Module:5 Functional materials 7 hours

❖ Composites - types and properties

❖ Polymers - thermosetting and thermoplastic polymers –
synthesis and application (ABS & BAKELITE)
❖ Conducting polymers- polyacetylene and effect of doping
❖ Nanomaterials – introduction, bulk vs. nano (quantum dots)
❖ Top-down and bottom-up approaches for synthesis, and
❖ Properties of nano Au.

1
Module 5
Functional
Materials
 What is a Composite Material?

❑ A composite material is a combination of two

materials with different physical and chemical
properties.

❑ The materials combined to produce a new material

which is specific to a definite work, for instance, to
become stronger, lighter, or resistant to electricity and
also improve strength and stiffness.

❑ The components maintain their identity within the

composite, i.e. they do not dissolve or completely
merge into one another, though they act in concert.
 Constituents of composites
❑ Matrix (Continuous phase) : Continuous or bulk material

❑ Reinforcement (Dispersed Phase) : Added primarily to increase the strength

and stiffness of matrix

❑ Reinforcement is generally - form of fibers, particles, whiskers or flakes

Interface

Matrix Composite
Composite
Reinforcement
Re-inforcement
(Dispersed Phase)
Functions (requirements) of matrix:
1. Keep the fibers in place in the structure

2. Help to distribute or transfer loads

3. Protect fillers, both in structure & before & during
fabrication
4. Control electrical & chemical properties of composite
5. Carry interlaminar shear

5
 Types of composites

Natural Composites
(Exist in animal and Synthetic composites
plants) (Man-Made)
Wood = Cellulose + Mud Bricks = Mud+
Lignin Straw
Bone= Hydroxyapatite Reinforced Concrete
+ Collagen Fibre glass etc.
 Classification of
composite materials

Based on the matrix Based on the

materials geometry of
reinforcement

⮚ Polymer matrix composite (PMCs)

⮚ Particulate reinforced composites
⮚ Metal Matrix composite (MMCs)
⮚ Whisker/Flakes reinforced composites
⮚ Ceramic matrix composite (CMCs)
⮚ Fibre reinforced composites
⮚ Carbon/carbon composites (c/Cs)
 Polymer matrix Composites
o Polymers constitute the most important matrix
materials and are used in more than 95% of the
composite products in use today.

• Polymer
•Resin

•Thermosets

•Thermoplastic

•Elastomer

8
 Polymer matrix composites
⮚ Thermoplastic polymer matrices
• Thermoplastics are incorporated in the
composite system by melting and ⮚ Elastomer based composites
solidifying by cooling. - The greater extensibility and
high-energy storing capacity
• The physical reaction being reversible in make them a suitable
nature. continuous phase for
composite materials.
• Thermoplastics have low creep resistance
and low thermal stability compared to - Unlike plastics, a wide variety
thermosetting resins. of flexible products can be
made using elastomers as the
⮚ Thermoset polymer matrices
matrix phase.
▪ Thermosetting resins are more common
for the development of composite systems. - They offer elastic strain higher
▪ Solidification from the liquid phase takes than that of metals and can
be stretched rapidly, even
place by the action of an irreversible under small loads.
chemical cross- linking reaction, generally
in the presence of heat and pressure.

9
Applications of Polymer matrix composites

The Fiber-line Bridges,Denmark

 Metal- matrix composites (MMC)
❖ Metal Matrix Composites are composed of a metallic matrix (Al,Mg,Fe,Cu
etc) and a dispersed ceramic (oxide, carbides) or metallic phase( Pb,Mo,W
etc).

❖ Ceramic reinforcement may be silicon carbide, boron, alumina, silicon

nitride, boron carbide, boron nitride etc.,whereas metallic reinforcement
may be tungsten, beryllium etc.

❖ From a material point of view, when compared to polymer matrix

composites, the advantages of MMCs lie in their retention of strength and
stiffness at elevated temperature, good abrasion and creep resistance
properties.

❖ Most MMCs are still in the development stage or the early stages of
production and are not so widely established as polymer matrix composites.
The biggest disadvantages of MMCs are their high costs of fabrication.

❖ There are also advantages in some of the physical attributes of MMCs such
as no significant moisture absorption properties, non-inflammability and
resistance to most radiations.
11
 Metal- matrix composites (MMC)
❖ Only light metals are responsive, with their low density proving an advantage.
Titanium, aluminium and magnesium are the popular matrix metals currently
in vogue, which are particularly useful for aircraft applications.

❖ If metallic matrix materials have to offer high strength, they require high
modulus reinforcements.

❖ The strength-to-weight ratios of resulting composites can be higher than most

alloys.

❖ The melting point, physical and mechanical properties of the composite at

various temperatures determine the service temperature of composites.

❖ They can withstand elevated temperature in corrosive environment than

polymer composites. However, practically, the choices for low temperature
applications are not many.

❖ The choice of reinforcements becomes more stunted with increase in the

melting temperature of matrix materials.

12
 Applications of Metal matrix composites (MMC)
o Carbide drills are often made from a tough cobalt
matrix with hard tungsten carbide particles inside.

o Modern high-performance sport cars, such as those

built by Porsche, use rotors made of carbon fiber
within a silicon carbide matrix.

o Metal Matrix Composite (MMC) are used in Diesel

Piston, disk break
Diesel Piston
o The F-16 Fighting Falcon uses monofilament silicon
carbide fibres in a titanium matrix for a structural
component of the jet's landing gear.

o Today these applications are found most often in

aircraft components, space systems and high-end
or "boutique" sports equipment.

o MMCs are used for Space Shuttle, commercial

airliners, electronic substrates, bicycles,
automobiles, golf clubs and a variety of other
applications. Cast Brake
Disk
13
 Ceramic Matrix composite (CMC)
o A given ceramic matrix can be reinforced with either
discontinuous reinforcements, such as particles,
whiskers or chopped fibres, particulates having
compositions of Si3N4, SiC, AlN, titanium diboride,
boron carbide, and boron nitride or with continuous
fibres.
o Characteristics of CMC
❖ High-temperature stability
❖ High thermal shock resistance
❖ High hardness
❖ High corrosion resistance
❖ Light weight
❖ Nonmagnetic and nonconductive properties
❖ Versatility in providing unique engineering solutions

14
 Ceramic matrix composites (CMC)
❖ Ceramics can be described as solid materials which exhibit very
strong ionic bonding in general and in few cases covalent bonding.

❖ Naturally, ceramic matrices are the obvious choice for high

temperature applications.

❖ High melting points, good corrosion resistance, stability at

elevated temperatures and high compressive strength, render
ceramic-based matrix materials a favourite for applications
requiring a structural material that doesn’t give way at
temperatures above 1500ºC.

15
Applications:

❖ CMCs find promising applications in the area of cutting tools and

in heat engines where the components should withstand aggressive
environments.

❖ In Aircraft engines - use of stator vanes formed of CMC in the hot

section of the F136 turbofan engine is under consideration.

16
 Applications of CMC
• Ceramic-matrix composites are now also commercially available as brake rotors
for automobiles.

✔ Ceramic-matrix composite brake rotors have also been demonstrated for the
Inter-City Express high-speed trains in Germany, where a total weight savings of
5.5 metric tons is obtained per train set.
 Classification based on molecular forces

POLYMER

Thermo Thermosetting
polymer polymer

Linear long chain polymer with weak Rigid link between polymer chains –
intermolecular forces – softened on once shaped, cannot be softened by
heating and hardened on cooling application of heat
reversibly

18
 Thermoplastics
Thermoplastics: Softened on heating and
hardened on cooling reversibly. Can be
processed repeatedly. Linear, long chain
polymer, flexible.

Chains are linked by weaker intermolecular

forces and there is no cross-linking so the
chains can move when heated - softens,
becomes hard on cooling and weak links
reformed.

Thermoplastics can be crystalline or

amorphous

Eg. PE, PP, PVC, PS, PTFE (teflon) etc.

Applications: Polyethylene buckets,

polystyrene cups, nylon ropes etc.
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 Amorphous and crystalline

Crystal Amorphous

20
 Thermosetting plastics
Thermosetting polymers: Once
shaped, cannot be softened by the
application of heat.
Rigid, 3D cross-linked polymer.
Thermosetting polymers – adjacent
polymer chains held through strong
covalent bonds - 3D network. Once
set cannot be remoulded.

Excess heat char the material.

Eg. Phenol-formaldehyde, urea-

formaldehyde, melamine-
formaldehyde, epoxy-resin etc.
Application: Bakelite - electrical
switches, melamine-formaldehyde -
cutlery etc.
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 Thermo Vs Thermosetting polymers

Thermoplastic polymer Thermosetting polymer

Softened on heating Do not softened on heating

Polymer chains linked by weak Polymer chains linked by strong

intermolecular forces covalent bonds
Formed mostly by addition Formed mostly by condensation
polymerization polymerization
Can be reshaped and reused Cannot be reshaped and reused

Usually soft, weak and less brittle Usually, hard, strong and more
brittle
Can be reclaimed from waste Cannot be reclaimed from waste

Usually soluble in some organic Insoluble in almost all organic

solvents solvents
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 Properties and engineering
applications

Types of Thermoplastic resins:

Vinyl resins
(i) PVC
(ii) TEFLON or FLUON
(iii) ABS (Acrylonitrile Butadiene Styrene)

Types of Thermosetting resins:

Phenolic resins or phenoplasts

(i) Bakelite
(ii) Novolac
THERMO POLYMERS

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Acrylonitrile-Butadiene-Styrene (ABS) Copolymer

ABS:

25
Acrylonitrile-Butadiene-Styrene (ABS) Copolymer

ABS copolymer has three monomers, Acrylonitrile-

Butadiene-Styrene - based on relative amount of
monomers the final product varied considerably.

There are large range of ABS copolymers!

ABS polymers have high impact strength and

softening points.
26
 Preparation of ABS Copolymer
Grafting – acrylonitrile and styrene polymerized in the
presence of polybutadiene latex.

50 ˚C

A wide range of products is possible depending upon the

amounts of reactants used.

ABS polymer prepared in this way consist of styrene-

acrylonitrile (SAN) copolymer with polybutadiene27
dispersed throughout matrix.
 Properties of ABS Copolymer

ABS copolymers have three monomers – based on

relative amount of monomers the final product varied
considerably.

There are large range of ABS copolymers!

ABS polymers have high impact strength and

softening points.

Moulded ABS polymer have a better surface

appearance.

ABS is a thermo polymer - it can be injection moulded

and extruded.
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 Application of ABS Copolymer

ABS polymers used in places where high

toughness, rigidity and good appearance is
required.

Used in automobile fascia panels and radiator

grilles

House hold appliances

Telephones

Pipe and pipe fittings.

29
THERMOSETTING POLYMERS

30
 Thermosetting polymers-Phenolic resin

Thermoset polymers - once formed cannot be

reshaped due to high degree of cross linking.

Thus thermoset polymers prepared in molds

that yields desired object.

Most important of this class of polymers are

Phenol-formaldehyde (PF)
Urea-formaldehyde,
Melamine-formaldehyde etc.
31
 Thermosetting polymers-Phenolic resin
Excess formaldehyde and allowing reaction to continue to
almost all the available o- and p- positions of phenol
molecules, a cross-linked 3D polymer resulted - bakelite

32
 Uses of Bakelite

Electric insulator parts like switches, plugs,

switch-boards, heater-handles, etc.

Moulded articles like telephone parts, cabinets

for radio and television etc.

For impregnating fabrics, wood, asbestos and

paper,

For making bearing for propeller shafts used in

paper industry and rolling mills.
33
CONDUCTING POLYMERS

34
 CONDUCTING POLYMERS
[Link]

The Nobel Prize in Chemistry 2000

The Nobel Prize in Chemistry 2000 was awarded jointly to Alan J. Heeger, Alan G. MacDiarmid and Hideki
Shirakawa "for the discovery and development of conductive polymers". 35
 Conducting polymers

Polymers – (mostly) insulator i.e poor conductor of

electricity – due to non-availability of free e- for conduction.

Polymers which could conduct electricity – conducting

polymers

The conducting polymer was first discovered by Japanese

scientist, Hideki Shirakwa in 1977 and polymer made is
‘polyacetylene’.

For his discovery he has been awarded Nobel Prize along

with Alan Mac Diarmid and Alan Heeger in the year 2000.

36
Energy bands

37
 Conducting polymers

Certainly, if polymer has to conduct electricity it

should have e- in conduction band i.e in Lowest
Unoccupied Molecular Orbital (LUMO)

or

It should have positive hole in valence band i.e

Highest Occupied Molecular Orbital (HOMO)

38
 Conducting polymers
Electrical conductivity of conducting polymers ranges
from insulators (10-10 S/cm) to semiconductor (~10-5
S/cm) to those near (104 S/cm) to good conductor
such as copper (5 x 105 S/cm).
Polymer Electrical conductivity
s (ohm-1 m-1)
Phenol- 10-9 – 10-10
formaldeh
yde
PMMA <10-12 σ*

Nylon-6,6 10-12 – 10-13

PS <10-14
10-15 –of10conducting
PE Advantage -17
polymer is that they canσ
Energy diagram of polymers
be fabricated
PTFE <10-17 into light, flexible sheets. which has saturated back
bone PTFE, PE, PS
39
 Conducting polymer

Conductin
g polymers

Extrinsi
Intrinsic Doped
c

40
INTRINSIC CONDUCTING POLYMERS (ICP)

41
 Intrinsic Conducting Polymers (ICP)
ICP are conjugated polymers (i.e) alternate single and double
bond.
Eg. Polyacetylene

Polypyrrole

Polydialkylfluorene

42
 Intrinsic Conducting Polymers (ICP)

Polyaniline (PANI) Polyazomethine

Poly-p-phenylene

Poly-p-phenylenesulphide

Polyanthrylene

Polythiophene Polyphenylvinylidene
Poly(3,4-ethylene-dioxythiophene) (PEDOT)
43
Synthesis of Polyacetylene

cis-polyacetylene

Trans-polyacetylene

44
 Intrinsic Conducting Polymers (ICP)
Hybridization of carbon in polyacetylene – sp2 σ*
Equivalent to
conduction band π*

Equivalent to
valence band π
Conjugated π-bond -
delocalized π e-
σ

σ-bond for mechanical strength and delocalized π e- Relative energies of MOs of

bonding and antibonding of σ
for electrical and optical properties and π bonds of polyacetylene

45
 Intrinsic Conducting Polymers (ICP)
Overlapping of orbitals over entire backbone
(i.e) extended delocalization
results in formation of valence bands as well as
conduction bands.

46
 Intrinsic Conducting Polymers (ICP)

ICP – possess low

conductivity 10-5 Ω-1 cm-1

Energy gap between valence

and conduction band of ICPs
in the range of
semiconductors

Conductivity of ICPs - in the

range
of semiconductors

Thus, ICPs are

semiconductors
47
 Intrinsic Conducting Polymers (ICP)

Conductivity of semiconductors usually increased by

doping. Because doping increases concentration of
charge carrier (e- or positive hole)

Like semiconductors - conductivity of ICPs can increased

by creating either positive or negative charge on the
polymer backbone by oxidation or reduction. This is called
doping.

Like p- and n-doping in semiconductors - positive charge

on ICP is p-doping and negative charge on ICP is n-
doping

ICPs have low ionization potential and high e- affinity i.e it

can be easily oxidized or reduced.

48
DOPED INTRINSIC CONDUCTING
POLYMERS

49
 Intrinsic Conducting Polymers (ICP)
Doping, increases electrical conductivity of ICP
dramatically

addition of e- (charge carrier)

to conduction band (n-
doping)

π-bond e- removal e- from

valence bands (p-doping)

50
 p-Doped Intrinsic Conducting Polymers
When polyacetylene doped with Lewis acid – oxidation takes
place and positive charge created on polymer backbone.
p-dopant – I2, Br2, AsF5, PF6, naphthylamine etc.

Conductivity of
polyacetylene
Vs
I2
concentration

51
 p-Doped Intrinsic Conducting Polymers
The I2 molecule attracts e- from the
polyacetylene chain and becomes I3ֿ. The
polyacetylene molecule, now positively
charged with unpaired e- termed as radical
cation or polaron.

Lone e- of polaron moves easily along the

double bond.

Positive charge is fixed by electrostatic

attraction to the iodide ion.
52
p-Doped Intrinsic Conducting Polymers

53
P-Doping of polyacetylene

54
 n-Doped conducting polymers

ICP with Lewis base – reduction takes place

and negative charge created on polymer
backbone.

n-dopant – Li, Na, Ca, sodium naphthalide etc.

55
 Chemistry of display devices specific to OLEDs
An organic light-emitting diode (OLED or organic LED), also known
as organic electroluminescent (organic EL) diode, is a light-emitting diode
(LED) in which the emissive electroluminescent (EL) layer is a film of organic
compound that emits light in response to an electric current.

56
 Working principle of OLEDs

⮚ The holes lie in the valence band, while the free electrons are in the conduction
band of material.
⮚ When there is a forward bias in the p-n junction, the electron which is a part of the
n-type semiconductor material would overrun the p-n junction and join with the
holes in the p-type semiconductor material. Therefore, regarding the holes, the free
electrons would be at the higher energy bands.
⮚ When this movement of free electron and hole takes place, there is a change in the
energy level as the voltage drops from the conduction band to the valance band.
⮚ There is a release of energy due to the motion of the electron.
⮚ In standard diodes, the release of energy in the manner of heat. But in LED the
release of energy in the form of photons would emit light energy.
⮚ This entire process is known as electroluminescence, and the diodes are known
as a light-emitting diode.
58
§ Introduction to Nanomaterials
• A nanoparticle is an entity with a width of a few nanometers to a few
hundred, containing tens to thousands of atoms. Their defining
characteristic is a very small feature size in the range of 1-100 (nm).

• Nano size:
One nanometre is a millionth part of the size of the tip of a needle.
1 nm = 10-6 mm = 10-9 m
Table 1. Some examples of size from macro to molecular
Size Examples Terminology
(nm)
0.1-0.5 Individual chemical bonds Molecular/atomic
0.5-1.0 Small molecules, pores in Molecular
zeolites
1-1000 Proteins, DNA, inorganic Nano
nanoparticles
103-104 living cells, human hair Micro
>104 Normal bulk matter Macro
59
 Size and shape dependent colors of Au and Ag nanoparticles
Gold NPs in Glass Silver NPs in Glass
25 nm
100 nm
Sphere
Sphere
reflected
reflected

50 nm 40 nm
Sphere Sphere
reflected reflected

100 nm
100 nm prism
Sphere reflected
reflected

60
60
Categories of Nanomaterials

61
 Properties of Semiconductor Nanomaterials

⮚ Properties of nanosized semiconductor particles very

sensitive on particle size .

⮚ Physical properties of semiconductor nanocrystals are

dominated by spatial confinement of excitations
(electronic & vibrational).

⮚ Quantum confinement that manifests itself in widening

of HOMO-LUMO gap or bandgap increase with
decreasing crystallite size & its implications on the
electronic structure & photophysics of crystallites has
generated considerable interest. 62
 Quantum Confinement
❑ In the nanoparticles with some of its dimensions smaller
than 10nm, show new effects, since the laws of classical
physics no longer valid and we need quantum physics to
explain them.
❑ For example, the minimum potential energy of an electron
confined in a nanoparticle is higher than expected in
classical physics and energy levels of different electronic
states are discrete.
❑ Due to quantum confinement, the particle size has a
drastic effect on the density of electronic states and thus
on the optical response 63
 Quantum Dots and applications
Quantum dots (QDs) are semiconductor particles of few nanometers (<10
nm) in size, having optical and electronic properties that differ from larger
particles.

5 nm

Cancer cell imaging Metal ions sensing Light emitting diode

64
 Emission properties of Quantum Dots

1. Band gap decreases as the QDs size increases

2. Emission wavelength becomes red shifted with increase in size of QDs

65
 Synthetic Procedures of Quantum Dots
1. High temperature synthesis

2. Hydrothermal synthesis 4. Ultrasonication synthesis

3. Microwave synthesis

66
• Nanomaterials show unusual
⮚ Mechanical
⮚ Electrical
⮚ Optical
⮚ Magnetic properties.

Hence it has potential applications in

⮚ Different industries
⮚ Biomedical
⮚ Electronic applications.
⮚ For example, long lasting medical implants of
biocompatible nanostructured ceramic and
carbides,
⮚ Biocompatible coating
⮚ Drug delivery
⮚ Protection coatings
⮚ Composite materials
⮚ Anti fogging coatings for spectacles and car
windows etc. 67
⮚ At the nanomaterial level, some material properties are
affected by the laws of atomic physics, rather than behaving
as traditional bulk materials.
⮚ Nanomaterials can be metals, ceramics, polymeric materials,
or composite materials.

⮚ The beautiful ruby red color of some glass is due to gold

nanoparticles (Au NPs) trapped in the glass matrix.
⮚ The decorative glaze known as luster, found on some
medieval pottery, contains metallic spherical nanoparticles
dispersed in a complex way in the glaze.

Rod shaped
Spherical nano Au
AuNPs

68
 Gold : Bulk vs. Nano
Bulk Gold Nano Gold
1 Lustrous–they have a shiny surface Are never gold in colour but found in a
when polished range of colours
2 Malleable–they can be hammered, bent Size & Shape of the nanoparticles
or rolled into any desired shape determines the colour
3 Ductile–they can be drawn out into wires For example, Gold particles in glass
25 nm > red reflected
50 nm > green reflected
100 nm > orange reflected
4 Is metallic, with a yellow colour when in Are not “metals” but are semiconductors
a mass (Band gap energy = 3.4 eV)
5 Good conductors of heat and electricity Are very good catalysts
6 Generally have high densities
7 Have high melting point (~1080oC) Melts at relatively low temp (~940º C)
8 Are often hard and tough with high
tensile strength
9 Having high resistance to the stresses
of being stretched or drawn out
10 Not easily breakable
11 Inert-unaffected by air & most reagents 69
70
 BAND GAP IN NANO AND BULK MATERIALS

⮚ Band Gap

71
 Schematic representation of the ‘bottom up’ and top down’
synthesis processes of nanomaterials

High-energy By
wet ball milling atom-by-atom
molecule-by-molecule
cluster-by-cluster
Less waste
More economical

72
Any fabrication technique should provide the followings:
⮚Identical size of all particles (also called mono sized or with
uniform size distribution
⮚Identical shape or morphology
⮚Identical chemical composition and crystal structure
⮚Individually dispersed or mono dispersed i.e., no
agglomeration

73
 Nanoparticles preparation:
❖ Top-down approaches
⮚ High-energy ball milling/Machining

⮚Electrochemical Oxidation Process (Graphite rod to QDs)

⮚Etching/Cutting

⮚Atomization

❖Bottom-up approaches
⮚Chemical Vapour Condensation (CVC)
⮚ Atomic or Molecular Condensation
⮚Wet Chemical Synthesis of nanomaterials (Sol-gel process)
⮚ Precipitation method
⮚Self-Assembly 74
Schematic representation of the principle of mechanical milling

WC coated
50 µm powder ball

75
❖ Procedure of milling process
⮚ Particle size reduction, solid-state alloying, mixing or blending,

⮚ Restricted to relatively hard, brittle materials which fracture &/or deform

⮚ To produce nonequilibrium structures including nanocrystalline,

amorphous and quasicrystalline materials

⮚ Different milling process: tumbler mills, attrition mills, shaker mills,

vibratory mills, planetary mills etc.

⮚ Powders diameters of about 50 µm with a number of hardened steel or

tungsten carbide (WC) coated balls in a sealed container which is
shaken or violently agitated. The most effective ratio for the ball to
powder mass is 5 : 10. 76
A-ball mill,
B-planetary mill,
C-vibration mill,
D-attritor (stirring ball mill)
E-pin mill,
F-rolling mill 77
• Shaker mills (e.g. SPEX model 8000) uses small batches of powder
(approximately 10 cm3 is sufficient

❖ Advantage: High production rates

❖ Limitation
⮚ Severe plastic deformation associated with mechanical attrition due to
generation of high temp in the interphase, 100 to 200 oC.
⮚ Difficulty in broken down to the required particle size
⮚ Contamination by the milling tools (Fe) and atmosphere (trace
elements of O2, N2 in rare gases) can be a problem (inert condition
necessary like Glove Box)(Fe <1-2% and Trace elements<300 ppm)
⮚ Protective coating to reduce milling tools contamination (MTC)
increases cost of the process
⮚ Working duration (>30 h) increases MTC (>10%)
78
 Wet Chemical Synthesis of nanomaterials (Sol-gel process)
SOL - nanoparticle dispersion
GEL - crosslinked network

Thermal
evaporation
Calcine

800oC

Schematic representation of sol-gel process of synthesis of nanomaterials.

79
 Wet Chemical Synthesis of nanomaterials (Sol-gel process)

 Aerogel - liquid phase of a gel is replaced by a gas in such a

way that its solid network is retained, with only a slight or no
shrinkage in the gel. Shrinkage < 15%

 Xerogel - liquid phase of a gel is removed by evaporation. It

may retain its original shape, but often cracks due to the
extreme shrinkage that is experienced while being dried.
Shrinkage >90%

 Hydrogel - a water-based gel.

 Cryrogel - flexible aerogel composite blanket designed for

insulating cold temperature environments ranging from
cryogenic to ambient.
80
Sol-gel process)

81
• Overall Steps:
• Step 1: Hydrolysis - formation unstable silicon hydroxide.
• Step 2: Unstable silicon hydroxide turns into turbid colloidal solution called
sol. Sols - dispersions of colloidal particles in solvent
• Step 3: Gelation resulting from – polycondensation (Gel - is an inter-
connected, rigid network with pores of sub-micrometer dimensions &
polymeric chains whose average length is greater than a micrometer)
• Step 4: Aging of the gel, during which the polycondensation reactions
continue until the gel transforms into a solid mass, accompanied by
contraction of the gel network and expulsion of solvent from gel pores.

• Step 5: Drying of the gel, when water and other volatile liquids are removed
from the gel network.

– If isolated by thermal evaporation, the resulting monolith is termed a

xerogel.
– If the solvent (such as water) is extracted under supercritical or near
super critical conditions, the product is an aerogel.

• Calcination: Dehydration, during which surface- bound M-OH groups are

removed, thereby stabilizing the gel against rehydration. This is normally
achieved by calcining the monolith at temperatures up to 8000C.

• Step 6: Densification and decomposition of the gels at high temperatures

(T>8000C). The pores of the gel network are collapsed, and remaining organic
species are volatilized. The typical steps that are involved in sol-gel 82
processing are shown in the schematic diagram above.
❖ Advantages
• Synthesizing nonmetallic inorganic materials like glasses,

glass ceramics or ceramic materials at very low

temperatures compared to melting glass or firing ceramics
• Monosized nanoparticles possible.

• Disadvantages

• Controlling growth of particles & then stopping newly fo

rmed particles from agglomerating.

• Difficult to ensure complete reaction so that no
unwanted reactant is left on the product
• Production rates of nano powders very slow by this process
83