/Nano Sized
Particles

Sono-Processed Sample
(stratified Mix)

Submicron/
nano
Particles

Micron
Sized
Particles

Sono-Blending
(Particle Size De-stratification)

High
Frequency
Sonication

Submicron/
nano
Particles

Micron
Sized
Particles

Sono-Blended Particles For

Composite Formulation
Drying
out at 105
Deg C

High
Frequency
Sonication

Submicron/
nano
Particles

Micron
Sized
Particles

Good Blend of
Sub-micron
/Micron-sized
particle

Blended sample
Ready for
composite
Formulation

Polymer Precursor Preparation

Solvent
e.g CHCl3

Blended sample
Ready for
composite
Formulation

Polymer Precursor Preparation

Solvent
e.g CHCl3

Sonication
For 2 mts

Blended sample
Ready for
composite
Formulation

Polymer
Precursor

( Particles
Dispersed in
solvent)

Polymer Matrix

Particle Reinforced Polymer Matrix

Particle
Polymer Matrix

Caviation Erosion On the ceramic

Particle Reinforced Polymer Matrix

Particle

Cavitation
Bubble

Polymer Matrix

Superior Cavitation Erosion Resistance on

Nano-Composites
Erosion Resistance Ehancement

Mass loss (grams)

0.001

with filler material

0.0005

without filler material

0
0

10

Sonication time (minutes)

Erosion Resistance Enhancement, PMMA

1.2

Turbidity N.T.U

- Mass loss and turbidity

data show same relative
trends

0.9
Withfiller material

0.6

with out filler material

0.3
0
0

10

Sonication T ime
(minutes)

-Sono-Cavitation test results shown to correlate with classical impacterosion test results.

Thicknes
s (m)

Unfilled PMMA

Filled PMMA

Den
sity

mu

LAM
BDA

nu

VL

VS

0.541

1.232

0.675

1.1

0.501

0.669

1.288

0.286

0.501

0.8712

1.421

0.846

1.16

0.83

0.683

2.034

0.226

0.83

E = Youngs Modulus in GPa.

G = Shear Modulus in GPa.

Nu = Possions ratio.
VL= longitudinal velocity mm/micro sec.
VS= Shear velocity mm/micro sec.
Lamda and mu are Lamis constant

WFA Filled PMMA

has Higher E.moduli
and shear moduli

Conclusion
Nano-particulate technology is gaining
prominence as nano-science becomes old
news (& pico-science, femto-science begin to
emerge!)
Opportunities abound in scale-up &
commercialization of nano-particle synthesis
Bottom-up & Top-down methods are both
used
pros & cons must be weighed for specific application

PSP Lab in ChE Dept @ IITM has cutting-edge

research program in various aspects of nanotechnology