Chapter 1 – Elementary Materials Science Concepts

2019 08 21 Lecture

▪ To review what you should have known and learned

Chapter 1
1.1 Atomic Structure and Atomic Number
1.2 Atomic Mass and Mole
1.3 Bonding and Types of Solids
1.4 - 1.4.2 Thermal Expansion
1.8 Review of Crystal Systems and Lattice

MatE 153-01, Fall 2019, T Pan P. # 1

 Atomic Structure (Freshman Chem.)

• atom – electrons – 9.11 x 10-31 kg

protons
neutrons } 1.67 x 10 -27 kg

• atomic number = # of protons in nucleus of atom

= # of electrons in neutral species

• A [=] atomic mass unit = amu = 1/12 mass of 12C

Atomic wt = wt of 6.022 x 1023 molecules or atoms

1 amu/atom = 1 g/mol
C 12.011
H 1.008 etc.

MatE 153-01, Fall 2019, T Pan P. # 2

 Atomic Mass and Mole
▪ Atomic mass unit (amu) u = 1/12 of the mass of a neutral carbon atom
which has a mass number A = 12 (6 protons and 6 neutrons).
▪ amu = 1.66054 x 10-27 kg
▪ Atomic mass, relative atomic mass, or atomic weight Mat of an element:
the average atomic mass, in atomic mass units, of all the naturally
occurring isotopes of the element
▪ Avogadro’s number NA : the number of atoms in exactly 12 grams of
carbon-12 atom.
This is because the atomic mass of an element is the weighed average of the atomic masses of
all the isotopes of an element.

For example, oxygen occurs in nature as a mixture of isotopes16O,17O and 18O having atomic
masses of 15.995 u, 16.999 u and 17.999 u respectively. The relative abundance of the three
isotopes is 99.763%,0.037% and 0.2%.
Thus the atomic mass of oxygen is expressed as the weighed average of the atomic masses of
these three isotopes.

Atomic mass of oxygen= [(99.763*15.995)+(0.037*16.999)+(0.2*17.999)]/100

MatE 153-01, Fall 2019, T Pan P. # 3
 The Periodic Table

Figure 2.8 The periodic table of the elements. The numbers in parentheses are the atomic
weights of the most stable or common isotopes.

MatE 153-01, Fall 2019, T Pan P. # 4

 Elementary Materials
▪ Carbon atom, with atomic number, Z, of 6
▪ i.e. 6 protons in the nucleus, also 6 electrons for a neutral atom

Fig 1.1 The shell model of the atom in which electrons are confined to live
within certain shells and in subshells within shells
MatE 153-01, Fall 2019, T Pan P. # 5
 Simplified Bohr Atomic Model
One early outgrowth of quantum mechanics
was the simplified Bohr atomic model,
1) electrons to revolve around the atomic
nucleus in discrete orbitals,
2) the energies of electrons are quantized.
An electron may change energy, but in doing
so, it must make a quantum jump either
to an allowed higher energy (with
absorption of energy) or to a lower
energy (with emission of energy).

Figure 2.1 Schematic representation of the Bohr atom

Note: this could be a neutral Magnesium with the
electron configuration of 1𝑠 2 2𝑠 2 2𝑝6 3𝑠 2

Source: Materials Science and Engineering: An Introduction, 9th Edition, by Callister

MatE 153-01, Fall 2019, T Pan P. # 6
 Hydrogen Atom

Figure 2.2
(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
hydrogen atom.

Source: Materials Science and Engineering: An Introduction, 9th Edition, by Callister

MatE 153-01, Fall 2019, T Pan P. # 7
 Bohr vs. Wave
Mechanical Models for
Atom

Figure 2.3 Comparison of

the (a) Bohr and (b) wavemechanical
atom models in terms of electron
distribution. (Adapted from Z. D.
Jastrzebski, The Nature and Properties of
Engineering Materials, 3rd edition,
p. 4. Copyright © 1987 by John Wiley &
Sons, New York. Reprinted by
permission of John Wiley & Sons, Inc.)

MatE 153-01, Fall 2019, T Pan P. # 8

 Electronic Structure
• Electrons have wavelike and particulate properties.
– This means that electrons are in orbitals defined by a
probability.
– Each orbital at discrete energy level is determined by
quantum numbers.

Quantum # Designation
n = principal (energy level-shell) K, L, M, N, O (1, 2, 3, etc.)
l = subsidiary or secondary
(orbital angular momentum) s, p, d, f (0, 1, 2, 3,…, n-1)
ml = magnetic 1, 3, 5, 7 (-l to +l)
ms = spin ½, -½
Four Quantum Numbers (Definition)
• Principal quantum number, n, specifies electron shell
• Second quantum number, l, specifies the subshell
• Third quantum number, ml, specifies the specific orbital within the subshell
• Fourth quantum number, ms, specifies electron spin moment

MatE 153-01, Fall 2019, T Pan P. # 9

 Electron Shells and Subshells

Source: Materials Science and Engineering, an Introduction,

by Callister and Rethwisch

MatE 153-01, Fall 2019, T Pan P. # 10

 Four Quantum Numbers
▪ Maximum number of electrons in the shells and subshells

MatE 153-01, Fall 2019, T Pan P. # 11

 Electron Configuration
▪ Valence electrons: the electrons occupying the outer shells, playing a
major role in atomic interactions, as in chemical reactions
▪ Fig. 2.7, Electron configuration of Sodium, Na,
▪ A neutral Na atom with 11 electrons
▪ One valence electrons

Figure 2.7 Schematic

representation of the filled and
lowest unfilled energy states for
a sodium atom.

Source: Materials Science and Engineering, an

Introduction, by Callister and Rethwisch

MatE 153-01, Fall 2019, T Pan P. # 12

 Electronic
Configurations
of Elements

Table 2.2
Expected Electron
Configurations for
Some Common
Elements

MatE 153-01, Fall 2019, T Pan P. # 13

13
 Electron Configuration
• Most elements: Electron configurations not stable.
Element Atomic # Electron configuration
Hydrogen 1 1s 1
Helium 2 1s 2 (stable)
Lithium 3 1s 2 2s 1
Beryllium 4 1s 2 2s2
Boron 5 1s 2 2s 2 2p 1
Carbon 6 1s 2 2s 2 2p 2
... ...
Neon 10 1s 2 2s 2 2p 6 (stable)
Sodium 11 1s 2 2s 2 2p 6 3s 1
Magnesium 12 1s 2 2s 2 2p 6 3s 2
Aluminum 13 1s 2 2s 2 2p 6 3s 2 3p 1
... ...
Argon 18 1s 2 2s 2 2p 6 3s 2 3p 6 (stable)
... ... ...
Krypton 36 1s 2 2s 2 2p 6 3s 2 3p 6 3d 10 4s 2 4p 6 (stable)

• Why not stable? Valence (outer) shell usually not

completely filled.
MatE 153-01, Fall 2019, T Pan P. # 14
 General Bonding Principles
▪ General principle of molecule formation is illustrated below
▪ When 𝐹𝑁 = 𝐹𝐴 + 𝐹𝑅 = 0, an equilibrium is reached, and the equilibrium separation is
effectively the bond length. The system achieves its minimum in potential energy
𝑑𝐸
▪ The potential energy 𝐸 𝑟 of the two atoms is, 𝐹𝑁 = −
𝑑𝑟

Fig 1.3 (a) Force vs. interatomic separation, (b) Energy vs. interatomic separation
MatE 153-01, Fall 2019, T Pan P. # 15
 General Bonding
Illustration
▪ General principle of molecule
formation

Fig 1.3 (a) Force vs. interatomic

separation,
(b) Energy vs. interatomic
separation

MatE 153-01, Fall 2019, T Pan P. # 16

 Covalent Bonding
▪ Covalent bond results from the sharing of valence electrons to complete
the subshells of each atom

Fig 1.4 Formation of a covalent bond

between two hydrogen atoms leads to
the H2 molecule. Electrons spend
majority of their time between the two
nuclei which results in a net attraction
between the electrons and the two
nuclei which is the origin of the
covalent bond.

MatE 153-01, Fall 2019, T Pan P. # 17

 Covalent Bonding Example – CH4
▪ Hybridization of carbon: the 4 valence electrons (2 in 2S and 2 in 2P) can
form 4 SP3 hybrid orbitals, in order to form 4 covalent bonds

Fig 1.5 (a) Covalent bonding in

methane, CH4, involves four
hydrogen atoms sharing Bonds with
one carbon atom. Each covalent bond
has two shared electrons.

The four bonds are identical and repel

each other.
(b) Schematic sketch of CH4 in paper.
(c) In three dimensions, due to
symmetry, the bonds are directed
towards the
Corners of a tetrahedron.

MatE 153-01, Fall 2019, T Pan P. # 18

 Hbridization of Carbon (I)

hybridization

MatE 153-01, Fall 2019, T Pan P. # 19

 Hbridization of Carbon (II)
In order for one carbon to bound to 4
Ground state of carbon
hydrogen atoms, an electron is
excited to 2p orbital

This leaves 4 valence electrons which will

each overlap with the s orbital of a
Hydrogen to form a σ (sigma) bond. These
hydrogens space themselves as far apart
as possible, leading to the tetrahedral
structure of methane.
The excitation changes the forces on
valence electron. This and other
forces create a new hybridized
orbital, called 𝑠𝑝3

MatE 153-01, Fall 2019, T Pan P. # 20

 Covalent Bonding Example – Diamond
▪ Covalent bonds are strong and directional, as a result, diamond with covalent bond
has very low Atomic Packing Factor
▪ Coordination number (CN) is the number of nearest neighbors for a given atom.
The CN for a carbon atom in diamond is 4
▪ All valence electrons are lock in the bond, therefore, poor electrical conductivity

Fig 1.6 The diamond crystal is a

covalently bonded network of
carbon atoms. Each carbon atom is
covalently bonded to four
neighbors forming a regular three
dimensional pattern of atoms
which constitutes the diamond
crystal.

MatE 153-01, Fall 2019, T Pan P. # 21

 Metallic Bonding
▪ When many metal atoms come together and form a solid, the valence
electrons become delocalized and collectively shared by all the ions
▪ The metallic bond is nondirectional, results in
high coordination number, and high Atomic
Packing Factor (APF).
▪ Cu ions form the face-centered cubic
structure, FCC.
▪ FCC has the highest possible APF, in a hard-
sphere crystal structure model.
▪ “free” valence electrons result in high electrical
and thermal conductivities.

Fig 1.7 In metallic bonding the valence electrons

from the metal atoms form a “cloud of electrons”
which fills the space between the metal ions and
“glues” the ions together through the coulombic
attraction between the electron gas and the positive
metal ions.
MatE 153-01, Fall 2019, T Pan P. # 22
 Ionic Bonding (I)
▪ Transferring the valence electron of Na to Cl results in two oppositely charged
ions, Na+ and Cl-, which are called cation and anion.
▪ The ion 𝑁𝑎+ has same electron configuration as Ne, the ion 𝐶𝑙 − has the same
electron configuration as Ar.

Fig 1. 8 The formation of ionic bond between Na and Cl atoms in NaCl. The
attraction is due to coulombic forces.
MatE 153-01, Fall 2019, T Pan P. # 23
 The Periodic Table
▪ The cation Na+ looks like inert element Ne, but with a positive charge.
▪ The anion 𝐶𝑙 − looks like inert element Ar, but with a negative charge.

MatE 153-01, Fall 2019, T Pan P. # 24

 Ionic Bonding (II)
▪ In NaCl crystal, the collection of ions is held together by the Coulombic attraction
between the Na+ and Cl- ions

(a) (b)

Fig 1.9 (a) A schematic illustration of a cross section from solid NaCl. NaCl is made of Cl-
and Na+ ions arranged alternatingly so that the oppositely charged ions are closest to each other
and attract each other. There are also repulsive forces between the like ions. In equilibrium the
net force acting on any ion is zero. (b) Solid NaCl.
MatE 153-01, Fall 2019, T Pan P. # 25
 A Unit Cell of NaCl
▪ A FCC unit cell ▪ A unit cell of NaCl (rock salt,
sodium chloride)

▪ For the NaCl solid to be stable, each 𝑁𝑎+

ion must have 𝐶𝑙 − ions as nearest
neighbors and vice versa, so that like-ions
are not close to each other.

MatE 153-01, Fall 2019, T Pan P. # 26

 Ionic Bonding (III)
▪ Initially, energy is needed to remove the electron from Na, the energy of ionization.
However, the energy of Coulombic attraction between the cation and anion results
in a net lowering the potential energy of the cation and anion pair.

Fig 1.10 Sketch of the potential energy per ion-pair in solid NaCl. Zero energy
corresponds to neutral Na and Cl atoms infinitely separated.
MatE 153-01, Fall 2019, T Pan P. # 27
 Secondary Bonding

▪ The magnitude of net force

between two dipoles does
not depend on their
separation r as 1/r2, and
the net force is only weakly
attractive.

Fig 1.11 (a) A permanently polarized molecule is called an electric dipole moment.
(b) Dipoles can attract or repel each other depending on their relative orientations.
(c) Suitably oriented dipoles can attract each other to form van der Walls bonds.
MatE 153-01, Fall 2019, T Pan P. # 28
 Secondary Bonding - Example
▪ Although each H2O is neutral overall, the molecules attract each other to form
liquid below 100°C and solid below 0C.
▪ The van der Waals-London force : a net eletcrostatic attraction between the
election distribution of one atom and the positive nucleus of the other.

Hydrogen bonding: when

the positive charge of a
dipole arises from an
exposed H nucleus, as in
H2O
Fig 1.12 The origin of van der Walls bonding between water molecules.
(a) The H2O molecule is polar and has a net permanent dipole moment
(b) Attractions between the various dipole moments in water gives rise to van der
Walls bonding
MatE 153-01, Fall 2019, T Pan P. # 29
 Secondary Bonding from Induced Dipoles
▪ van der Waals attraction also occurs between neutral atoms and nonpolar molecules.
▪ Induced synchronization of charge distribution results in a net attraction, lowering of the
net energy, and bonding

Fig 1.13 Induced dipole-

induced dipole interaction
and the resulting van der
Waals force

MatE 153-01, Fall 2019, T Pan P. # 30

 Comparison of Bond Type

MatE 153-01, Fall 2019, T Pan P. # 31

 Elastic Modulus (I)
▪ In elastic region, the increase separation between atoms results in a net attractive
force δFN between neighboring atoms attempting to restore the separation to
equilibrium.

Fig 1.14 (a) Applied forces F stretch the solid elastically from L0 to δL. The force is divided
amongst chains of atoms that make the solid. Each chain carries a force δFN. (b) In
quilibrium, the applied force is balanced by the net force δFN between the atoms as a
result of their ncreased separation.
MatE 153-01, Fall 2019, T Pan P. # 32
 Elastic Modulus (II)
▪ Modulus is proportional to the slope of the interatomic force–separation curve at the
𝑑𝐹
equilibrium spacing: 𝐸 ∝
𝑑𝑟 𝑟0

Figure 6.7 Force versus interatomic separation for weakly and strongly bonded atoms. The
magnitude of the modulus of elasticity is proportional to the slope of each curve at the
equilibrium interatomic separation 𝑟0 .
MatE 153-01, Fall 2019, T Pan P. # 33
 Bond Energy vs. Modulus
▪ The bonding energy is the minimum of E versus r at 𝑟0 . Solids with higher bond
energies tend to have higher elastic moduli among the same type of bonds

MatE 153-01, Fall 2019, T Pan P. # 34

 Thermal Expansion
▪ Thermal expansion is due to
the asymmetric nature of the
interatomic forces and the
increase in the amplitude of
atomic vibrations with
temperature, as expected
from kinetic molecular theory.
• PE curve U(r) is
asymmetric, broader in the
r > r0 region,
1
𝑟𝑎𝑣 = 𝑟𝐵 + 𝑟𝐶
2
▪If PE curve U(r) were KE at T2
symmetric, there would be
no thermal expansion.

Fig. 1.18 The potential energy PE curve has a minimum when the atoms in the solid attain the
interatomic separation r = ro. Due to thermal energy, the atoms will be vibrating and will have
vibrational kinetic energy. At T = T1, the atoms will be vibrating in such a way that the bond will be
stretched and compressed by an amount corresponding to the KE of the atoms. A pair of atoms will
be vibrating between B and C. This average separation will be at A and greater than ro.
MatE 153-01, Fall 2019, T Pan P. # 35
 Vibrations of atoms about their equilibrium positions
▪ Atoms executing simple harmonic motion and maintaining E = U + KE= constant

Fig. 1.19 Vibrations of atoms in the solid. We consider, for simplicity a pair of atom. Total
energy E = PE + KE and this is constant for a pair of vibrating atoms executing simple
harmonic Motion. At B and C KE is zero (atoms are stationary and about to reverse direction
of oscillation) and PE is maximum.
MatE 153-01, Fall 2019, T Pan P. # 36
 Thermal Expansion (III)
▪ Thermal coefficient of linear expansion, or simply, thermal expansion coefficient λ is
defined as,
1 𝛿𝐿
𝜆= ×
𝐿0 𝛿𝑇
 = thermal coefficient of linear expansion or thermal expansion coefficient, Lo =
original length, L = length at temperature T

Thermal Expansion

L = Lo [1+  (T − To )]
L = length at temperature T, Lo = length at temperature To

▪ Thermal expansion is an unharmonic effect, because the restoring force is not

proportional to the displacement alone. Such oscillations are unharmonic, and the
PE curve is said to possess an unharmonicity.

MatE 153-01, Fall 2019, T Pan P. # 37

 Thermal Expansion (IV)
▪ Thermal expansion coefficient is a function of temperature.
In very general terms, except for very
low and very high temperatures, λ for
most metals does not depend strongly
on the temperature.

X10-6

Fig 1.20 Dependence of the linear

thermal expansion coefficient  (K-1) on
temperature T (K) on a log-log plot.
HDPE, high density polyethylene; PMMA,
Polymethylmethacrylate (acrylic); PC,
polycarbonate; PET, polyethylene
terepthalate (polyester); fused silica, SiO2;
alumina, Al2O3.
SOURCE: Data extracted from various
sources including G.A. Slack and S.F.
Bartram, J. Appl. Phys., 46, 89, 1975.

MatE 153-01, Fall 2019, T Pan P. # 38

 Thermal Expansion (V)
▪ Thermal expansion coefficients of some common materials.

▪ Polymers, with weak, secondary, intermolecular bonds (low melting points) have
very high expansion coefficients.
▪ Ceramics which are strongly bonded (i.e., ionic or network covalent) have low
thermal expansion coefficients.
▪ Metals with high melting points (strong bonding) have low thermal expansion
coefficients. Low melting point metals have high thermal expansion coefficients.
MatE 153-01, Fall 2019, T Pan Source: Wikipedia P. # 39
 Six Lattice Paramters

Figure 3.5 A unit cell with x, y, and z coordinate

axes, showing axial lengths (a, b, and c) and
interaxial angles (a, b, and g).

MatE 153-01, Fall 2019, T Pan P. # 40

 Seven Crystal Systems (I)
Table 3.2 Lattice Parameter Relationships and Figures Showing Unit Cell
Geometries for the Seven Crystal Systems

MatE 153-01, Fall 2019, T Pan P. # 41

 Seven Crystal Systems (II)

MatE 153-01, Fall 2019, T Pan P. # 42

 7 Crystal Systems & 14 Lattices (I)

MatE 153-01, Fall 2019, T Pan P. # 43

 7 Crystal Systems & 14 Lattices (II)

MatE 153-01, Fall 2019, T Pan P. # 44

 Alternate
View of 7
Crystal
Systems
& 14
Lattices

MatE 153-01, Fall 2019, T Pan P. # 45

 FCC Structure
Fig. 1.31
(a) The crystal structure of
copper is face centered cubic
(FCC). The atoms are
positioned at well defined
sites arranged periodically
and there is a long range
order in the crystal.
(b) An FCC unit cell with
closed packed spheres.
(c) Reduced sphere
representation of the unit
cell. Examples: Ag, Al, Au,
Ca, Cu, γ-Fe (>912 ˚C), Ni,
Pd, Pt, Rh.

MatE 153-01, Fall 2019, T Pan P. # 46

 BCC Structure

Fig 1.32 Example: Alkali metals (Li, Na, K, Rb), Cr, Mo, W, Mn, α-Fe (< 912
˚C), β-Ti (> 882 ˚C) Body centered cubic crystal (BCC) crystal structure.
(a) A BCC unit cell with closely packed hard spheres representing the Fe atoms.
(b) A reduced-sphere unit cell.

MatE 153-01, Fall 2019, T Pan P. # 47

 HCP Structure
Fig 1.33 The Hexagonal Close
Packed (HCP) Crystal Structure.
(a) The Hexagonal Close Packed
(HCP) Structure. A collection of
many Zn atoms. Color difference
distinguishes layers (stacks).
(b) The stacking sequence of
closely packed layers is ABAB
(c) A unit cell with reduced
spheres
(d) The smallest unit cell with
reduced spheres.

MatE 153-01, Fall 2019, T Pan P. # 48

 The Diamond Unit Cell
Fig 1.34 The diamond
unit cell is cubic. The cell
has eight atoms. Grey Sn
(α-Sn) and the Elemental
semiconductors Ge and Si
have this crystal structure.

Actually, the diamond unit

cell is an FCC structure,
with 2 carbon atoms at
each lattice point, i.e. the
basis consists of two
carbon atoms

MatE 153-01, Fall 2019, T Pan P. # 49

 Review Problems for Chapter 1
▪ A list of “Review Problems” for Chapter 1 is provided, to be posted on Canvas.
▪ These problems are there to help you study on the key concepts of Chapter 1
▪ You should first study the Chapter 1 by reviewing the Lecture Notes and relevant
Textbook Chapter/sections. You should then attempt to answer each of the review
problems without referring to Lecture Notes or Textbook. After completing your
answers to the problems, check with Lecture Notes and Textbook to find the correct
answers.
▪ You do not need to turn in your answers
▪ We will review the answers of selected problems in Class.

MatE 153-01, Fall 2019, T Pan P. # 50