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ENGINEERING Materials: Dept. of Chemistry, MIT
ENGINEERING Materials: Dept. of Chemistry, MIT
• Fundamental Principles
• Bonding in solids
• Polymers
• Liquid Crystals
• Ceramics
• Composites
• Biomaterials
• Thin Films
• Nano materials
Classification of materials
4
Solid Materials:
Nanomaterials
10
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Covalent Bond
Formed by overlap of atomic orbitals and mutual sharing
of electrons.
Typically formed by two non-metals having similar electro-
negativities and hence the atoms must share the electrons
Ex: H2, O2
13
Metallic bond
The bonding which holds the metal atoms firmly together
by force of attraction between metal ions & the mobile
electrons.
If many metal atoms are brought together, the outer
electrons of each can merge together and overlap.
Then they are in a position to move around and between
all the atoms.
A block of metal can be thought of as an array of
positive ions immersed in a sea of delocalized electrons.
Modern Materials, Dept. of Chemistry, MIT 14
Metallic bond
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Characteristic properties of metals
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Secondary Bonds
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Dipole-dipole bonds: The strongest secondary bonding type exists
between adjacent polar molecules.
The associated binding energies are significantly greater than for
bonds involving induced dipoles.
Ex: HCl
22
An ion-induced dipole attraction is a weak attraction that
results when the approach of an ion induces a dipole in an atom
or in a nonpolar molecule by disturbing the arrangement of
electrons in the nonpolar species.
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24
Ion-dipole
25
Dipole-induced dipole bonds: Permanent dipole moments exist in
some molecules by virtue of an asymmetrical arrangement of
positively and negatively charged regions; polar molecules will
induce a dipole in adjacent nonpolar molecules, and a bond will
form as a result of attractive forces between the dipole and
induced dipole
Ex: H2O and Ne
H2O and O2
26
London forces:
Atoms vibrate, at any instant the cloud is likely to be slightly off
center. This creates an instantaneous dipole
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The momentary attraction between the molecules/atoms caused by
instant dipole and induced dipole are called London forces
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POLYMERS
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Polymers
Response to Properties
Origin Structure Methods of
heat and or
formation
crystallinity Applications
Branched polymer
Cross linked
polymer
Polymerization
CONDENSATION
ADDITION POLYMERISATION POLYMERISATION
36
Tacticity of Polymers
Isotactic
On one side
Syndiotactic
Alternating sides
Atactic
Randomly placed
• Strength
• Plastic deformation
• Crystallinity
• Chemical Resistance
• Elasticity
Modern Materials, Dept. of Chemistry, MIT 38
Tensile Strength
This can be discussed based on the forces of attraction
and slipping power
39
These attractive forces are of two different types
40
Based on slipping power:
It is defined as the movement of molecules one over
the other
It depends on the shape of the molecule
E.g., polyethylene molecule is simple and uniform
the movement of molecules one over
other is easy i.e., slipping power is high
Hence it has less strength.
In case of poly vinyl chloride (PVC), the bulky
chlorine atoms are present along the chain length
hence movement is restricted
i.e., slipping power is less
Hence PVC has higher strength than PE
Cl Cl Cl Cl
Cl Cl Cl Cl
Cl Cl Cl Cl
Cl Cl Cl Cl
Polystyrene (PS) possess greater strength when
compared to PE and PVC because of the presence of
bulky phenyl group.
+ H
+ H2 0
alternating random
Poly(styrene - ethylene) poly(styrene - ethylene) copolymer
Copolymer
e.g.,
Stretched
Returned to
randomization
When a polymer is stretched the snarls begin to
disentangle and straighten out
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However when the strain is released snarls return to
their original arrangement
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In the glassy state of the polymer, there is neither
molecular motion nor segmental motion. When
all chain motions are not possible, the rigid solid
results. On heating beyond Tg segmental motion
becomes possible but molecular mobility is
disallowed. Hence flexible
67
Factors affecting glass transition Temperature
70
Molecular weight of polymers
Number – average molecular weight
• Number fraction
• Lower value
• Determined by colligative
properties
Weight – average molecular weight
• Weight fraction
• Higher value
• Determined by ultracentrifugation & light scattering expts
72
Numerical Problems
74
• Ratio of Mw to Mn is known as the polydispersity
index (PI)
vs.
vs.
Anisotropic
Anisotropic
Liquid Crystals
Liquid Crystals
have orientational order
have orientational order
LCs - Classification
Based on the response to temperature or concentration
Thermotropic LCs
Lyotropic LCs
79
LCs – Mol. Structures and examples
Calamitic
Rʹ A L B Rʺ
p-sexiphenyl
Modern Materials, Dept. of Chemistry, MIT 80
The general molecular formulae of Calamitic LCs
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LCs – Mol. Structures and examples
Discotic
3,1-polycatenary mesogen
2,2-polycatenary mesogen
(hemiphasmidic)
(hemiphasmidic)
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Nematics
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Smectics
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Smectic A Smectic C
Smectic B
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Columnar
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LCs - Properties
The LC molecules must satisfy the following properties for
applications
2. LC Thermometers
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Electric field off Electric field on
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LC Thermometers
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CERAMICS
1. Glasses
2. Clay products
3. Refractories
Acid
Neutral
Basic
4. Abrasive materials
5. Cements
6. Advanced ceramics
102
Feldspar and quartz may be added which influence the
changes that occur during firing.
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Refractories
104
A refractory material is one that retains its strength
at high temperatures
Acid refractories
consist of mostly acidic materials like alumina (Al2O3) and
silica (SiO2). They include substances such as silica,
alumina, and fire clay brick refractories
105
Basic refractories
The refractories that are rich in periclase, or magnesia (MgO)
are termed basic; they may also contain calcium, chromium,
and iron compounds.
Neutral refractories
Used in areas where slags and atmosphere are either acidic
or basic and are chemically stable to both acids and bases.
The common examples of these materials are chromia
(Cr2O3) and carbon.
106
Properties
1. In refractories
Strength
load bearing capacity
resistance to attack by corrosive materials
Non porous
Advanced ceramics
Many of our modern technologies use advanced ceramics
because of their unique mechanical, chemical, electrical
magnetic and optical properties and property
combinations. Examples: ceramic ball bearings,
piezoelectric ceramics.
108
CEMENT
A material possessing adhesive and cohesive properties, and capable of
bonding materials like stones, bricks & building blocks
Granular substance
110
GLASS
A hard, brittle, noncrystalline, super cooled
liquid of infinite viscosity more or less
transparent substance produced by fusion of
many metallic silicates like Na, K & Ca,
along with soda and lime.
Main ingredients
1. Limestone (CaCO3), CaCO3
112
Brittle fracture
113
Fracture toughness is the ability of the ceramics to
resist the fracture and is directly proportional to
applied stress and length of the crack.
114
Flexural or fracture strength σfs
Example: The maximum tensile stress value that can
be sustained before the beam or rod fails is its
flexural strength
115
fracture strength is directly proportional to load at
fracture and indirectly proportional to the thickness
of the material
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Elastic behavior
117
Elastic deformation can be due to tension /
compression / shear force.
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COMPOSITES
Sandwich composite
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COMPOSITES
122
Many composite materials are composed of two phases
matrix phase and dispersed phase.
Matrix
It is a continuous phase in composite which completely surrounds the
other phase (or dispersed phase)
Ex: metal (MMC), polymer (PMC), ceramic (CMC)
123
Dispersed phase or reinforcing phase
It is a discontinuous phase that is surrounded by the matrix
phase.
It is the structural constituent which determines the internal
structure of the composite
124
Advantages Drawbacks
• Strong and stiff, yet very • More expensive than
light in weight conventional materials
• Better fatigue properties • Manufacturing methods
• Can be designed such that for shaping composite
they do not corrode materials are often slow
• Possible to achieve • polymer based composites
combinations of subject to attack by
properties not attainable chemicals or solvents
with metals, ceramics, • anisotropic
polymers alone
• Particle reinforced
Composites • Fiber reinforced
• Structural
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Large particle reinforced composites
• The particulate phase is harder and stiffer than the matrix.
• The matrix transfers some of the applied stress to the
particles, which bear the friction of the load.
Particles can have quite a variety of geometries, but they
should be of approximately the same dimension in all
direction.
Particle size is large and present in large conc.
Fibre phase:
On the basis of diameter and character fibres are grouped into
three different classifications as
Whiskers
Fibres
Wires.
131
Whiskers
Thin single crystals that have large length to
diameter ratios (lower than fiber)
Possess high strength due to its small size that have
extremely high degree of crystallinity
they are very expensive and difficult to incorporate
into matrix.
Ex: graphite, silicon carbide, silicon nitride.
134
The strength of fiber-reinforced composite depends
on fiber orientation and its concentration
a) Parallel alignment of the longitudinal axis of the
fibers in a single direction
b) Totally random alignment
135
Structural composites
It is composed of both homogenous and composite materials.
The properties depend on properties of constituent materials and on
the geometrical design of various structural elements
Laminar composites:
It is made of two dimensional sheets or panels that have a
preferred high strength direction
Layers are stacked and subsequently cemented together such that
the orientation of high strength direction varies with each
successive layer. Ex: Ply wood
136
Sandwich panels
Consists of two strong outer sheets, or faces separated by a
layer of less dense material or core which has lower stiffness
and lower strength
Faces or skin: Laminates of glass or carbon fiber-
reinforced thermoplastics or mainly thermoset polymers
Core:polymericfoams
like polyvinylchloride, polyurethane, polyethylene
or polystyrene, synthetic rubber
Foam 137
POLYMER COMPOSITES
138
Advantages of polymer composites:
-Light weight.
-High strength to weight ratio.
-More durable than conventional materials like steel and
aluminium.
-Good corrosion resistance.
-High fatigue strength.
-High temperature resistance.
Applications:
-Composites of phenolic resins and nylon are used in heat
shields for space crafts.
-Are used in automotive and railway applications.
-As structural material in construction industries.
139
Examples of polymer composites
Fibre glass or glass-reinforced plastic (GRP)
Matrix: Made by reacting a polyester with carbon-carbon double bonds
in its backbone and styrene- a mix of the styrene and polyester
Fibre: glass fibre
Ex: Used in car engines components, aeroplane parts and boat hulls
140
Kevlar composites
141
Advantages:
-Light weight, high strength, thermally stable
-Resistant to impact and abrasion damage. It can be used as
protective layer on graphite laminates.
-Can be mixed with graphite to provide damage resistance and to
prevent failure.
Disadvantages:
142
Carbon fibre composites
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Composite sandwich structure panel used for testing at NASA
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Classification based on materials used
Polymeric Biomaterials
Metallic Biomaterials
Ceramic Biomaterials
Composite Biomaterials
can be
metals, ceramics, polymers, glasses, carbons,
composite materials
Classification
1. Biocompatibility:
• Biocompatible materials are more readily integrated into the
body without inflammatory signs.
2. Physical requirement:
• Tubing (replace a defective blood vessel) must be flexible and
must not collapse under bending or other distortions
3. Chemical requirement:
• “medical grade”, approved for use in any particular medical
application
Modern Materials, Dept. of Chemistry, MIT 147
Biomaterial applications
Vascular grafting:
• Tube-shaped synthetic material surgically implanted in the veins
and arteries are known as Vascular grafts
Artificial tissue:
• lab-grown tissues can be used to replace grafts
n HOCH2COOH + n HOCH(CHO)COOH
-O-CH2-COO-[CH(CHO)-COO-CH2-COO]n
Hip replacement:
• provides joint mobility and structural support
• stable under considerable load, have high fatigue resistance,
abrasion resistance and biocompatibility
Modern Materials, Dept. of Chemistry, MIT 148
Advantages & disadvantages
Materials Advantages Disadvantages Examples
Polymers: Resilient Not strong, Deform Sutures, blood
Nylon , Silicones Easy to fabricate with time, May vessels, hip socket, ear,
Teflon degrade nose, other
Dacron soft tissues
Metals Strong, May corrode, Dense Joint replacement,
Titanium tough bone plates and
Stainless steels Ductile screws, dental
Co-Cr alloys root implants
Gold
Ceramics Biocompatible Brittle, Difficult to Dental; hip socket
Aluminum oxide Inert, Strong in make, Not resilient
Carbon compression
Hydroxyapatite
Composites Strong, tailor-made Difficult to make Joint implants;
Carbon-carbon heart valves
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THIN FILMS
Uses
Techniques of deposition
physical vapor deposition (PVD)
chemical vapor deposition (CVD)
153
Physical Vapor deposition
• Methods
Thin films, Dept. of Chemistry, MIT 154
Vacuum deposition
Eg. Optical lenses coated with inorganic materials such as MgF2, Al2O3 and SiO2.
• dimensions - 1 to 100 nm
Based on
• origin
Natural nanomaterials
Artificial nanomaterials
•Dimension
Zero dimensional (all the dimensions are within the nanoscale range )
1 dimensional (two dimensions are at nanoscale range, other dimension is not.)
2 dimensional (one dimension is at nanoscale range, other two dimensions are
not)
3 dimensional (not confined to the nanoscale in any dimension)
• Bottom up
Chemical synthesis (sol-gel process)
• Top down
Ball milling
Sol-gel method
164
Ball milling