CHAPTER 2

ATOMIC AND CRYSTAL STRUCTURE OF

MATERIALS
 The atomic structure
• An atom is basic unit of an element
• Crystal structure is a description of the
ordered arrangement of atoms, ions or
molecules in a crystalline material
• An element is a substance that is made up of
one type of atom.
• Atom composed of a nucleus surrounded by
electrons.
• The nucleus is positively charged surrounded
and neutralized by negatively charged
electrons revolving in orbits at varying
distances from the nucleus
• The negatively charged electrons are held to
the nucleus by an electrostatic attraction.
• The electrical charge q carried by each
electron and proton is 1.60 * 10-19 coulomb
(C).
• The atomic number of an element is equal to
the number of protons in each atom.
• The atom as a whole is electrically neutral
because the number of protons and electrons
are equal.
• Most of the mass of the atom is contained
within the nucleus.
• The mass of each proton and neutron is 1.67
*10-24 g, but the mass of each electron is only
9.11 * 10-28 g.
• The atomic mass M, which is equal to the
total mass of the average number of protons
and neutrons in the atom (in atomic mass
units amu),
• The quantity NA = 6.02*1023 atoms mole is
the number of atoms or molecules in a mole.
• Therefore, the atomic mass has units of g/mol
or amu.
• Calculations involving a material’s atomic mass
and the NA are helpful to understanding more
about the structure of materials.
 The Periodic Table
• Arrangement of the chemical elements, ordered by
their atomic number (number of protons), electron
configurations, and other chemical properties.
• The periodic table contains valuable
information about specific elements
• Columns typically refer to the number of
electrons in the outermost shell
• It also helps us in predicting or rationalizing
trends in properties of elements and
compounds.
• This is why the periodic table is very useful to
both material scientists and engineers.
• In engineering, we are mostly concerned
with:
(a) Polymers (plastics) (primarily based on
carbon, which appears in Group 4B);
(b) Ceramics (typically based on combinations of
many elements appearing in Groups 1 through
5B, and such elements as oxygen, carbon, and
nitrogen); and
(c) Metallic materials(typically based on
elements in Groups 1, 2 and transition metal
elements).
 Atomic Bonding
• There are four important mechanisms by
which atoms are bonded in engineered
materials. These are:
1. Metallic bonds;
2. Covalent bonds;
3. Ionic bonds; and
4. Mixed bonds.
• The first three types of bonds are relatively
strong and are known as primary bonds The
van der Waals bonds are secondary bonds
and are relatively weaker
 The Metallic Bond
• The metallic elements have electropositive
atoms
• Aluminum, for example, gives up its three
valence electrons, leaving behind a core
consisting of the nucleus and inner electrons.
• Since three negatively charged electrons are
missing from this core, it has a positive charge
of three.
• The valence electrons move freely within the
electron sea and become associated with
several atom cores.
• The positively charged Al cores are held
together by mutual attraction to the electrons,
thus producing a strong metallic bond.
• Because their valence electrons are not fixed
in any one position, most pure metals are
good conductors of electricity at relatively low
temperatures (T less than 300 K)
• Metals show good ductility since the metallic
bonds are non-directional
• Ductility refers to the ability of materials to be
stretched or bent and return to its original
shape and size
• In general MP of metals are relatively high.
• However many metals such as iron tend to
undergo corrosion or oxidation.
• Many pure metals are good conductors of
heat and are effectively used in many heat
transfer applications.
• In selection of materials metallic bonding is
one of the factor
• However other factors are also available as
well for consideration.
 The Covalent Bond
• Materials with covalent bonding are
characterized by bonds that are formed by
sharing of valence electrons among two or
more atoms.
• For example, a silicon atom, which has a
valence of four, obtains eight electrons in its
outer energy shell by sharing its valence
electrons with four surrounding silicon atoms
The covalent bond
• Each instance of sharing represents one
covalent bond; thus, each silicon atom is
bonded to four neighboring atoms by four
covalent bonds.
• In order for the covalent bonds to be formed,
the silicon atoms must be arranged so the
bonds have a fixed directional relationship
with one another.
• This arrangement produces a tetrahedron,
with angles of 109.5° between the covalent
bonds (see figure in the previous slide above)
• Covalent bonds are very strong and hard.
• For example, diamond (C), silicon carbide
(SiC), silicon nitride (Si3N4), and boron nitride
(BN).
• These materials also exhibit very high melting
points, which means they could be useful for
high-temperature applications
• They have limited ductility because the bonds
tend to be directional.
 Example
• How Do Oxygen and Silicon Atoms Join to
Form Silica?
• Solution:
• Silicon has a valence of four and shares
electrons with four oxygen atoms, thus giving
a total of eight electrons for each silicon atom.
• Oxygen has a valence of six and shares
electrons with two silicon atoms, giving
oxygen a total of eight electrons.
Diagram
 The Ionic Bond
• When more than one type of atom is present
in a material, one atom may donate its
valence electrons to a different atom.
• Both atoms now have filled (or emptied) outer
energy levels.
• The atom that contributes the electrons is left
with a net positive charge and is called a
cation, while the atom that accepts the
electrons acquires a net negative charge and is
called an anion.
 Example
• The attraction between sodium and chloride
ions to form table salt.
 Mixed Bonding
• In most materials, bonding between atoms is
a mixture of two or more types.
• Iron, for example, is bonded by a combination
of metallic and covalent bonding.
• Many ceramic and some semiconductors
compounds,.. have a mixture of covalent and
ionic bonding.
• As the electronegativity difference between
the atoms increases, the bonding becomes
more ionic.
• The fraction of bonding that is covalent can be
estimated from the following equation:
• Fraction covalent exp(-0.25changeE2)
• Where E is the difference in electro
negativities
 Example
• Sio2 is an example of a covalently bonded
material. In reality, silica exhibits ionic and
covalent bonding. What fraction of the
bonding is covalent?
• Solution:
• The electronegativity of silicon is 1.8 and that
of oxygen is 3.5. The fraction of the bonding
that is covalent is
• Fraction covalent = exp.-[0.25(3.5 - 1.8)2]
= 0.486 = 48.6%
 Binding Energy and Interatomic Spacing
• The binding energy, is the minimum energy
required to create or break the bond.
• Materials having a high binding energy also
have a high strength and a high melting
temperature.
• Ionically bonded materials have a particularly
large binding energy
• Metals have lower binding energies.
• Inter atomic spacing in a solid metal is
approximately equal to the atomic diameter,
or twice the atomic radius r. That is the sum of
• ..Not all properties of engineered materials
are microstructure sensitive.
• Modulus of elasticity is one such property.
• Modulus of elasticity of a material (the slope
(E) of the stress-strain curve in the elastic
region, also known as Young’s modulus
• A steep slope, which correlates with a higher
binding energy and a higher melting point,
• If we have two aluminum samples that have
essentially the same chemical composition but
different grain size, we expect that the
modulus of elasticity of these samples will be
about the same;
• However, yield strengths, the level of stress at
which the material begins to permanently
deform, of these samples will be quite
different
• ..The coefficient of thermal expansion (CTE).
The CTE, α, is the fractional change in linear
dimension of a material per degree of
temperature rise
• It can be written (1/ LdT)(dL ), where L is
length and T is temperature
• Materials with a low coefficient of thermal
expansion maintain their dimensions more
closely when the temperature changes
• Materials that have very low expansion
are useful in many applications where
the components are expected to
repeatedly undergo relatively rapid
heating and cooling.
 Atomic and Ionic arrangement
• Three types of atomic or ionic arrangements
exists
• No order arrangement: Irregular arrangement
• Short-range order (SRO)- The regular and
predictable arrangement of the atoms over a
short distance
• Long-range order (LRO) - A regular repetitive
arrangement of atoms in a solid which
extends over a very large distance.
 Lattice, Unit Cells, Basis, and
Crystal Structures
• Lattice - A collection of points that divide
space into smaller equally sized segments.
• Basis - A group of atoms associated with
a lattice point.
• Unit cell - A subdivision of the lattice.
• Crystal structure: is a unique
arrangement of atoms in a crystal.
• Packing factor - The fraction of space in
a unit cell occupied by atoms.
(a ) (b ) (c) (d) (e)
• There are fourteen unique ways to arrange
atoms/points in three dimensions.
• These unique three-dimensional
arrangements of lattice points are known as
the Bravais lattices named after Auguste
Bravais (1811–1863) who was an early French
crystallographer
Crystal Structure of Metals – of
engineering interest
 ATOMIC PACKING FACTOR
• Atomic packing factor (APF),packing efficiency
or packing fraction is the fraction of volume in
a crystal structure that is occupied by
constituent particles.
 Determining the Number of Lattice Points in
Cubic Crystal Systems
• Determine the number of lattice points per cell in the cubic
crystal systems.
• Calculate the number of atoms per unit cell.
• Example:
• In the SC unit cell: lattice point / unit cell = (8 corners)1/8
=1
• In BCC unit cells: lattice point / unit cell = (8 corners)1/8
+ (1 center)(1) = 2
• In FCC unit cells: lattice point / unit cell = (8 corners)1/8
+ (6 faces)(1/2) = 4
• The number of atoms per unit cell are: 1, 2, and 4, for the
simple cubic, body-centered cubic, and face-centered
 Relationship between Atomic Radius and
Lattice Parameters

The relationship between the atomic radius and the lattice

parameter in SC, BCC, and FCC is as follows:
We find that atoms touch along the edge of the cube in SC
structures.

a0  2r
In BCC structures, atoms touch along the body diagonal. There are
two atomic radii from the center atom and one atomic radius from
each of the corner atoms on the body diagonal, so
4r
a0 
3
In FCC structures, atoms touch along the face diagonal of the
cube. There are four atomic radii along this length—two radii
from the face-centered atom and one radius from each corner,
so:
4r
a0 
2
 Simple Cubic Structure (SC)
• Rare due to low packing density (only Po – Polonium --
has this structure)
• Close-packed directions are cube edges.

•
 Atomic Packing Factor (APF)
Volume of atoms in unit cell*
APF =
Volume of unit cell
*assume hard spheres
• APF for a simple cubic structure = 0.52
volume
atoms atom
a 4
unit cell 1 p (0.5a) 3
R=0.5a 3
APF =
a3 volume
close-packed directions
unit cell
contains (8 x 1/8) =
1 atom/unit cell
Adapted from Fig. 3.23,
Callister 7e.
 Body Centered Cubic Structure (BCC)
• Atoms touch each other along cube diagonals within a
unit cell.
--Note: All atoms are identical; the center atom is shaded
differently only for ease of viewing.
ex: Cr, W, Fe (), Tantalum, Molybdenum

Adapted from Fig. 3.2,

Callister 7e.

2 atoms/unit cell: (1 center) + (8 corners x 1/8)

 Atomic Packing Factor: BCC
3a

2a
Close-packed directions:
R
a length = 4R = 3 a

atoms volume
4
unit cell 2 p ( 3a/4) 3
3 atom
APF =
3 volume
a
unit cell
• APF for a body-centered cubic structure = 0.68
 Face Centered Cubic Structure (FCC)
• Atoms touch each other along face diagonals.
--Note: All atoms are identical; the face-centered atoms are shaded
differently only for ease of viewing.

ex: Al, Cu, Au, Pb, Ni, Pt, Ag

4 atoms/unit cell: (6 face x ½) + (8 corners x 1/8)

 Atomic Packing Factor: FCC
• APF for a face-centered cubic structure = 0.74
The maximum achievable APF!
Close-packed directions:
2a length = 4R = 2 a
(a = 22*R)
Unit cell contains:
6 x 1/2 + 8 x 1/8
a = 4 atoms/unit cell
atoms volume
4
unit cell 4 p ( 2a/4) 3
3 atom
APF =
volume
a3
unit cell