Nanoparticle Technology

Definitions

Nanotechnology wants to control the smallest

structures built of atoms and molecules. It is con-
nected with colloidal chemistry and physics, biol-
ogy, medicine, pharmacy and engineering (materi-
als and processes).

Nanoparticles (from Greek nanos – dwarf) are or-

ganic or inorganic solid particles. The dimension of
nanoparticles is not defined in a uniform manner.

a) particles in the sub micron range ( < 1 µm) ,

b) materials science : < 100 nm (nano scaled
particles)
c) pharmaceutics : < 500 nm, < 1000 nm = 1µm

Usually nanoparticles are dispersed in a continu-

ous phase ( see dispersed systems).
 Historical overview – Nanotechnology and nanoparticles
2697 BC Tien-Lcheu: petroleum lamp soot for Indian ink used in China
400 BC Lycurgus cup (with gold nanoscaled particles covered glass cup, British Museum
London
1600 Manufacturing of church windows, shining red by colloidal gold nanoparticles

1857 Faraday Synthesis of colloidal gold nanoparticles, colour effects

1915 Ostwald, Wolfgang Colloids - „world of neglected dimensions“
1931 Ruska, Knoll development of an electron microscope TEM, 1938 built commercially by Siemens
1942 Knöpfer Aerosil process (Degussa) – pyrogenic silica, 1953 aluminium oxide, 1954 titanium
dioxide
1959 Feynman lecture on the prospects of miniaturisation, “There’s plenty of room at the bottom“
1968 Stöber, Fink, Bohn Synthesis of monodisperse silica, described before in 1956 by Kolbe in PhD thesis
1974 Taniguchi, Norio “Nanotechnology” for processing of separation, consolidation, and deformation of
materials by one atom or one molecule
1985 Smalley, Curl, Kroto Buckminster fullerenes, e.g. C60 carbon
1986 Binnig, Quate, Gerber construction of an atomic force microscope AFM, 1981 Binnig, Rohrer construction
of a scanning tunnelling microscope
1989 Eigler, Schweizer IBM logo written with 35 Xe-atoms on Ni
1991 Iijima Carbon nanotubes
 Disperse Systems

dispersed continuous phase

phase gaseous liquid solid
gaseous bubbles porous solids
xerogels, aerogels, cryogels
liquid aerosol fog emulsion porous solids with liquids
microemulsion hydrogels, alcogels
solid aerosol smoke nanoparticles composite materials
 Nanoparticles: Numerous fields of application

• Ceramics for membranes • Sun creams

• Batteries and fuel cells
• Catalysis and electrolysis reactors
• Gas storage
• Protective coating of plastic
surfaces
• Thermal and scratch protection
• Reflection avoidance in windows
• Electronics, lasers, displays
• Photochromic coatings
• Automotive coatings
• Bioceramics, drug carriers
• Magnetic nanoparticles for
hydrothermal treatment of cancers
 bioavailability

quantum effect

strong surface
effects
10-9 m 10-6 m
0.001 0.01 0.1 1µm

1 10 100 1000 nm
polymers

proteins

metal powders

viruses, DNA

ceramics

tobacco smoke

aerosols

nanoparticle for
life sciences

Sizes and properties of nanoparticle materials

 Properties of nanoparticles

The outstanding importance of nanoparticles and nano

structured systems can be ascribed to :

1. particle size
bioavailability : in water non soluble substances can be
transported as nanoparticles in an organism of human
beings (application in life sciences)

2. large specific surface area

strong surface area effects (e.g. reactivity, high energy
of surface area, adsorption, higher solubility, lower melt-
ing point etc.)

3. change of electronic properties

quantum effects of particles < 10 nm, importance for
electronic and optoelectronic application
 Characterisation of nanoparticles

Nanoparticles and nanopowders are characterised by :

particle size (1 nm – 100 nm) Laser diffraction

Optical spectroscopy
Light scattering

Transmission electron microscopy (TEM)

Scanning electron microscopy (SEM)

large specific surface area Gas adsorption (BET – Brunauer, Emmett, Teller)
(BJH – Barrett, Joyner, Halenda)

(electrostatic) stabilisation Zeta - potential

 Preparation of silica nanoparticles
Process : Sol - Gel - Synthesis - Precipitation
Chemical reactions : Hydrolysis - Polycondensation

Hydrolysis :
suspension in ethanol
Si(OC2H5)4 + 4 H2O Si(OH)4 + 4 C2H5OH
pH 11 - 12 (NH3)

Tetra ethyl orthosilicate (TEOS) Silicon tetra hydroxide Ethanol

Polycondensation :
suspension in ethanol
Si(OH)4 nano- SiO2 (Sol) + 2 H2O
pH 11 - 12 (NH3)

Silicon tetra hydroxide Silica

Principles : nucleation, nucleus growth, Ostwald ripening, (agglomeration)

Controlled double jet precipitation (CDJP)
 Principle of dynamic light scattering
correlation function

Laser Optics Sample g (τ)= e-2·D·K²·τ

D diffusion constant
K scattering light vector
τ delay time
Photo multiplier correlator
Optical Unit

Stokes – Einstein – equation

Optical unit of photon correlation spectroscopy

kB ⋅T
d= 3⋅ π⋅η⋅ D
I(t) small particle g(τ )
large particle d particle diameter

small particle kB Boltzmann constant

T absolute temperature
η dynamical viscosity
large particle
time τ
Scattering light intensity – time – function auto correlation function
Particle size frequency distribution q0 (log d) in nm-1 Particle size distribution of titanium dioxide nanoparticles

method: dynamic light scattering method

4.0
instrument : Zetamaster (Malvern)
detector angle 90 °
3.0 wave length 630 nm
temperature 25 °C

2.0
Particle size distribution of titanium
dioxide after peptization within 24 hours
1.0

Mean particle diameter:

5 10 50 100 dm, 3 = 18.6 nm (volume density)

Particle diameter in nm dm, 0 = 12.0 nm (number density)
Determination of the zeta – potential for nanoparticle characterisation

cathode anode

Charge distribution around a moving particle in an electrical field

laser beams interference pattern scattering light detector

particle

Detection of particle velocity in an interference pattern system of two lasers

Stabilisation of titanium dioxide nanoparticles in suspension

40
Zeta - Potential in mV

30 Zeta - Potential in mV

20

10

0
0,0 0,5 1,0 1,5 2,0 2,5
pH - value of suspension

Zeta potential of TiO2 ranging from + 20 mV to + 40 mV for a pH < 3.0

 Stabilisation of titanium dioxide nanoparticles in suspension

OH2+ OH O-

+ H+ +OH-
OH OH
Ti Ti Ti
OH2+ OH2+ O- O-
acid base

OH2+ O-
OH

Zeta potential of TiO2 ranging from + 20 mV to + 40 mV for a pH < 3.0

 Processes for the production of nanoparticles

Production processes

in a liquid phase in a gaseous phase

Precipitation process Aerosol process

• in homogeneous solution • Flame hydrolysis
• in surfactant based systems • Spray pyrolysis

Sol - gel process

Hydrothermal process
 Chemical and physical processes for nano particle synthesis

Process: precipitation – in homogeneous solution

synthesis of silver bromide

Chemical reaction:
(gelatine)
Ag+ + Br - AgBr
Silver bromide
Principle: precipitation (Controlled double jet precipitation CDJP - technique)

AgNO3
ions
KBr

complex and cluster formation

embryos

cluster formation
nuclei

growth
primary particle

growth, coagulation, ...

colloids

Precipitation homogeneous solution - controlled double jet precipitation CDJP

nucleus formation, followed by growth
reaction and Ostwald ripening

Particle size: AgBr : 7 nm - 60 nm, particle system dependent

a lot of syntheses on a laboratory scale

T. Sugimoto : J. Colloid Interface Sci. 150 (1992) 208 - 225

 Precipitation reactions in homogeneous solution

AgBr – nanoparticle, produced by CDJ - technique at pBr 2,0 (a), 2,8(b), 4,0 (c)

Images (scanning electron microscopy) of typical monodisperse nanoscale

oxides by conversion of metal alkoxides in alcoholic solution
 Precipitation reactions in homogeneous solution

Images (transmission electron microscopy left - scanning electron microscopy right) of

CdS – nanoparticles, produced in homogeneous solution at 26°C by CDJ - technique

Image (scanning electron microscopy) of PbS – nanoparticles, produced in homo-

geneous solution at 26°C by CDJ - technique
 Precipitation reactions in homogenous solutions

Scanning electron microscopy image of aluminium(III)-oxide, 100°C, left

Transmission electron microscopy image of chromium(III)-oxide, 75°C, right,
produced by precipitation reaction in homogeneous solution

Images (scanning electron microscopy) of zinc oxide, 90°C, pH 8,8 (left) and
150°C, pH 13,3 (right), produced by precipitation reaction in homogeneous
solution
Precipitation reactions in surfactant based systems

Images (scanning electron microscopy) of mullite (aluminium silicate) and barium

titanate, produced by precipitation in surfactant based systems (microemulsion)

Image (transmission electron microscopy) of silica, produced by precipitation in

surfactant based systems (microemulsion)
 Chemical and physical processes for nanoparticle synthesis

process: sol - gel process / precipitation

synthesis of silica (Kolbe (1956), Stöber, Fink, Bohn (1968))

chemical reaction :

hydrolysis :
ethanolic suspension
Si(OC2H5)4 + 4 H2O Si(OH)4 + 4 C2H5OH
pH 11 – 12 (NH3)
tetraethylorthosilicate silicon tetra hydroxide ethanol

polycondensation :
ethanolic suspension
Si(OH)4 SiO2 + 2 H2O
pH 11 – 12 (NH3)
silicon tetra hydroxide silica

principle: nucleus formation, followed by growth reaction and Ostwald ripening,

controlled double jet precipitation CDJP

ammonia / water
ethanol
0,2 M tetraethylorthosilicate

ethanol

particle 500 nm – 10 μm
tetraethylorthosilicate / ethanol

products : titanium (IV) – oxide , aluminium oxide, zirconium (IV) - oxide

nuclear power materials ThO2, UO2, PuO2

advantages: often mono disperse, spherical particles of controlled size

disadvantages: reactions have to be carried out with low particle
concentrations, low production output
Sol - gel synthesis / precipitation reaction

Image (transmission electron microscopy) of Stöber particles (silica)

Image (scanning electron microscopy) of Stöber particles (silica)

 Morphology of nanoparticles

Si(OH)4
Dimers
Cycles
pH < 7 or
Particles pH 7 – 10 without salts
pH 7 - 10 with salts
1 nm

5 nm

10 nm

30 nm

3 – dimensional gel network

100 nm

Sol (Stöber – Particles)

Brinker, C.J.; Scherer, G.W. : Sol-Gel-Science, The Physics and Chemistry of Sol-Gel-Science, Academic Press, San Diego, 1990
 Sol - gel process

dehydratisation
Aerosil
chemical reaction chemical reaction drying
Precursor Sol Gel Aerogel

coating organic suspension drying

dipping surfactants

spherical particle in gel structure Xerogel

Calcination Calcination
Calcination

thin layer structure powder ceramics

C.J. Brinker, G.W. Scherer : Sol - Gel Science

 Aerosol processes

Images (transmission electron microscopy) of different

oxides, produced by direct oxidation in an arc