Methods to produce

p
Nanoparticles
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Nanoparticles
Nanoparticles are the building blocks for
realising a wide range of nanostructured
materials and devices, hence their synthesis
plays a key role in the development of
nanosciences and nanotechnologies.
A nanoparticle is defined as a nano-object with
all three external dimensions in the nanoscale
(1-100 nm)
nm).

Definition from ISO/TS 27687:2008

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Why produce nanoparticles

Nanoparticles are used to fabricate nanostructured
materials with unique properties compared to their bulk
material counterparts. These properties include:
Mechanical
Thermal
Optical
El t i l conductivity
Electrical d ti it
Catalytic activity
Magnetic properties Source: http://en.wikipedia.org/wiki/Nanoparticle

The properties of these nanostructured materials can

then be harnessed to manufacture value added products
with benefits to the consumer and environment.

Methods for Nanoparticle synthesis
Bottom-up
Begins from nanostructured
building blocks and then
assembles them into the final
material.
Example methods: liquid
h
phase or gas ((vapour)) phase
h Typically leads to wastage
synthesis.
Nanoparticle synthesis focus has primarily been on the
bottom-up
bottom up approach.
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Two methods to produce
nanoparticles
Top-Down
Begin with the bulk material
and process to obtain
nanoparticles
nanoparticles.
Example methods: milling,
etching or lithography.
material, broad distribution of
nanoparticles
p and impurities.
p
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Liquid phase synthesis

There are a variety of different liquid phase synthesis
methods to p
produce nanoparticles
p such as:
Coprecipitation
g p
Sol-gel processing
g
Microemulsions
Hydrothermal/Solvothermal synthesis
Microwave synthesis
Sonochemical synthesis
Template synthesis
Biomimetic synthesis
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Liquid phase synthesis

M th d
Method S l
Scale C t
Cost
Coprecipitation Industrial Low
Sol-gel processing Industrial Low
Microemulsions Industrial Low
Hydrothermal / Solvothermal Industrial Medium
Microwave synthesis Lab High
p
Template synthesis
y Lab High
g
Biomimetic synthesis Not actually used High
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Gas phase synthesis

There are a variety of different gas phase
synthesis methods to produce nanoparticles
such as:
Laser pyrolysis
Inert gas condensation
Pulsed laser ablation This technique has
Spark discharge generation been used within
NanoHex to produce
Ion sputtering nanoparticles
ti l
Chemical vapour deposition
Spray pyrolysis
Flame synthesis
Thermal plasma synthesis
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Gas phase synthesis

Method Scale Cost
Laser pyrolysis Industrial Medium
Inert gas condensation Lab High
Pulsed laser ablation Industrial High
Spark discharge Industrial Medium
generation
g
Ion sputtering Industrial Medium
Chemical vapour Industrial Medium
deposition
Spray pyrolysis Industrial Medium
Flame synthesis
y Industrial Medium
Thermal plasma Industrial Medium
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Nanoparticle formation by gas phase synthesis

The basic principle for the formation of nanoparticles from the
vapour phase requires the establishment of supersaturation
b chemical
by h i l or physical
h i l methods.
th d

{ P= vapour pressure
Pe=saturation vapour pressure
S ((supersaturation
p ) S=P/Pe

If the concentration of condensable products is sufficient,

homogeneous nucleation occurs with the formation of nuclei
or embryonic droplets which grow by
coagulation/coalescence.
coagulation/coalescence
Condensable
products

Nucleation
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Nanoparticles formation by gas phase synthesis

Schematic below shows the stage for nanoparticle formation.
Particle
vapour Condensable Agglomeration
products

Nucleation Particle
Growth
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Nanoparticles production by laser pyrolysis

This technique has been of employed within NanoHex to
produce nanoparticles
p p for the synthesis
y nanofluids.

Pre-requisites for energy

li iin th
coupling t
the system:
One of the reactants should
absorb the laser radiation to
be optically excited.
Alternatively, a reaction
sensitiser must be added that
absorbs
b b llaser radiation
di ti
without being dissociated.
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Nanoparticles production by laser pyrolysis

Rapid cooling rates

Small particles
All the p
particles experience
p the
same fate

Narrow size distribution

Wall-less reactor

High
g purity
p y particles
p

The nanoparticle average size can be

tailored (in the range 5-50 nm) by
changing the process parameters
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Nanoparticles production by laser pyrolysis

The nano-particle average size can be
Thee pa
particle
tces size
e increases
c eases by
by: varied ((in the range
g 5-50 nm)) by
y
Increasing the residence time of the changing the process parameters in
particles in the interaction region the reactor

HOW ?
By reducing gas flow
By increasing the total pressure in
the reactor

Increasing the condensable product

concentration
HOW ?
Increasing the laser power
I
Increasing
i the
h partial
i l pressure off the
h
gas-phase reactants

13
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Production of Nanoparticles by CO2 laser pyrolysis

Method is very flexible for

Capable of Producing Nanoparticles: the production of a variety of
Si,, SiC,, TiO2, SiO2 nanoparticles in
developmental quantities
Typical Precursors:
Gas: SiH4, C2H2, C2H4, NH3
Liquid: TTIP, TEOS
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Production of SiC nanoparticles

The basic principle and reactants to produce SiC
nanoparticles are as follows:

SiH4 + C2H2 SiC

gas gas Laser pyrolysis

The produced SiC nanoparticles are

Spherical
Mono disperse in size
High purity
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SiC Nanoparticle Analysis

100

FTIR spectra:
CH SiH H2O Presence of typical
90
InfraRed feature of
SiO
mission

SiC
Transm

80 SiC11 nozzle=3mm, (C2H2)=240 sccm

SiC12 nozzle=3mm, (C2H2)=230 sccm
SiC13 nozzle=4mm, (C2H2)=235 sccm
(SiH4)=500 sccm, (Ar)=5 slm
100
70 p=600 torr,
torr Plaser=630 W

SiC
80
4000 3600 3200 2800 2400 2000 1600 1200 800
Wavenumber (cm
(cm-1)
1)

Intensity (a.u.)
60
SiC 12

XRD 40

-crystalline 20

SiC
0
26 28 30 32 34 36 38
2 (degrees)
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SiC Nanoparticle Analysis

SEM image indicates mean size of about 20-25 nm and

uniform nanoparticle size
size.
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Nanoparticle Synthesis Challenges

Key challenges related to nanoparticles
synthesis are:
Technological:
Control over size and shape
shape.
Producing uniform distribution of particles.
Reproducibility
Reproducibility.
Ability to prevent agglomeration or aggregation of
particles.
particles
Economics:
Scale up
up.
Low Cost.
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Nanoparticle Applications
This diagram show some example sectors where
nanoparticles can be applied:

Textiles

Food
Energy
and
Production
Agriculture

Nanoparticle
A li ti
Applications Steel and
Healthcare
Metal
Applications
Processing

Surface
Electronics
g
Coatings
For further information HENIX 228882 Project

Borsella, E. et al., IR multiple-photon

p p excitation of p
polyatomic
y molecules: a
route towards nanostructures, 2008 Phys. Scr. 78 058112.
Borsella, E. et al. Synthesis of nanoparticles by laser pyrolysis: from
research to applications,
pp , Energia,
g , Ambiente e Innovazione,, Vol. 4-5/2011,,
54-64 (2011)
http://www.enea.it/it/produzione-scientifica/energia-ambiente-e-
innovazione 1/anno 2011/n.%204 5%202011%20Luglio
innovazione-1/anno-2011/n.%204-5%202011%20Luglio-
ottobre2011/Bacteria-endosimbionts-a-source-of-innovation-in-
biotechnology-for-vector-borne-diseases-control%20
Herlin Boime, N. et al., Synthesis of Covalent Nanoparticles by CO2 Laser,
Encyclopedia of Nanoscience and Nanotechnology, Vol. 10 (2004) pp. 301-
326.
Swihart M
Swihart, M.T.,
T Vapor
Vapor-phase nanoparticles Current Opinion in
phase synthesis of nanoparticles,
Colloid and Interface Science 8 (2003) 127133.
http://courses.washington.edu/overney/NME498_Material/NME498_Lecture
s/Lecture4-Overney-NP-Synthesis pdf
s/Lecture4-Overney-NP-Synthesis.pdf
http://www.me.berkeley.edu/ltl/research/Max/max2%28Nanoparticle%20syn
thesis%29.html
htt //
http://en.wikipedia.org/wiki/Nanoparticle
iki di / iki/N ti l