ChE ELNT: Nanotechnology

Lecture 2
Introduction to the Synthesis of
Nanomaterials
Dr. Lorico DS. Lapitan Jr.

Department Of Chemical Engineering, CHE ELNT

University Of Santo Tomas, España, Manila 5CHE A-B-C
 How Do You Naomanufacture?
Sculpt’ from bulk
• Lithography
• Etching
• Ion beam milling
• Ball milling

Assemble Nanoscale building blocks (BBs)

• Nanocrystal Synthesis
• Vapour Deposition
• Sol-gel
• Pyrolysis
• Self assembly
Approaches
• Obviously there are two approaches to the synthesis of
nanomaterials and the fabrication of nanostructures:

Starting material is in the

The nanoparticles are
macro or micro scale and
formed starting from
using different techniques
atomic level to the
the particles are transformed
nanoscale level
to the nanoscale
Synthesis of Nanomaterials
OUTLINE
• Top-Down Approach
1. Ball-Milling
2. Nanoscale Lithography (UV, X-ray and e-beam)

• Bottom-Up Approach
1. Thermal Methods (Hydrothermal and Solvothermal)
2.Vapour Phase Deposition (Physical and Chemical)
3. Self-Assembly Techniques (Self-Assembled Monolayers,
Layer-by-Layer Approach)
4. Sol-Gel Techniques
 Ball Milling
• These mills are equipped with grinding media composed of
wolfram carbide or steel.

• Ball mills rotate around a horizontal axis, partially filled with

the material to be ground plus the grinding medium.

• Size reduction is achieved by impact and attrition

Ball Milling
• The balls rotate with high energy inside a drum and then fall on
the solid with gravity force and crush the solid into nano
crystallites.

Equipment
• Hollow cylindrical shell rotating about its axis

• The axis of the shell may be either horizontal

or at a small angle to the horizontal

• Partially filled with balls (stainless steel,

ceramic, or rubber).

• The inner surface of the cylindrical shell is

usually lined with an abrasion-resistant
material such as manganese steel or rubber.
Nanoscale Lithography
Nanolithography is the branch of nanotechnology
concerned with the study and application of fabricating
nanometer-scale structures, meaning patterns with at
least one lateral dimension between 1 and 100 nm.
Photolithography
• Optical lithography or UV lithography, is a process used in
microfabrication to pattern parts of a thin film or the bulk of
a substrate. It uses light to transfer a geometric pattern
from a photomask to a light-sensitive chemical
"photoresist", or simply "resist," on the substrate.
• A series of chemical treatments then either engraves the
exposure pattern into, or enables deposition of a new
material in the desired pattern upon, the material
underneath the photo resist.
• Projection Printing Technique
• Limited by diffraction limit
Photolithography
• Resist film
➢ Negative resist: After development, the
exposed structure is higher than the
surrounding due to crosslinking of
polymer chains.
➢ Positive resist: After development, the
exposed structure is deeper than the
surrounding due to chopping of polymer
chains.

◆PMMA (Poly-methyle-metacrylate)
-one of the first e-beam resists (1968)
-standard positive resist
-resolution<10 nm
-available with high (950K) and low (50k)
molecular weight
Photolithography
 Photolithography
• A photoresist is a light-sensitive material used in several
industrial processes, such as photolithography and
photoengraving, to form a patterned coating on a surface.

• A positive resist is a type of photoresist in which the portion

of the photoresist that is exposed to light becomes soluble
to the photoresist developer. The portion of the photoresist
that is unexposed remains insoluble to the photoresist
developer.

• A negative resist is a type of photoresist in which the portion

of the photoresist that is exposed to light becomes insoluble
to the photoresist developer. The unexposed portion of the
photoresist is dissolved by the photoresist developer.
Photolithography
• Typical photolithographic process consists of producing a mask
carrying the requisite pattern information and subsequently
transferring that pattern, using some optical technique into a
photoactive polymer or photoresist.
Photolithography
• Wafer preparation---cleaning
1) Typical contaminants that must be removed prior to
photoresist coating:
•dust from cleaving (minimized by laser cleaving)
•atmospheric dust (minimized by good clean room practice)
•abrasive particles (from lapping or CMP)
•lint from wipers (minimized by using lint-free wipers)
•

2) Standard degrease:
– 2-5 min. soak in acetone with ultrasonic agitation
– 2-5 min. soak in methanol with ultrasonic agitation
– 2-5 min. soak in DI H2O with ultrasonic agitation
– 30 sec. rinse under free flowing DI H2O
– spin rinse dry for wafers; N2 blow off dry for tools and chucks

• For particularly troublesome grease, oil, or wax stains:

– Start with 2-5 min. soak in 1,1,1-trichloroethane (TCA) or
trichloroethylene (TCE) with ultrasonic agitation prior to acetone
Photolithography
• Wafer preparation - primers

➢ Adhesion promoters are used to assist resist coating.

➢Ideally want no H2O on wafer surface
– Wafers are given a “singe” step prior to priming and coating
•15 minutes in 80-90°C convection oven

➢Used for silicon:

– primers form bonds with surface and produce a polar (electrostatic)
surface
– most are based upon siloxane linkages (Si-O-Si)
•1,1,1,3,3,3-hexamethyldisilazane (HMDS), (CH3)3SiNHSi(CH3)3
•trichlorophenylsilane (TCPS), C6H5SiCl3
•bistrimethylsilylacetamide (BSA), (CH3)3SiNCH3COSi(CH3)3
 Photolithography
• Photoresist Spin Coating

• Wafer is held on a spinner chuck by vacuum and resist is coated to uniform

thickness by spin coating.
• Typically 3000-6000 rpm for 15-30 seconds.
• Resist thickness is set by:
– primarily resist viscosity
– secondarily spinner rotational speed
• Resist thickness is given by t = kp2/w1/2, where
– k = spinner constant, typically 80-100
– p = resist solids content in percent
– w = spinner rotational speed in rpm/1000
• Most resist thicknesses are 1-2 mm for commercial Si processes
Photolithography
• Prebake

Used to evaporate the coating solvent and to densify the resist after spin coating.
• Typical thermal cycles:
– 90-100°C for 20 min. in a convection oven
– 75-85°C for 45 sec. on a hot plate
• Commercially, microwave heating or IR lamps are also used in production lines.
• Hot plating the resist is usually faster, more controllable, and does not trap
solvent like convection oven baking.
Photolithography
• Align/Expose/Develop
Photolithography
• Etching/remove photoresist

photoresist has same polarity as final film;

photoresist never touches the substrate wafer.
Electron-beam Lithography
• Electron-beam lithography (often abbreviated as e-beam
lithography) is the practice of scanning a focused beam of
electrons to draw custom shapes on a surface covered
with an electron-sensitive film called a resist
("exposing").The electron beam changes the solubility of
the resist, enabling selective removal of either the
exposed or non-exposed regions of the resist by
immersing it in a solvent ("developing").
• Allows accuracy down to as small as 10nm dimensions
• highly accurate and reliable pattern writing
E-beam Lithography
E-beam lithography
• Challenge

➢Charging effect: Complicate exact

focusing of electron-beam, displacement
and distortion of exposed structures.

➢Proximity effect: Scattering of

electrons in resist film and substrate,
unwanted additional exposure.
X-Ray Lithography
• X-ray lithography, is a process used in electronic industry
to selectively remove parts of a thin film. It uses X-rays to
transfer a geometric pattern from a mask to a light-
sensitive chemical photoresist, or simply "resist," on the
substrate. A series of chemical treatments then engraves
the produced pattern into the material underneath the
photoresist.

• Allowing smaller feature sizes. Having short wavelengths

(below 1 nm), X-rays overcome the diffraction limits of
optical lithography
E-beam Lithography
Summary of Lithographic Techniques
Source Form Disadvantages Advantages

Photolithography UV Light Projection Limited by UV Cheap

Printing Wavelength

Electron-beam focused Direct Writing Expensive Highly

lithography beam of Accurate
electrons
X-Ray X-Ray Proximity Expensive/Fr Accurate/
Lithography Printing agile Masks Efficient
Fast
Synthesis of Nanomaterials
OUTLINE
• Top-Down Approach
1. Ball-Milling
2. Nanoscale Lithography (UV, X-ray and e-beam)

• Bottom-Up Approach
1.Thermal Methods (Hydrothermal and Solvothermal)
2.Vapour Phase Deposition (Physical and Chemical)
3. Self-Assembly Techniques (Self-Assembled Monolayers,
Layer-by-Layer Approach, Langmuir-Blodgett Films)
4. Sol-Gel Techniques
 Hydrothermal Synthesis
• The reactants are dissolved (or placed) in water
or another solvent (solvothermal) in a closed
vessel
• Bomb is heated above BP
• Conventional or MW oven
• Hydrothermal synthesis is used for oxide
nanoparticle synthesis as the solubility is high in
the alkaline medium.

Nazari, G.A., Pistoria, G. Lithium Batteries; Klumer Academic Pubs.: Boston, 2004.
 Hydrothermal Synthesis
• Hydrothermal synthesis involves the chemical reaction of materials
in aqueous solution heated (usually above BP; supercritical water)
in a sealed vessel (bomb)

• Alkaline solution used to increase solubility (for a dissolution-

precipitation reaction)

• Useful for Nanomaterials!

• Oxides (TiO2, VOx, MxMnO2)
• Layered oxides: nanowires/tubes
• C-nanotubes can be formed this way
• Some elemental nanostructures (eg: Bi)

• It is difficult to predict the resultant morphology of the product

Hydrothermal Synthesis: Conditions
Closed autoclave: Autogenous pressure
Critical temperature: 374.15˚C,
Critical pressure: 220 bar (22.064 MPa)
Critical density: 0.321g/cm3
Above the critical temperature and critical pressure: supercritical, fluid
phase
 BaTiO3 Nanoparticles
• Ba(OH)2 + TiO2 → BaTiO3 nanoparticles
• 300 - 450°C, HT
• Two proposed mechanisms:
• Dissolution-recrystallization
• In situ crystallization

Hakuta, R., Ura, H. Hayashi, H, and Arai, K. Ind. Eng. Chem. Res. 2005, 44, 840-846
 In-situ crystallization
• Non-dissolved TiO2 reacts with barium and hydroxide ions

Eckert, J.O., Hung-Houston, C.C., Gersten, B.L., Lencka, M.M., Riman, R.E., J. Am.
Ceram. Soc. 1996, 79, 2939.
Examples of nano- and (A) SnO2 hollow spheres, (B) TiO2 spheres, (C)
TiO2 nanowire arrays, (D) NiO flake-flowers, (E)
SnO2 flower-like particles, (F) peachstone-like
CuO architectures, (G) cubic Fe2O3, and (H)
microstructures obtained with hexagonal (KxNa1 − x)NbO3 perovskite.
Based on J. Yuan, C. Chen, Y. Hao, X. Zhang, B.
Zou, R. Agrawal, C. Wang, H. Yu, X. Zhu, Y. Yu,
hydrothermal methods. Z. Xiong, Y. Luo, H. Li, Y. Xie, SnO2/polypyrrole
hollow spheres with improved cycle stability as
lithium-ion battery anodes, J. Alloys Compd. 691
(2017) 34–39; E. Grabowska, M. Marchelek, T.
Klimczuk, G. Trykowski, A. Zaleska-Medynska,
Noble metal modified TiO2 microspheres: surface
properties and photocatalytic activity under UV–vis
and visible light, J. Mol. Catal. A: Chem. 423
(2016) 191–206; Z. Yu, X. Qu, W. Yang, J. Peng,
Z. Xu, A facile hydrothermal synthesis and
memristive switching performance of rutile
TiO2 nanowire arrays, J. Alloys Compd. 688 (Part
B) (2016) 37–43; R. Miao, W. Zeng, Q. Gao, SDS-
assisted hydrothermal synthesis of NiO flake-
flower architectures with enhanced gas-sensing
properties, Appl. Surf. Sci. 384 (2016) 304–310; Q.
Wang, N. Yao, D. An, Y. Li, Y. Zou, X. Lian, X.
Tong, Enhanced gas sensing properties of
hierarchical SnO2nanoflower assembled from
nanorods via a one-pot template-free hydrothermal
method, Ceram. Int. 42 (2016) 15889–15896; J.
Xia, H. Li, Z. Luo, K. Wang, S. Yin, Y. Yan, Ionic
liquid-assisted hydrothermal synthesis of three-
dimensional hierarchical CuO peachstone-like
architectures, Appl. Surf. Sci. 256 (2010) 1871–
1877; W.X. Jin, S.Y. Ma, Z.Z. Tie, X.H. Jiang,
W.Q. Li, J. Luo, X.L. Xu, T.T. Wang, Hydrothermal
synthesis of monodisperse porous cube, cake and
spheroid-like α-Fe2O3 particles and their high gas-
sensing properties, Sens. Actuators B Chem. 220
(2015) 243–254
Hydrothermal Route
• Advantages
• New materials
• Easy, relatively cheap

• Disadvantages
• Difficult to control morphology, size
• Not for all materials
• May obtain variation in size
• Inability to monitor the growing crystals in the
autoclave
Solvothermal Synthesis
• In a typical solvothermal method, all reagents (metal
oxide precursors, pH stabilizer, and H2O/solvent) are
mixed together, introduced into a Teflon-lined stainless
steel autoclave, and heated.

• After the reaction is complete, the autoclave is cooled to

room temperature and the product is washed and dried in
an atmosphere of oxygen, nitrogen, or argon
Solvothermal Synthesis
• The solution pH during the synthesis has great influence
on the morphology and crystalline phase of the
particles.

FE-SEM images of micro-flowers composed of sheets of grown ZnO

nanostructures (A, B) at pH 10, (C, D) at pH 11, and (E, F) at pH 12.
Reference: R. Wahab, Y.-S. Kim, H.-S. Shin, Synthesis, characterization and effect of pH variation
on zinc oxide nanostructures, Mater. Trans. 50 (2009) 2092–2097.
 Evaporation and Condensation
• The evaporation and condensation are the fundamental
phenomena in preparing thin films with nano meters
thickness.
Substrate If a condensible vapor is produced by
physical means and subsequently
Condensation deposited on a solid substrate, it is
called physical vapour deposition.
vapor
If a volatile compound of a material
react, with or without other gases, to
produce a nonvolatile solid film, it is
Evaporation called the chemical vapour
energy deposition.
Source
Physical Vapour Deposition (PVD)
• Physical methods produce the atoms that deposit
on the substrate
• Evaporation
• Sputtering
• Sometimes called vacuum deposition because
the process is usually done in an evacuated
chamber
• PVD is used for metals.
• Dielectrics can be deposited using specialized
equipment
Evaporation
• Rely on thermal energy supplied to the crucible or boat to
evaporate atoms
• Evaporated atoms travel through the evacuated space
between the source and the sample and stick to the
sample
• Few, if any, chemical reactions occur due to low
pressure
• Surface reactions usually occur very rapidly and there is
very little rearrangement of the surface atoms after sticking
• Thickness, uniformity and coverages are issues
Thermal Evaporation
1. Vacuum (10-4 – 10-8 Torr)
2. Source material is heated
and evaporates
3. Source material deposits on
substrate
 Control concentration of
growth species in vapor
 Thickness measured in
situ
 Angstroms to 100’s nm
thick layers
 Sputtering
1. Rough Vacuum (10’s of
mTorr) with a constant
stream of gas
2. High voltage forms plasma
ex: Ar gas → Ar+ + e-
3. Plasma (Ar+) accelerated
towards target
4. Ar+ hits target, neutral target
atoms (Au) are ejected
5. Ejected atoms (Au) deposit
on substrate
Sputtering
◼ Sputter deposition is done in
a vacuum chamber
(~10mTorr) as follows:
– Plasma is generated by
applying an RF signal
producing energetic ions.
– Target is bombarded by these
ions (usually Ar+).
– Ions knock the atoms from the
target.
– Sputtered atoms are
transported to the substrate
where deposition occurs.
Deposition Conditions
• Temperature: Room to higher
• Pressure: 100 mtorr
• compromise between increasing number of Ar
ions and increasing scattering of Ar ions with
neutral Ar atoms
• Power
• Heating of target material
• Low temperature metals can melt from
temperature rise caused by energy transfer
from Ar ions
Sputter sources
• Magnetron
• Magnetic field traps freed electron near target
• Move in helical pattern, causing large number of scattering
events with Ar gas – creating high density of ionized Ar
• Ion beam
• Plasma of ions generated away from target and then accelerated
toward start by electric field
• Reactive sputtering
• Gas used in plasma reacts with target material to form compond
that is deposited on wafer
• Ion-assisted deposition
• Wafer is biased so that some Ar ion impact its surface, density
the deposited film. May sputter material off of wafer prior to
deposition for in-situ cleaning.
Chemical Vapour Deposition (PVD)
• Chemical Vapor Deposition is the formation of a non-
volatile solid film on a substrate by the reaction of vapour
phase chemicals (reactants) that contain the required
constituents.

• The reactant gases are introduced into a reaction

chamber and are decomposed and reacted at a heated
surface to form the thin film.
Chemical Vapour Deposition (PVD)
• Fundamental principle is that a chemical reaction takes
place between the source gases.

• The product of that is a solid material that condenses on

all surfaces inside the reactor.

• Precursor gases (often diluted in carrier gases) are

delivered into the reaction chamber at approximately
ambient temperatures.
Chemical Vapour Deposition (PVD)
Sequential Steps:
1. Transport of reacting to the substrate surface
2. Absorption of species on the substrate surface
3. Heterogeneous surface reaction catalyzed by the substrate
surface.
4. Desorption of gaseous reaction byproducts
5. Transportation of reaction by-products away from the
substrate
Events in a CVD
Coating Characteristics
• CVD coatings are typically:
• Fine grained
• Impervious
• High purity

• CVD coatings are usually only a few microns

thick and are generally deposited at fairly slow
rates, usually of the order of a few hundred
microns per hour.
The CVD Apparatus

Schematic diagram of CVD apparatus

 The CVD Apparatus
• A CVD apparatus will consist of several basic components:
1. Gas delivery system – For the supply of precursors to the reactor
chamber
2. Reactor chamber – Chamber within which deposition takes place
3. Substrate loading mechanism – A system for introducing and
removing substrates, mandrels etc
4. Energy source – Provide the energy/heat that is required to get the
precursors to react/decompose.
5. Vacuum system – A system for removal of all other gaseous species
other than those required for the reaction/deposition.
6. Exhaust system – System for removal of volatile by-products from the
reaction chamber.
7. Exhaust treatment systems – In some instances, exhaust gases may
not be suitable for release into the atmosphere and may require
treatment or conversion to safe/harmless compounds.
8. Process control equipment – Gauges, controls etc to monitor process
parameters such as pressure, temperature and time. Alarms and safety
devices would also be included in this category.
Energy Sources
• There are several suitable sources of heat for CVD
processes. These include:
• Resistive Heating e.g. tube furnaces
• Radiant Heating e.g. halogen lamps
• Radio Frequency Heating e.g. induction heating
• Other energy sources may include UV-visible light or
lasers as a source of photo energy.
Precursors
• Materials are deposited from the gaseous state during
CVD. Thus precursors for CVD processes must be
volatile, but at the same time stable enough to be able to
be delivered to the reactor.
• Typical Precursor Materials: Halides - TiCl4, TaCl5, WF6,
etc
• Hydrides - SiH4, GeH4, AlH3(NMe3)2, NH3, etc
• Metal Organic Compounds –
• Metal Alkyls - AlMe3, Ti(CH2tBu)4, etc
• Metal Alkoxides - Ti(OiPr)4, etc
• Metal Dialylamides - Ti(NMe2)4, etc
• Metal Diketonates - Cu(acac)2, etc
• Metal Carbonyls - Ni(CO)4, etc
• Others – include a range of other metal organic compounds,
complexes and ligands
Self-Assembled Monolayers
Adsorbate
A molecular species of gas, dissolved substance or liquid which adheres to or is
adsorbed in an extremely thin surface layer of a solid substance.

Substrate
surface where the a chemical specie is adsorbed.

Interactions between substrate and adsorbate:

Physisorption - the enthalpies of interactions are rather low (∆H < 10
kcal/mol, typically from van der Waals forces)
Chemisorption - the formation of covalent bonds, more stable than their
physisorbed counterparts (∆H > 10 kcal/mol)
Other forms: hydrogen bonding, donor–acceptor and ion pairing, etc.
 53

Self-Assembled Monolayers (SAMs)

SAMs are organic assemblies that are formed spontaneously by
the adsorption of molecular constituents from solution or gas phase
onto a substrate with a specific affinity of its headgroup.

alkanethiol on HS(CH2)nX where X is the end group of the chain

gold (Au) –CH3, –OH, or –COOH

Review article: J.C. Love, et al., Chem. Rev. 2005, 105, 1103 (G. Whitesides group, Chem
Dept, Harvard University)
 54

History and Models

In 1980, SAMs of alkyltrichlorosilane on glass
In order to form a complete monolayer, the silane
groups condense with surface hydroxyl groups to
form a thin layer of polysiloxane.
In 1983, SAMs of dialkyldisulfides on Au
The assembly is held together by the bonds
between the sulfur headgroups and the gold
surface as well as van der Waals interactions
between neighboring hydrocarbon chains.
In 1985, SAMs of alkanoic acids on Al2O3
Others: other sulfur head compounds, like disulfides
and sulfides, on metals (especially Au, but also Ag, Cu,
and even Pt, Fe, and Ni) and semiconductors (GaAs);
trialkyl-, trichloro-, or trialkoxysilanes on SiO2/Si,
Al2O3/Al, mica, glass; fatty acids on metal oxides
(Al2O3, AgO); hydrocarbons on Si.
 55

Adsorbates and Substrates that Form

SAMs
 56

Why n-alkanethiolate SAMs on Au

Well-ordered SAMs can be formed from a variety of sulfurcontaining species (i.e.,
thiols, sulfides, disulfides).
Covalent bond strength between gold and thiolate = 44 kcal/mol, one of the highest
between a non-metal and a metal, forms rapidly, typically within seconds to minutes.
The gold surface is relatively chemically inert; it does not readily form a surface oxide
nor keep a strong hold of adventitiously adsorbed material, and therefore SAMs can
easily be prepared in ambient conditions.
At low surface coverage, the alkanethiolate molecules lie flat with their hydrocarbon
backbones parallel to the gold surface.
At higher surface coverages, the molecules begin to stand up, with the hydrocarbon
tails tilting approximately 30˚ from the surface normal and nominally in the all-trans
configuration so as to maximize van der Waals interactions.

[sqrt(3)×sqrt(3)]R30°alkanethiolate lattice
on Au(111); the alternating orientation of the
alkane chains defines a c(4 x 2) superlattice
structure.
Self-Assembly of a Thiophene Derivative

Lapitan Jr, L. D., Tongol, B. J. V., & Yau, S. L. (2010). Molecular assembly and electropolymerization of
3, 4-ethylenedioxythiophene on Au (111) single crystal electrode as probed by in situ electrochemical
STM in 0.10 M HClO4. Langmuir, 26(13), 10771-10777.
Self-Assembly of a Thiophene Derivative

High-resolution STMimage of EDOT adlayer in the ordered domain labeled I in Figure

3d on Au(111) electrode obtained at E = þ0.600 V with (b) the corresponding
molecular model structure.
Self-Assembly of a Thiophene Derivative

Lapitan Jr, L. D., Tongol, B. J. V., & Yau, S. L. (2010). Molecular assembly and electropolymerization of
3, 4-ethylenedioxythiophene on Au (111) single crystal electrode as probed by in situ electrochemical
STM in 0.10 M HClO4. Langmuir, 26(13), 10771-10777.
Layer-by-Layer (LbL) Self-assembly
Charge interaction
++ ++
++ + ++ +
++ + ++ +
+++ +++

++ ++
Multilayer
++ + ++ + Multifunctional
++ + ++ +
+++ +++ Film
Langmuir-Blodgett(L-B)films
Hydrophobic/hydrophilic interaction
 Sol-Gel Techniques
The sol-gel process (gelation): a change from a liquid
state to a gel state through poly-condensation reactions.

A sol is a stable dispersion of colloidal particles or

polymers in a solvent. The particles may be amorphous
or crystalline. Typical size few nm.

A gel consists of a three dimensional

continuous network of the sol particles,
which encloses a liquid phase.

• Sol-gel may be used to prepare materials

with a variety of shapes, such as porous
structures, thin fibres, dense powders and
thin films.
 Sol - Gel

During gelation covalent bonding, van der Waal- and H-

bondings are formed.

Particulate sols: Gelling via agglomeration

Polymeric sols: Gelling via condensation
If the gel is dried by evaporation, then the capillary forces will result in shrinkage,
the gel network will collapse, and a xerogel is formed. If drying is performed under
supercritical conditions, the network structure may be retained and a gel with large
pores may be formed. This is called an aerogel, and the density will be very low.
 How is a sol stabilised?
• A sol consists of a liquid with colloidal particles which are not
dissolved, but do not agglomerate or sediment.
• Small particles tend naturally to agglomerate due to van der
Waals forces and a tendency to decrease the total surface
energy. In order to counter act the van der Waals
interactions, repulsive forces must be established.
Steric hindrance (surfactant): Adsorption Electrostatic repulsion: Adsorption of charged
of a layer of organic molecules → species onto the surface of the particles
particles are prevented from approaching →repulsion between the particles and
each other →reducing the role of the van agglomeration will be prevented. Aqua
der Waals forces. Works best in solutions.
concentrated dispersions and organic
media.
 Point of Zero Charge – PZC
- All particles have ionic groups that control the surface potential
- Counter ions in the solution will cover this layer, shielding the rest
of the solution from the surface charges
- For hydrous oxides the surface potential will be determined by
reactions with the ions H+ and OH- the surface potential is pH
dependent.
M-OH + H+ → M-OH2+
M-OH + OH- → M-O- + H2O

• For pH > PZC the surface is negatively charged

• For pH < PZC the surface is positively charged
Typical values: MgO 12.0, Al2O3 9.0, TiO2 6.0, SnO2 4.5, SiO2 2.5
The Double Layer In an electric field the particle will move
toward the electrode with the opposite
charge. It will carry the adsorbed layer
and part of the counter ions.

The “slip plane” divides the part that

moves with the particle and the solution.
The potential at the slip plane is called
the zeta (z) potential fz. The pH for which
fz=0 is called the isoelectrical point (IEP)

The stability of a colloid depends on fz;

the larger the fz the more stable the
colloid. Should be > 30-50 mV.

Given the same surface potential, the

repulsive forces will increase with the
particle size.
Silica gel through sol-gel Processing
• A sol-gel process occur in several steps:
• Hydrolysis and condensation of molecules. (Formation of
a sol)
• Gelation (sol-gel transformation)
• Ageing
•Drying
Hydrolysis and Condensation
• The starting point for formation of a silica gel may be
alkoxides or silanols. These are reacted to give siloxane
groups.
 Network Formation
-During reaction, objects will grow.
However, a gel may not form
- As the sol aggregates the viscosity
will increase until a gel is formed.
The sol-gel transition (gel-point) is
reached when a continuous
network is formed.
- The gel-time is determined as the
time when it is possible to turn the
container upside-down. All fluid is
kept in the gel, and the volume is
maintained.
 Ageing
• As the viscosity rapidly increase, the solvent is “trapped” inside the
gel. The structure may change considerably with time, depending
on pH, temperature and solvent. The gel is still “alive”.

• The liquid phase still contains sol particles and agglomerates,

which will continue to react, and will condense as the gel dries.

• The gel is originally flexible. Groups on neighboring branches will

condense, making the gel even more viscous. This will squeeze
out the liquid from the interior of the gel, end shrinkage occur. This
process will continue as long as there is flexibility in the gel.

• Hydrolysis and condensation are reversible processes, and

material from thermodynamically unfavorable points will dissolve
and precipitate at more favorable points. (Note the similarity to the
sintering process)
Drying
• When the liquid is removed from the gel several things may happen.
When the liquid in the gel is replaced by air, major changes to the
network structure may occur. If the structure is maintained, an aerogel is
formed If the structure collapses, a xerogel is formed.

• Normal drying of the gel leads to structural collapse due capillary forces
drawing the walls of the pores together, and reducing the pore size.

• OH groups on opposite sides may react and form new bonds by

condensation.

• Cracking may occur when the tension in the gel is so large that it cannot
shrink anymore.

• Gas will enter the pores with a thin film of liquid on the walls. This will
evaporate and only isolated spaces with liquid are left.
Drying