MEN 215- Material Science

Instrcutor: Dr. Poyraz Aydiner

Email: poyraz.aydiner@aydin.edu.tr
Office:
Course Description and Objectives

A general introductory course to basic concepts and methods in materials

engineering, covering fundamental concepts including crystal structure,
defects, diffusion, phase diagram and phase transformation, corrosion as well
as properties (focusing on mechanical properties) and practical processing
and applications of major categories of engineering materials including metals
and alloys, ceramics and glass, polymers, and composites.

This course endeavors to introduce the basic concepts and methods in

materials engineering to undergraduate engineering students and help
students develop preliminary understanding of the inter-relationships
between composition, processing, structure, properties, and performance for
common solid-state engineering materials.
Textbook & Other Materials
Materials Science and Engineering
An Introduction,
William D. Callister, Jr. and David G Rethwisch, John
Wiley & Sons Inc, 9th ed. (2013)

Any other earlier versions are OK!

 Course Policy

Attendance required

• Cell phones and other device on silent mode

• Can discuss homework problems, but must independently finish them

• Exams will be closed-book

• Grading Objections– resolve within the specified time only

• “Make-up” exams only for emergency cases with valid proof

• No cheating or plagiarism
 The necessity of studying materials science

➢ Materials used by humans are deeply rooted in human culture.

➢ Transportation, communication, housing, clothing, food, and more are influenced by

humanity's progress in obtaining materials.

➢ Early civilizations were named based on their access to and advancements in materials:
the Stone Age, Bronze Age, and Iron Age.

➢ Many of humanity's past and even current needs require finding the appropriate material.

➢ Ceramic layers in shuttles, carbon fibers in aircraft, semiconductor production, optical

fibers and high-speed data transmission, metal sheets for car body production.
 The necessity of studying materials science

➢ The age of human knowledge regarding the effect of manufacturing processes and the
combination of materials on improving their properties is no more than 100 years.

➢ Gradually, humans realized that to understand the behavior of materials, they must comprehend
the structure of materials.

Materials drive our society

Stone Age
Bronze Age
Iron Age
Now?
Silicon Age?
Polymer Age?
 WHY STUDY MATERIALS SCI. & ENG.?

•To be able to select a material for a given use based

on considerations of cost and performance.

•To understand the limits of materials and the change

of their properties with use.

•To be able to create a new material that will have

some desirable properties.
 MATERIALS SICENCE VS MATERIALS ENG.

On the basis of structure-property correlations:

•Materials science involves investigating the relationship btw structures

& properties of materials.

•Materials Eng. is designing or engineering the structure of a material to

produce a predetermined set of properties.
 MATERIALS SICENCE VS MATERIALS ENG.

On the basis of functional prospective:

•The role of materials scientist is to develop or synthesize new materials

•Materials Eng. is called upon to create new products or systems using

existing materials, and/or develop techniques for processing materials.
 Material Science & Engineering

In materials science and engineering, special attention is given to the relationship between the structure and
properties of materials.

Structure (structure): Refers to the internal arrangement of the components of a material.

Structure is examined at various scales:

•Subatomic: Issues such as atomic structure and the position of electrons within the atom.

•Atomic: Issues such as the bonds between atoms and the relationships between atoms.

•Microscopic: Several atoms or molecules grouped together, visible through special instruments, such as the
grain structure of materials.

•Macroscopic: Features visible to the naked eye, such as color, polishability, and so on.
 Material Properties

Material properties (property) are intrinsic characteristics of a material, and in order to identify them, specific
stimuli must be applied to the material. Properties are expressed in terms of type and magnitude in response to
specific stimuli and are independent of the shape and size of the material.

•Mechanical Properties:

•Strength: The ability of a material to withstand an applied force without breaking.

•Elasticity: The ability of a material to return to its original shape after deformation.
•Plasticity: The ability of a material to permanently deform without breaking.
•Hardness: Resistance to surface indentation or scratching.
•Ductility: The ability to be stretched into a wire.
•Brittleness: The tendency to break or shatter under stress without significant deformation.

•Thermal Properties:

•Thermal Conductivity: The ability to conduct heat.

•Heat Capacity: The amount of heat required to change a material's temperature.
•Thermal Expansion: The tendency of a material to expand when heated.
•Melting Point: The temperature at which a material transitions from solid to liquid.
 Material Properties
•Electrical Properties:

•Conductivity: The ability of a material to conduct electric current.

•Resistivity: The resistance of a material to electric current.
•Dielectric Strength: The maximum electric field a material can withstand without breaking down.

•Optical Properties:

•Refractive Index: The measure of how much light bends when passing through the material.
•Transparency: The ability of light to pass through a material.
•Reflectivity: The ability of a material to reflect light.

•Chemical Properties:

•Corrosion Resistance: The ability to withstand degradation caused by reactions with environmental elements.
•Oxidation: The tendency to react with oxygen, often leading to rust or tarnishing.
•Chemical Stability: Resistance to chemical change or decomposition.

•Magnetic Properties:

•Magnetism: The ability of a material to be attracted by or produce a magnetic field.

•Permeability: The degree to which a material can support the formation of a magnetic field.
 The Materials Selection Process
1. Pick Application Determine required Properties
Properties: mechanical, electrical, thermal,
magnetic, optical, deteriorative.

2. Properties Identify candidate Material(s)

Material: structure, composition.

3. Material Identify required Processing

Processing: changes structure and overall shape
ex: casting, sintering, vapor deposition, doping
forming, joining, annealing.

Chapter 1 - 14
 Processing & Performance
Process: Refers to the method of manufacturing or shaping materials.

Performance: The response of the material under the required working conditions.

Fig 1.1 The four components of the discipline of materials science and engineering and their interrelationship

▪ In materials science, the relationship between the structure of materials and its impact on their properties is
examined.
▪
In materials engineering, based on the knowledge gained from the relationship between structure and properties,
there is an effort to design the structure of a material to achieve a specific characteristic ex: hardness vs structure
of steel.
▪
The structure of materials is a function of the manufacturing process, and the performance of materials is a
function of their properties Ex: structure vs cooling rate of steel.
Example

• The impact of the process on the structure and properties of materials and, ultimately, the
performance of the material in response to light.
• Transmittance:
Material: Aluminum oxide: Through various manufacturing processes, one can obtain a single
crystal and transparent disc, a polycrystalline disc that is semi-opaque (light scatters at the grain
boundaries) translucent, or a polycrystalline disc with more defects that is completely opaque
depending on the material’s structure (i.e., single crystal vs. polycrystal, and degree of porosity).
polycrystal: polycrystal:
single crystal no porosity some porosity

Fig. 1.2, Callister &

Rethwisch 9e.
(Specimen preparation,
P.A. Lessing)
 STRUCTURE OF MATERIALS
• By structure we mean how some internal
components of the material is (are)
arranged.
• In terms of dimensionality, structural
elements include subatomic, atomic,
microscopic, and macroscopic

Chapter 1 -
 Structure, Processing, & Properties
• Properties depend on structure
ex: hardness vs structure of steel

(d)
600

Hardness (BHN)
30 μm
500 (c)
Data obtained from Figs. 12.31(a) and
12.32 with 4 wt% C composition, and from
400 (b) Fig. 17.8, Callister & Rethwisch 9e.
(a) Micrographs adapted from (a) Fig. 12.19;
4 μm
300 (b) Fig. 11.29; (c) Fig. 12.33; and (d) Fig.
12.21, Callister & Rethwisch 9e. (Figures
30 μm 12.19, 12.21, & 12.33 copyright 1971 by United
200 30 μm States Steel Corporation. Figure 9.30 courtesy
of Republic Steel Corporation.)

100
0.01 0.1 1 10 100 1000
Cooling Rate (ºC/s)
• Processing can change structure
ex: structure vs cooling rate of steel
Chapter 1 -
Question

▪ Why do we study materials science?

▪ Is it possible to have both high strength and good ductility in a single material?

In many engineering problems, we ultimately arrive at the selection of a material or its

manufacturing process, both of which influence the structure and properties of the
materials. Therefore, as a successful engineer, it is essential to have knowledge of the
structure and properties of materials and the impact of the manufacturing process on their
performance.
 TYPES OF MATERIALS

Most engineering materials can be classified into one of three basic categories:

1.Metals: Composed of metallic elements and a small amount of non-metallic

elements
2.Ceramics
3. Polymers

Their chemistries are different, and their mechanical and physical properties are
different
In addition, there is a fourth category:
4.Composites
-is a nonhomogeneous mixture of the other three types, rather than a unique category

5. Advanced materials
 TYPES OF MATERIALS (con’t)

Source: Fundamentals of Modern

Manufacturing materials: processes and
systems, M.P. Groover, 5th edition, John Wiley
& Sons Inc. (2007).
 METALS
Metallic bonds
– Strong, ductile, resistant to fracture
– High thermal & electrical conductivity
– Opaque, reflective.

Fig 1.8 Familiar objects that are made of metals and metal alloys
 METALS
➢ Metallic elements such as iron, copper, gold, aluminum, nickel, etc., can be combined with a small amount of non-
metallic elements like carbon, oxygen, and nitrogen.

➢ In the structure of metals, the atomic arrangement is much more orderly and denser than in the other two
categories, resulting in higher density.

➢ In terms of mechanical properties, metals are stiffer, stronger, and at the same time more ductile and more
resistant to crack propagation.

➢ Due to these advantages, they are used in most engineering applications. Their main disadvantage is their high
density.

➢ In the atomic structure of metals, there are many free electrons that do not belong to any specific atom, and many
of the properties of metals are related to these electrons, including high thermal and electrical conductivity.
 CERAMICS
Ionic bonding
–Brittle, glassy, elastic
–Non-conducting (insulative to the passage of heat & electricity)
–Transparent, translucent, or opaque
–Some exhibit magnetic behavior (e.g. Fe3O4)

13

Fig 1.8 Familiar objects that are made of ceramic materials

 CERAMICS

▪ The atomic structure of ceramics is a combination of metallic and non-metallic elements. They
often exist as compounds of oxygen (oxide), nitrogen (nitride), and carbon (carbide).

▪ Examples include alumina (Al₂O₃), silica (SiO₂), silicon carbide (SiC), and silicon nitride (Si₃N₄).

▪ A category of ceramics known as traditional ceramics is primarily derived from industrial clay:
porcelain, cement, and glass.

▪ Ceramic materials are relatively hard and have high strength (comparable to metals) but are very
brittle and fragile.

▪ Newly developed ceramics are fracture-resistant and are primarily used in cookware.

▪ Ceramics are electrical and thermal insulators and are resistant to corrosive environments.
 POLYMERS/PLASTICS
Covalent bonding → sharing of e’s
–Soft, ductile, low strength, low density
–Thermal & electrical insulators
–Optically translucent or transparent.
–Chemically inert and unreactive
–Sensitive to temperature changes

Fig 1.8 Familiar objects that are made of polymeric materials

 POLYMERS/PLASTICS
▪ These materials have organic compounds based on carbon and hydrogen, as well as other non-
metallic elements such as oxygen, nitrogen, and silicon.

▪ They generally have a large molecular structure and are chain-like based on carbon atoms.
Conventional polymers include polyvinyl chloride (PVC), polycarbonate (PC), polyethylene (PE),
nylon, etc.

▪ Polymers have low density with stiffness and strength, but their strength-to-weight ratio is
comparable to that of metals and ceramics.

▪ They are very flexible and malleable, making them suitable for producing complex shapes.
One of their disadvantages is their rapid degradation at relatively moderate temperatures.
 COMPOSITES
– Light, strong, flexible
– High costs
 COMPOSITES
▪ A composite material is a combination of two materials aimed at achieving enhanced combined
properties that do not exist in either component alone.

▪ There is a wide range of materials formed from the combination of metallic, ceramic, and polymeric
materials.

▪ One of the most well-known composites is fiberglass, where thin glass fibers are embedded in a
polymer matrix such as epoxy or polyester.

▪ Fiberglass derives its strength and stiffness from the glass fibers and its flexibility from the polymer. It
is very lightweight. Fiberglass is also referred to as GFRC (Glass Fiber Reinforced Concrete).

▪ Another category of composites is CFRC (Carbon Fiber Reinforced Concrete), which utilizes carbon
fibers instead of glass fibers.

▪ Carbon fibers are significantly stronger and more expensive than glass fibers.
 ADVANCED MATERIALS
Materials that are utilized in high-tech applications
•Semiconductors

Have electrical conductivities intermediate between conductors and insulators

•Biomaterials

Must be compatible with body tissues

•Smart materials

Could sense and respond to changes in their environments in predetermined manners

•Nanomaterials

Have structural features on the order of a nanometer, some of which may be designed on the
atomic/molecular level
 ADVANCED MATERIALS
Classification of Stimuli in Smart Materials:

•Shape Memory Alloy (SMA):

•These alloys can return to their original shape when heated after being
deformed at lower temperatures. Used in medical devices and actuators.

•Piezoelectric Ceramic:
•Generates an electric charge when stressed and changes shape under an
electric field. Commonly used in sensors and transducers.

•Magnetostrictive Material:
•Alters shape in response to a magnetic field. Used in sensors and actuators.

•Electro/magnetorheological Materials:
•Change viscosity with an electric or magnetic field, allowing them to switch
between solid and liquid states. Used in adaptive damping systems and
clutches.
 Example – HIP IMPLANT

• Requirements
– mechanical strength
(many cycles)
– good lubricity
– biocompatibility

Adapted from Fig. 22.26, Callister 7e.

 Types of Materials (Con’t)

Fig 1.3 Bar chart of room-temperature density values for various metals, ceramics, polymers, and
composite materials
 Types of Materials (Con’t)

Fig 1.4 Bar chart of room-temperature stiffness values for various metals, ceramics, polymers, and
composite materials
 Types of Materials (Con’t)

Fig 1.5 Bar chart of room-temperature strength (i.e. tensile strength) values for various metals,
ceramics, polymers, and composite materials
 Types of Materials (Con’t)

Fig 1.6 Bar chart of room-temperature resistance to fracture for various metals, ceramics, polymers,
and composite materials
 Research and Study

Research on Functionally Graded Materials

(FGMs):

What are these materials? What are their

applications? How are they produced?"
 Chapter 2: Atomic Structure &
Interatomic Bonding

Review…

▪ Atom and related basics and Atomic structure

▪ Atom electron configuration and valence electrons

▪ Bonding between atoms and types of bonds in materials (Atomic bonds)

 Chapter 2: Atomic Structure &
Interatomic Bonding
The Need to Study Atomic Structure:
•Some properties of materials are a function of the bonds between atoms (diamond and graphite).

•Diamond and graphite are both composed of carbon atoms but have vastly different properties.

•The structure of materials is influenced by:

• Type of atom
• Atomic bonds
• Arrangement of atoms
 Atomic Structure
Atom – electrons (-) 9.11 x 10-31 kg
protons neutrons (+) same mass as 1.67 x 10-27 kg
• Atomic number (Z) = # of protons in nucleus of atom = # of electrons for a neutral atom
• Isotope: Some elements have multiple atomic masses (their nuclei contain different numbers of
neutrons) Therefore, same Z, different number of neutrons

Two units are used to measure atomic mass:

1.The mass of a single atom (amu/atom)
2.The mass for one mole (6.022 × 10²³ atoms) (g/mol)
• Atomic mass unit (amu), It is equal to 1/12 of the atomic mass of 12C , the most common
isotope of the element carbon. This means the atomic mass of carbon is A=12 amu. Carbon has 6
protons and 6 neutrons.
• Atomic mass (or weight) A = averaged mass with respect to natural isotopes for an
element
A  Z + N 1 =1 amu g ATOMIC OR MOLECULAR WEIGHT =NA x WEIGHT PER
ATOM.
number of neutrons = N atom mol
number of protons = Z
Unit of atomic mass: g/mol (preferred) or amu/atom – 1 mole of atoms: Avogadro number
6.022 x 1023 = NA of atoms – Examples:
• For C, atomic mass = 12.011 g/mol, i.e., 12.011 g for 6.022x1023 of C atoms
• For H, atomic mass = 1.008 g/mol, i.e., 1.008 g for 6.022x1023 of H atoms
 Class Exercise: Review of Basics for Atom

Element name?
• # of electrons in a neutral atom? • # protons in such an atom? • Atomic number (Z)?• (Averaged)
Atomic mass (A) and Unit? Carbon Z=6, A=12.011 g/mol
 Example
From the periodic table using the information given for Aluminum answer the
followings:

•What is the atomic number (Z)? The atomic number is 13.

•How many protons are in the nucleus of an aluminum atom? There are 13 protons.

•What is the atomic weight (A) and its unit? The atomic weight is 26.98 g/mol.

•On average, how many aluminum atoms are there in one gram of aluminum?
• Given Avogadro's number (NA = 6.02 × 10²³ mol⁻¹), one gram of aluminum contains
approximately 2.23 × 10²² atoms.

•What is the averaged (over naturally occurring isotope) mass (weight) for one
aluminum atom?
 Position of the electron in the atom
Quantum Mechanics

Bohr Atomic Model: Explains the position and energy of the electron
WAVE MECHANICAL
Wave Mechanical Model: Electron Cloud MODEL OF ATOM

BOHR ATOM
 First, the smaller the principal quantum number, the lower the
energy level; for example, the energy of a 1s state is less than that
of a 2s state, which in turn is lower than the 3s. Second, within

Electronic Structure of atoms each shell, the energy of a subshell level increases with the value
of the l quantum number. For example, the energy of a 3d state is
• Electrons have wavelike and particulate properties. greater than a 3p, which is larger than 3s. Finally, there may be
overlap in energy of a state in one shell with states in an adjacent
– This means that electrons are in orbitals defined by a probability. shell, which is especially true of d and f states; for example, the
energy of a 3d state is greater than that for a 4s .
– Each orbital at discrete energy level is determined by quantum
numbers.
– Electrons occupy lower available energy state (orbitals) first

Quantum # Designation
n = principal (energy level-shell) K, L, M, N, O (1, 2, 3, etc.)
l = subsidiary (orbitals) s, p, d, f (0, 1, 2, 3,…, n -1)
ml = magnetic 1, 3, 5, 7 (-l to +l)
ms = spin ½, -½

Shell: K, L, M, (or 1, 2, 3) etc. from low to high energy

– Subshell: s, p, d, f, etc. within a shell from low to high energy
– Different orientations (orbits) of same energy within each subshell (for an isolated single atom)
Pauli exclusion principle: no more than two electrons in the same orbit, with one spin up & one spin down
Chapter 2 - 44
Electronic Structure of atoms

Pauli exclusion principle,

This principle stipulates that each electron state can hold no
more than two electrons, which must have opposite spins.
Thus, s, p, d, and f subshells may each accommodate,
respectively, a total of 2, 6, 10, and 14 electrons

Chapter 2 - 45
 Electron Energy States
Electrons...
• have discrete energy states
• tend to occupy lowest available energy state.

4d
4p N-shell n = 4

3d
4s

Energy 3p M-shell n = 3
3s
Adapted from Fig. 2.4,
Callister & Rethwisch 8e.
2p L-shell n = 2
2s

1s K-shell n = 1
Chapter 2 - 46
 SURVEY OF ELEMENTS
• Most elements: Electron configuration not stable.
Element Atomic # Electron configuration
In the conventional notation the number Hydrogen 1 1s 1
of electrons in each subshell is indicated Helium 2 1s 2 (stable)
by a superscript after the shell–subshell Lithium 3 1s 2 2s 1
designation. For example, the electron Beryllium 4 1s 2 2s 2
configurations for hydrogen, helium, Boron 5 1s 2 2s 2 2p 1 Adapted from Table 2.2,
and sodium are, respectively, Carbon 6 1s 2 2s 2 2p 2 Callister & Rethwisch 8e.
... ...
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? Valence (outer) shell usually not filled completely.

Chapter 2 - 47
 Electron Configurations
• Valence electrons – those electrons occupy outmost shells (and, for
transition metals, a few of inner shell electrons in the d-orbits)Filled shells
more stable
• Valence electrons are most available for bonding and tend to control the
chemical properties
– example: C (atomic number = 6)
1s2 2s2 2p2

valence electrons
Valence electrons determine the following properties
1) Chemical
2) Electrical
3) Thermal
4) Optical
• Atoms/ions with filled outmost shell will be stable:
For H, He, Li, Be: two(2) e- for 1s as the outmost shell is stable
Chapter 2 - 48
For others: outmost shell with eight (8) e- is stabl
 Electronic Configurations
ex: Fe - atomic # = 26 1s2 2s2 2p6 3s2 3p6 3d 6 4s2

4d
4p N-shell n = 4 valence
electrons
3d
4s

Energy 3p M-shell n = 3
3s
Adapted from Fig. 2.4,
Callister & Rethwisch 8e.
2p L-shell n = 2
2s

1s K-shell n = 1

Chapter 2 - 49
 Example

The electron configuration for Aluminum will be as

Chapter 2 - 50
Valence electrons
 The Periodic Table
• Columns: Similar Valence Structure– Group and similar chemical and physical properties
• Row: Same number of electron shells (not subshells) – Period

inert gases
give up 1e-
filled electron shells

give up 2e-
and stable electron

accept 2e-
accept 1e-
configurations

give up 3e-
one and two
electrons
deficient, H He
Li Be O F Ne
Adapted from
Na Mg S Cl Ar
halogens Fig. 2.6,
Callister &
K Ca Sc Se Br Kr
Rethwisch 8e.
Rb Sr Y Te I Xe
Groups IIIB through
IIB, are termed the transition Cs Ba Po At Rn
metals, which have partially filled d
electron states and in some cases Fr Ra
one or two electrons in the next
higher energy shell. Groups IIIA,
IVA, and VA (B, Si, Ge, As, etc.) Electropositive elements: Electronegative elements:
display characteristics that are
intermediate between the metals Readily give up electrons Readily acquire electrons
and nonmetals by virtue of their to become + ions. to become - ions.
valence electron structures.
Chapter 2 - 51
 Electronegativity
• Ranges from 0.7 to 4.0, which represents the tendency for an atom to acquire electrons
• Large values: tendency to acquire electrons.
• Right side of periodic table &
fewer number of shells
>>HIGHER electronegativity,
easier to GET electron(s)

• Left side of periodic table &

more number of shells >>
LOWER electronegativity, easier
to GIVE OUT electron(s)

Smaller electronegativity Larger electronegativity

Adapted from Fig. 2.7, Callister & Rethwisch 8e. (Fig. 2.7 is adapted from Linus Pauling, The Nature of the
Chemical Bond, 3rd edition, Copyright 1939 and 1940, 3rd edition. Copyright 1960 by Cornell University.

Chapter 2 - 52
 Bonding Energy
In materials, atoms are bonded together in certain ways

• Bonding energy - energy required to break the bonds between atoms

• Result of balance of attractive and repulsive forces

– minimum energy → most stable → stable inter-atomic distance
Interatomic forces between two atoms
Repulsive energy ER r₀ is approximately 0.3 nm. The two atoms will
counteract any attempt to separate them by an attractive force, or to push them
together by a repulsive action.

r
E N =  FN dr

Net energy EN
The attractive force FA depends on type of bonding between the two
atoms. While overlapping the outer electron shells of the two atoms
cause and a strong repulsive force FR comes into play.
Bond Attractive energy EA
energy Chapter 2 - 53
Adapted from Fig. 2.8(b), Callister & Rethwisch 8e
 Properties From Bonding: Tm
The properties of materials depend on E₀- it represents the energy that would be required to separate these
two atoms to an infinite separation

Chapter 2 - 54
 Different Bonds

• Primary Bonds

• Secondary Bonds

Chapter 2 - 55
 Ionic Bond (Primary)
• Occurs between + and - ions.
• Requires electron transfer.
• Large difference in electronegativity required.
• Example: NaCl
Na (metal) Cl (nonmetal)
unstable unstable
electron

Na (cation) + - Cl (anion)
stable Coulombic stable
Attraction
• Large bond energy
Chapter 2 - 56
ex: MgO Mg 1s2 2s2 2p6 3s2 O 1s2 2s2 2p4
[Ne] 3s2
Mg2+ 1s2 2s2 2p6 O2- 1s2 2s2 2p6

[Ne] [Ne]

Chapter 2 - 57
 Ionic Bond (Primary)

Energy –minimum
energy most stable
– Energy balance of
attractive and
repulsive terms

Figure 2.9 Schematic representation of

ionic bonding in sodium chloride (NaCl).
Adapted from Fig. 2.8(b),
Chapter 2 - 58
Callister & Rethwisch 8e.
Examples: Ionic Bonding (Primary)
• Predominant bonding in Ceramics
NaCl
MgO
CaF 2
CsCl

Give up electrons Acquire electrons

Adapted from Fig. 2.7, Callister & Rethwisch 8e. (Fig. 2.7 is adapted from Linus Pauling, The Nature of the
Chemical Bond, 3rd edition, Copyright 1939 and 1940, 3rd edition. Copyright 1960 by Cornell University.

Chapter 2 - 59
 Covalent Bonding (Primary)
• similar electronegativity  share electrons
• bonds determined by valence – s & p orbitals
dominate bonding
• Example: CH4
shared electrons
H
C: has 4 valence e-, CH 4
from carbon atom
needs 4 more
H: has 1 valence e-, H C H
needs 1 more
shared electrons
Electronegativities H from hydrogen
are comparable. atoms
2.1 for H and 2.5 for C
Adapted from Fig. 2.10, Callister & Rethwisch 8e.

Bond energy: usually large

Chapter 2 - 60
 Metallic Bond (Primary)
Metallic Bond -- Bonds between metal cations and delocalized electron cloud

Valence electrons do not

belong to a specific nucleus
and are free

Bond energy: usually large

Chapter 2 - 61
 Primary Bonding
• Metallic Bond -- delocalized as electron cloud

• Ionic-Covalent Mixed Bonding

 (X A −X B )2 
 −
4

% ionic character = 1− e  x (100%)
 
 
where XA & XB are Pauling electronegativities
Ex: MgO XMg = 1.2
XO = 3.5

 ( 3.5−1.2 )2 
 − 
% ionic character = 1 − e 4
 x (100%) = 73.4% ionic
 
 
Chapter 2 - 62
 SECONDARY BONDING
Arises from interaction between dipoles
• Fluctuating (induced) dipoles (e.g., for H2, Cl2)
asymmetric electron ex: liquid H 2
clouds H2 H2

+ - + - H H H H
secondary secondary
bonding Adapted from Fig. 2.13,
Callister & Rethwisch 8e. bonding

• Permanent dipoles-molecule induced (e.g., for HCl, H2O)

secondary
-general case: + - bonding
+ -
Adapted from Fig. 2.15,
Callister & Rethwisch 8e.
secondary
-ex: liquid HCl H Cl bonding H Cl

-ex: polymer secondary bonding between

individual polymer molecules
Chapter 2 - 63
 Hydrogen Bond (SECONDARY)
Strongest among all secondary bonds • A special case of permanent dipole
induced bonding
• Between individual molecules in which H is covalently bonded to F (e.g.,
HF), O (e.g., H2O), and N (e.g., NH3)

Hydrogen bond bonding energy is much higher than other types of secondary
bonding but still much weaker than bonding energy for primary bonds (i.e.,
covalent, ionic, or metallic bonds)

Chapter 2 - 64
 Summary: Bonding
Type Bond Energy Comments
Ionic Large! Nondirectional (ceramics)

Primary Covalent Variable Directional

bonds large-Diamond (semiconductors, ceramics
small-Bismuth polymer chains)

Metallic Variable
large-Tungsten Nondirectional (metals)
small-Mercury
Secondary smallest Directional
inter-chain (polymer)
inter-molecular
Chapter 2 - 65
 Summary: Primary Bonds
Ceramics Large bond energy
(Ionic & covalent bonding): large Tm
large E
small 

Metals Variable bond energy

(Metallic bonding): moderate Tm
moderate E
moderate 

Polymers Directional Properties

(Covalent & Secondary): Secondary bonding dominates
small Tm
small E
large 

• Metallic bonds are good conductors of electricity and heat.

Chapter 2 - 66
• Ionic and covalent bonds are electrical and thermal insulators
 Exercise
• Given the following electronegativity numbers
– χ (Na)=0.9;
– χ (F)=4.0;
– χ (Si)=1.8;
– χ (C)=2.5;
– χ (Mg)=1.2;
Determine the predominant primary bond type in the follow materials

– Sodium fluoride (NaF) Ionic bond

– Silicon carbide (SiC) Covalent bond

– Pure magnesium (Mg) Metallic bond

23

Chapter 2 - 67
 Class Exercise – Bonds
What is the bonding type between Oxygen and Oxygen atoms WITHIN a single
oxygen molecule?

Covalent bond
• Is the bonding between different oxygen molecules in liquid oxygen primary
bonding or secondary bonding?

Secondary bond
• What is the bonding type between Hydrogen (H) and oxygen WITHIN a single
water molecule?

Covalent bond
• What is the bonding type BETWEEN different water molecules in ice?
Secondary bond (Hydrogen bond, in particular)
Chapter 2 - 68