Materials Science

Lecture 1

Materials science is the investigation of the relationship among processing, structure,

properties, and performance of materials.
Engineering design problems related to the materials involve selection of the right
material regarding the
 in-service conditions
 decomposition of material properties
 economics
Structure of the material usually relates to the arrangement of its internal components.
Sub-atomic structure involves electrons within the individual atoms and interactions
within with their nuclei .
On an atomic level, structure includes the organization of atoms or molecules relative
to one another.
Microscopic structure contains large groups of atoms that are normally agglomerated
together and can be observed using some type of microscopes.
Structural elements which can be seen by naked eye are termed macroscopic.
Property is a material characteristic in terms of the type and magnitude of response to
a specific imposed stimulus.
Generally, definitions of properties are made independent of material shape and size.
For example; A specimen subjected to forces will experience deformation, or A polished
metal surface will reflect light.
Properties of solids:
 Mechanical Properties relate deformation applied to an load or force;
 e.g. Elastic modulus (stiffness; hardness), strength and toughness.
 For the electrical properties such as electrical conductivity and dielectric constant, the
stimulus is an electric field.
 Thermal behavior of solids can be represented in terms of heat capacity and thermal
conductivity.
 Magnetic properties demonstrate the response of a material to the application of a
magnetic field.
 The stimulus for optical properties is electromagnetic or light radiation; index of
refraction or reflectivity are representative optical properties.
 Materials Optimization Loop
!! Structure of the material depends on how it is processed.

Subatomic, Atomic Microscopic,

Macroscopic

Mechanical, Electrical Thermal,

Magnetic Optical, Deteriorative

Connected single crystals

Three specimens of aluminum oxide (Callister)

Pores scatter the reflected light and
render the material opaque
Classification of Materials
• Metals
• Ceramics
• Polymers
• Composites
• Advanced Materials (semiconductors, biomaterials, nanoengineered materials)
Metals
Structure:
Nonlocalized electrons(electrons are not bound to particular atoms) are present and many
properties of metals are directly attributable to those electrons.
 i.e. *Conductivity of electricity and heat; *Metals are
not transparent to visible light
Orderly arrangement of atoms

Properties: Strong, ductile, conduct electricity and heat well, are shiny if polished.
Ceramics
Structure: Compounds between metallic and nonmetallic elements. They are most frequently,
oxides, nitrides and carbides (Al2O3, SiO2, silicone nitride (Si3N4), clay minerals- i.e.porcelain)
Properties: Hard, strong, brittle, insulators.

Common objects that are made of ceramic materials: scissors, a china tea cup, a building brick, a
floor tile, and a glass vase. (Callister)
Polymers
Structure : Macromolecules based on carbon, hydrogen and other nonmetallic elements (oxygen,
nitrogen,etc) (PE, nylon, PVC, PTFE, PC, PS,…)
Properties : Light weight, Ductile and pliable (easily formed into complex shapes), Chemically
inert, Low electrical conductivity, Nonmagnetic, Decompose or soften at moderate temperatures

Composites
Structure : Two or more individual materials (metals, ceramics and polymers) combined to give
superior properties than the component materials.
i .e. Fiberglass is one of the most common composites, in which small glass fibers are embedded
within a polymeric material (an epoxy or polyester)
Glass fibers (strong, stiff(hard) but brittle) + polymer (flexible) = fiberglass (stiff, strong and
flexible)
MATERIALS OF IMPORTANCE
CARBONATED BEVERAGE CONTAINER A CASE STUDY

Advanced Materials
• Materials that are utilized in high technology applications are advanced materals; “materials of
future”…
• Nanostructured materials, with microstructure that has length scales between 1 and 100
nanometers with unusual properties. Electronic components, materials for quantum computing.
• Smart materials: are materials in which give a useful effect when under the influence of an
external stimulus.
• Environment-friendly materials: biodegradable or photodegradable plastics, advances in
nuclear waste processing, etc.
• Learning from Nature: shells and biological hard tissue can be as strong as the most advanced
laboratory-produced ceramics, produce biocompatible adhesives that we do not know how to
reproduce…
• Materials for lightweight batteries with high storage densities, for turbine blades that can
operate at 2500°C, room-temperature superconductors, chemical sensors (artificial nose) of
extremely high sensitivity, cotton shirts that never require ironing…
Learning ( Inspired ) from nature
Completely water resistant smart phones could be a reality one day!
Lecture 2
Atomic Bonding
-Lennard Jones Potential Diagram:a mathematically simple model that approximates the energy of
interaction between a pair of neutral atoms or molecules.

Magnitute of attractive and repulsive forces depends on separation distance (r).

Repulsive forces arise from interactions between the negatively charged electron clouds for the two
atoms and are important only at smaller values of r.
Types of bonding
Primary bonding : Chemical bonds
➢ ionic bonding
➢ covalent bonding
➢ metallic bonding
Secondary bonding: Physical bonds “van der Waals interactions “
➢ dipole-dipole interactions,
➢ hydrogen bonds
Ionic bonds
Ionic bonds are formed by the transfer of valence electrons of a metal to a
non-metal. (by coulomb interactions).
In the process, all atoms acquire stable or configurations. inert gas Due to
their electrical charge, they become ions.
Coulomb interactions: Attraction between negative and positive ions, in
proportion with their net electrical charges.
Covalent bonds
Covalent bonds are formed between non-metals by sharing a pair of electrons.

An atom can make at most (8-N’) covalent bonds

N’ = number of valence electrons.
Example: Cl2 molecule. ZCl =17 (1 s 2 2 s 2 2 p6 3 s 2 3 p5 )
N’ = 7 → 8 - N’ = 1 → Cl can form only one covalent bond

❑ Electronegativity is the tendency of an atom or a functional group to attract electrons toward itself.
❑ High electronegativity signifies that an element has a strong attraction for bonding electrons.
❑ The difference between electronegativites can tell whether a bond is polar or non-polar.
If the difference is;
< 0.5, it is non-polar
between 0.5 and 1.7, it is polar,
> 1.7, the bond is ionic.
EXAMPLE
1. Which bond is more polar; H−Cl∨H −O? EN H =2.1; EN Cl =3.0∧EN O =3.5
2. Predict the character of a possible bond between the following pairs of atoms as ionic , polar, or
non-polar: X– Z; X–W;Y–Z
You read from listed tables that the electronegativities of these elements are: W (1.7), X (1.8), Y (3.8), Z
(5.0). State your reasoning.
3. Arrange the following bonds in the order of increasing polarity and indicate for each of them
whether they are ionic, polar or non-polar bond?
H-Cl ; H-C ; H-F ; H-O
Electronegativities are EN(H) = 2.1; EN(Cl) = 3.0; EN(C) = 2.5; EN(F) = 4.0; EN(O) = 3.5
On the periodic table, the electronegativities tend to be greater on the top of the column and stronger
from left to right.

Electronegativity
 Metallic Bonding
Metallic bonding consists of positively charged metal
ions in a 3-dimensional lattice while loosely held
valence (delocalized) electrons move freely in a
fluidlike manner through the metal.

❑Metallic bond is not polar

❑Electrons move along the crystal structure of the metal
❑Due to the movement of delocalized electrons , they are good conductors
❑The “bonds” do not “break” when atoms are re-arranged. Therefore metals can experience a
significant degree of plastic deformation.
❑They are not brittle Examples of typical metallic bonding Cu, Al, Au, Ag, etc.

Secondary Bonding: Van der Waals Interactions

Van der Waals interactions:
➢arise from atomic or molecular dipoles.
➢interactions between partial charges (molecular dipoles).
➢include attractions and repulsions between atoms, molecules, and surfaces.
➢They are weaker than covalent bonds.
Van der Waals interactions are the total intermolecular forces;
❖Dipole-dipole interactions
❖London or dispersion interactions (Fluctuating induced dipole interaction)

Dipole-Dipole Interaction:
✓Dipole-dipole interactions are electrostatic interactions between permanent dipoles in molecules.
✓ Observed between polar molecules.
London or dispersion interactions (fluctuating induced dipole interactions)
o temporarily induced charges are observed in non-polar molecules by fluctuations (variations) in the
electron density. ( electrons are concentrated in one region of an atom)
o the newly formed dipoles are called “induced dipoles”.
o is observed between non-polar molecules

Van der Waals Interactions

Hydrogen bonds : X-H...X (XcanbeF,O,or N)
• A hydrogen bond is the attractive between interaction polar molecules, in which hydrogen is bound to
a highly electronegative atom, such as N, O or F.

Hydrogen bonding and water :

 Hydrogen bonding in water molecules
For water molecule, volume expansion occurs upon freezing (an exception!)
due to H bonding.
Solid ice molecules are not closely packed.
When ice melts, some of the H bonds are broken. This allows the water
molecules to be more compactly arranged and a decrease in volume
occurs. (more closely packed together)
As a result, the density increases
The arrangement of water molecules (a) solid ice, (b) liquid water when ice
melts.

Density of liquid water > solid water

Density decreases upon freezing.

Bonding in real materials

In many materials, more than one type of bonding is involved.
Metals: Metallic
Ceramics: Ionic and Covalent
Polymers: Covalent and Secondary bonds
Semiconductors: Covalent or Covalent / Ionic
Types of solids
Crystalline solids

Why study the structure of crystalline solids?

The properties of some materials are directly related to their crystal structures.
For example; pure and undeformed magnesium and beryllium, having one crystal structure, are much
more brittle (i.e., fracture at lower degrees of deformation) than metals such as gold and silver that have
yet another crystal structure.

Why study the structure of crystalline solids?

Significant property differences exist between crystalline and non-crystalline materials having the same
composition.
For example; non-crystalline ceramics and polymers normally are optically transparent; the same
materials in crystalline (or semicrystalline) form tend to be opaque or, at best, translucent.
The unit cell is the smallest boxlike unit from which you can imagine
constructing a crystal by stacking the units in three dimensions.

Coordination number
The number of atoms with which a given atom is in contact is called its coordination number.

Common Coordination Numbers

Six atoms around a central atom are located at the corners of an octahedron. An atom on the corner of a
simple cubic unit cell has a coordination number of 6
Eight atoms around a central atom are located at the corners of a cube. The atom in the center of a body
centered unit cell has a coordination number of 8
Each atom in a face-centered cubic unit cell and hexagonal closed-packed unit cell has a coordination
number of 12. The 12 particles, which make up the coordination sphere of the red particle lie in three
planes.
 Close Packed Structure
When spheres are stacked together there must always be unfilled
spaces.
In some arrangements, spheres come into as close contact as
possible, and the volume of the holes (voids) is at a minimum. This
arrangement is called closed-packed structure.
Each sphere is in contact
with six others arranged in a
hexagonal fashion around it

Close Packed Structures

CUBIC CLOSED PACKED
Cubic close-packed (ccp): (ABCABC... type of
arrangement)

ABCABC... structure is called face centered

cubic structure (FCC)

Crystal Structure Unit Cell

Crystal structures and numbers coordination

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Close Packed Structures

HEXAGONAL CLOSED PACKED

Green lines show the unit cell Unit The hexagonal prism showing parts of the shared
cell is a parallelepiped not a cube! spheres at the corners and the single sphere at the
centre of the unit cell
It has each atom with 12 nearest neighbors and the atoms fill 74.04% of the available space

Atomic Packing Fraction Calculation

 Atomic Packing Fraction (APF): In a crystal structure, the fraction of volume that is occupied
by atoms.

Spheres shared between unit cells are;

* In the middle of the unit cell, there is no sharing
* on a face = 1/2
* in a corner = 1/8 (for ccp)
* in a corner = 1/6 (for hcp)
Metallic crystal structures:Close-packed structures
➢Face-centered cubic (FCC, cubic close-packed)
There is a structural particle at the centre of each face as well as at each corner

Coordination number = 12
Packing Fraction=0.740
Examples: Al, Cu, Au, Pt, Pb, Ag, Ni
The spheres or ion cores touch one another across a face diagonal. The cube edge length (a) and the
atomic radius (r) are related through a=2 √ 2 r

Crystal Structure FCC ( ccp )

FCC-cubic close-packed
Au,Ag and Cu have a fcc packing structure, and are very ductile and very malleable.

Cubic closest packing (abcabc) (74%)

Examples:1- Assuming an atomic radius of 128 pm for a copper atom,
(a) What is the length of the unit cell of copper?
(b) What is the volume of the unit cell?
(c) How many atoms belong to the unit cell? (d) What is the packing fraction?

Example 2: Platinum crystals are face centered cubic cell. If the length of the unit cell
edge is 392 pm what is the radius of a platinum atom?

Hexagonal closed-packed crystal structure (hcp)

Top and bottom faces of the unit cell consists of 6 corner atoms (form hexagons) and
one atom in the center.
Another plane that provides 3 atoms to the unit cell is is situated between the top and
bottom planes.
Coordination number = 12
Packing Fraction=0.740
Examples: Cd, Co, Ti, Zn
Total number of atoms per unit cell for the hcp

N f Nc
Calculation of Number of Atoms for HCP N=N i+ +
2 6
Volume of the unit cell (hcp)
Volume = Base area x height
Base area = 3 x Area (ACDE)
Height = c
c/a = 1.633
Packing Fraction of HCP = 0.744
Volume = Base area x height
Base area = 3 x Area (ACDE)
A(ACDE)= |CD| x |CB|

Example 3: Cobalt (Co) has an HCP crystal structure, an atomic Radius of 0.1253 nm and a c/a ratio of
1.623. Compute the volume of the unit cell for Co?

Metallic crystal structures: deviation from close packed structure: Body Centered Cubic (BCC)
Centre and corner atoms touch each other along cube diagonal
Crystal Structure BCC
Center and corner atoms touch one another along cube diagonals , and unit cell length a and atomic
4r
radius r are related through a=
√3

Body Centered Cubic Structure (bcc)

Metallic crystal structures: deviation packed structure: Simple Cubic (SC)

Coordination # = 6
Packing Fraction=0.52
Example: Po
None of the metals have SC structure because of its relatively low atomic packing fraction. Only
polonium, a metalloid, has this crystal structure.
Metallic crystal structures

Close-packed
DENSITY COMPUTATIONS
nA
Theoretical density, ρ, of the crystal structure of a metal; ρ=
Vc NA
n= number of atoms associated with each unit cell
A=Atomic weight
Vc= Volume of the unit cell
NA= Avagadro’s number

Example 4: Calculate the radius of a tantalum (Ta) atom, given that Ta has a BCC crystal structure, a
density of 16.6g/cm3, and an atomic weight of 180.9 g/mol.

Ionic crystals

Ionic crystals: Rock salt structure

Special structure: Two interpenetrated face centered cubic structures (FCC in Cl and FCC in Na)
Coordination number = 6
Examples: NaCl, KBr, AgCl, MgO

Ionic crystals: Cesium Chloride Structure

Body centered cubic

Coordination number = 8
Examples: cesium chloride (CsCl), cesium cyanide (CsCn), brass (CuZn)

Ex 5. The ionic radii of Cs+ and Cl- are 169 and 181 pm, respectively. What is the length of the body
diagonal in the CsCl unit cell? What is the length of the side of this unit cell?

Molecular crystals: Composed of individual atoms held together by relatively weak intermolecular forces

Cubic close-packing of frozen methane: Methane adopts a

face centered cubic unit cell upon freezing

Molecular crystals: Ice

Network (Covalent) Crystals

Polymorphism and Allotropy
• Some materials (some metals as well as nonmetals) may exist in more than one crystal structure, this is
called polymorphism.
e .g. Iron: Pure iron has a BCC crystal structure at room temperature which changes to FCC iron at 912°C
• If the material is an elemental solid (not for compounds), it is called allotropy.
e .g. Carbon: graphite is the stable polymorph at ambient conditions whereas diamond is formed at
extremely high pressures.

Allotropes of Carbon