MCE 203: ENGINEERING MATERIALS

(3 Units)
Module-4

MECHANICAL ENGINEERING DEPARTMENT

Federal University of Agriculture, Abeokuta, Nigeria

BY: DR. A.T. OYELAMI

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Bohr Theory (Cont’d)
• Bohr’s original idea of orbits of discrete radii has been greatly
modified, but the concept that the electron in the hydrogen atom
occupies definite energy levels still applies.
• It can be calculated that an electron in a higher energy level is located
on average farther away from the nucleus than one in a lower energy
level.
• It is customary to refer to the successive energy levels as electron
shells.
• The terms energy level and shell are used interchangeably.
• The shells are sometimes designated by capital letters, with K
denoting the lowest energy level, as follows:

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Bohr Theory (Cont’d)
• Energy level 1 2 3 4 5 …
• Shell notation K L M N O ...
• The maximum number of electrons that can occupy a given shell
depends on the shell number.
• For example, in any atom, the first shell can hold a maximum of only
2 electrons, the second shell can hold a maximum of 8 electrons, the
third shell can hold a maximum of 18 electrons, and so forth.
• The maximum number of electrons that can occupy any particular
shell is 2n2, where n is the shell number.

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Quantum Numbers
• Using wave mechanics, every electron in an atom is characterized by four
parameters called quantum numbers.
• The size, shape, and spatial orientation of an electron’s probability density are
specified by three of these quantum numbers.
• Furthermore, Bohr energy levels separate into electron subshells, and quantum
numbers dictate the number of states within each subshell.
• The quantum numbers are named and have limitations as shown in Table 2.
• Each electron is specified in terms of its four quantum numbers that govern its
energy, its orientation in space, and its possible interactions with other electrons.
• Thus, listing the values of the four quantum numbers describes the probable
location of the electron.
• To learn to express the electronic structure of an atom, it is necessary to learn
• the names, symbols, and permitted values of the quantum numbers and
• the order of increasing energy of electrons as a function of their sets of quantum numbers. 4
Table 2: Quantum Numbers

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Principal Quantum Number
• The principal quantum number of an electron is denoted by n.
• Shells are specified by the principal quantum number.
• It is the most important quantum number in determining the energy of the electron.
• As previously stated, these shells are sometimes designated by the letters K, L, M,
N, O, and so on, which correspond, respectively, to n = 1, 2, 3, 4, 5, . . . as expanded
in Table 3.
• In general, the higher the principal quantum number, the higher the energy of the
electron.
• Electrons with higher principal quantum numbers are also apt to be farther away
from the nucleus than electrons with lower principal quantum numbers.
• The values of n can be any positive integer: 1, 2, 3, 4, 5, 6, 7, . . . . The first seven
principal quantum numbers are the only ones used for electrons in ground states of
atoms.
• This quantum number is related to the distance of an electron from the nucleus, or
its position.
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Angular Momentum Quantum Number
• The second quantum number, l, signifies the subshell, which
is denoted by a lowercase letter — an s, p, d, or f.
• It is related to the shape of the electron subshell.
• It is also referred to as the Azimuthal quantum number. It
affects the energy of the electron, but in general not as much
as the principal quantum number does.
• In the absence of an electric or magnetic field around the
atom, only n and l have any effect on the energy of the
electron.
• The value of l can be 0 or any positive integer up to, but not
including, the value of n for that electron.
• The values of the angular momentum quantum number are
often given letter designations, and the letter designations of 7
Magnetic Quantum Number
• The number of energy states for each subshell is determined by the
magnetic quantum number, denoted ml, which also determines the
orientation in space of the electron, but does not ordinarily affect the
energy of the electron.
• Its values depend on the value of l for that electron, ranging from −l
through 0 to +l in integral steps. Thus, for an electron with an l value
of 3, the possible ml values are −3,−2,−1, 0, 1, 2, and 3.

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Spin Quantum Number
• The spin quantum number, denoted ms, is related to the “spin” of the
electron on its “axis.”
• It ordinarily does not affect the energy of the electron. Its possible
values are −½ and +½.
• The value of ms does not depend on the value of any other quantum
number.

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Table 3: The Number of Available Electron States in
Some of the Electron Shells and Subshells

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Energies of Electrons
• The energy of the electrons in an atom is of paramount importance.
• The n and l quantum numbers determine the energy of each electron
(apart from the effects of external electric and magnetic fields).
• The energies of the electrons increase as the sum n + l increases; the
lower the value of n+l for an electron in an atom, the lower is its
energy. For two electrons with equal values of n+l, the one with the
lower n value has lower energy.
• Thus, we can fill an atom with electrons starting with its lowest-energy
electrons by starting with the electrons with the lowest sum n + l.

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EXAMPLE 1. Arrange the electrons in the following
list in order of increasing energy, lowest first:

Ans.
• Electron (b) has the lowest value of n+l (2+1 = 3), and so it is lowest in energy of the four
electrons.
• Electron (d) has the next-lowest sum of n+l (4+0 = 4) and is next in energy (despite the fact that
it does not have the next-lowest n value).
• Electrons (a) and (c) both have the same sum of n + l (4 + 1 = 3 + 2 = 5). Therefore, in this case,
electron (c), the one with the lower n value, is lower in energy.
• Electron (a) is highest in energy.

The Pauli exclusion principle states that no two electrons in the same atom can have the same set of four
quantum numbers. Along with the order of increasing energy, we can use this principle to deduce the order of
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filling of electron shells in atoms.
Shells, Subshells, and Orbitals
• Electrons having the same value of n in an atom are said to be in the
same shell.
• Electrons having the same value of n and the same value of l in an
atom are said to be in the same subshell.
• Electrons having the same values of n, l and ml in an atom are said to
be in the same orbital

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Wave-Mechanical Model
• Wave-mechanical model, in which
the electron is considered to exhibit
both wave-like and particle-like
characteristics.
• With this model, an electron is no
longer treated as a particle moving
in a discrete orbital; rather, position
is considered to be the probability of
an electron’s being at various
locations around the nucleus.
• In other words, position is described
by a probability distribution or
electron cloud. Figure 14: Comparison of Bohr & Wave-Mechanical Models for the hydrogen atom.
a) The first three electron energy states for the Bohr hydrogen atom.
(b) Electron energy states for the first three shells of the wave-mechanical H atom.
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CRYSTAL STRUCTURE
• It is convenient to subdivide the structure of solids into two broad
categories: crystalline and non-crystalline or amorphous.
• Many solids have a crystalline structure that is described by an ordered
geometric array of atoms that stretches endlessly in all directions in a
repetitive fashion.
• Despite external appearances to the contrary, materials like metals are,
in fact, crystalline based on the scientific criterion of an orderly
internal arrangement of atoms.
• On the other hand, atoms are not positioned in predictably ordered
arrays in amorphous solids like silica glass and most hydrocarbon
polymers.

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Crystal Structure (Cont’d)
• To create actual crystal structures one must first imagine a three-dimensional array
of points in space distributed such that each has identical neighbors.
• There are only 14 ways to arrange points in space having this geometrical
property.
• These special point arrays are known as Bravais point lattices.
• It must be appreciated that the space of any one of these point lattices can be
delineated into cells in a number of arbitrary ways.
• The lines drawn in Figure 12 have been found to be the most convenient way to
outline unit cells of points that can be used to distinguish each of the Bravais
lattices.
• Table 4 summarizes the lengths and inter-axial angular relationships among the 14
unit cells that can be further classified as belonging to one of seven crystal
systems.
• The unit cell dimensions, a, b and c are known as lattice parameters or constants, 16
and these can be measured with high precision by the X-ray diffraction (XRD)
Table 4 : Space Lattices and Crystal
Geometries

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The 14 Bravais Point Lattices

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DEFECTS / IMPERFECTIONS IN CRYSTALS
• Perfect long-range atomic order does not exist in crystalline solids
even in most carefully prepared materials.
• Various types of imperfections or irregularities exist in the atomic
arrangement in all solid materials.
• The most common imperfections in crystalline solids include
• vacancies,
• interstitials,
• solute (or impurity) atoms,
• dislocations,
• grain boundaries, and
• surfaces and interfaces.
• Many physical and mechanical properties of crystalline solids are
determined by the nature of the defects, and their distribution and
concentration in the material. 19
 Vacancies
Vacancies or vacant atomic sites (Figure 16) exist in solids at all
temperatures; their concentration increases exponentially with
temperature according to the Boltzmann distribution function,
N = N0 exp(-Q/kT )
where
• N is the equilibrium number of vacancies per unit volume of
the material at an absolute temperature, T,
• N0 is the total number of atomic sites per unit volume
• Q is the activation energy to form the vacancy and
• k is the Boltzmann’s constant (13.81 × 10-24 J/K).
Vacancies increase the disorder (entropy) in the crystal, thus making
Figure 16: Schematic illustration of two types of point
their presence a thermo-dynamic necessity. defects in crystalline solids: a vacancy and a self-interstitial.

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Interstitials
• Unlike a vacancy, an interstitial defect forms when either a
host atom or an impurity atom resides in a preexisting
void in the crystal lattice.
• Figure 16 shows the formation of a self-interstitial when a
host atom is dislodged from its normal site and forced into
the (smaller) void between atoms.
• Most practical engineering materials are alloys rather than
pure elemental solids.
Figure 17: The atom positions around an
• Alloys are solid solutions and form when an impurity edge dislocation; extra half-plane of atoms
atom either substitutes a host atom (substitutional solid shown in perspective.
solution) or enters the interstices of the parent lattice
(interstitial solid solution).
• Figure 17 shows substitutional and interstitial impurity
atoms in a crystal lattice. Solute atoms in a host crystal
lattice can also form a compound (e.g., intermetallic
compounds in which the different types of atoms are 21
Hume-Rothery Rules
• High solubility of impurity atoms in substitutional solid solutions is
favored when a set of criteria, called the Hume-Rothery rules, are
satisfied.
• These rules stipulate that solid solutions form when one or more of the
following criteria are met:
1. the difference in the atomic radii of the two atom types should be less than
15%,
2. crystal structure of the two metals should be the same,
3. the electronegativity difference between the two atom types should be small
(metals widely separated in the periodic table, i.e., those exhibiting large
electronegativity difference, are more likely to form an intermetallic
compound rather than a solid solution), and
4. a metal of higher valence will dissolve more readily in the host metal than a
metal of valence lower than the host metal.
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