Materials and Heat Treatment

Course:

VẬT LIỆU HỌC VÀ XỬ LÝ

MATERIALS AND HEAT TREATMENT

Faculty of Mechanical Engineering

Instructor: Pham Quang Trung, Ph.D.

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 Chapter 1 Atomic Structure and
Interatomic Bonding
Learning Objectives

After studying this chapter you should be able to do the following:

1. Name the two atomic models cited, and note the differences between them.

2. Describe the important quantum-mechanical principle that relates to electron

energies.

3. (a) Schematically plot attractive, repulsive, and net energies versus

interatomic separation for two atoms or ions.
(b) Note on this plot the equilibrium separation and the bonding energy.

4. (a) Briefly describe ionic, covalent, metallic, hydrogen, and van der Waals
bonds.
(b) Note which materials exhibit each of these bonding types.
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 Overview of Chapter 1
• Review of Atomic Structure
Electrons, protons, neutrons, quantum mechanics of atoms, electron states, the periodic
Table

• Atomic Bonding in Solids

Bonding energies and forces

• Primary Interatomic Bonding

Ionic
Covalent
Metallic

• Secondary Bonding
Three types of dipole-dipole bonds

• Molecules and molecular solids

Understanding of interatomic bonding is the first step towards understanding/explaining

materials properties 3
 Review of Atomic Structure
The bonding mechanisms between atoms are closely related to the structure
of the atoms themselves.

Atoms = nucleus (protons and neutrons) + electrons

Charges:
Electrons and protons have negative and positive charges of the same
magnitude, 1.6 × 10-19 Coulombs.
Neutrons are electrically neutral.
Masses:
Protons and Neutrons have the same mass, 1.67 × 10-27 kg.
Mass of an electron is much smaller, 9.11 × 10-31 kg and can be neglected in
calculation of atomic mass.
The atomic mass (A) = mass of protons (Z) + mass of neutrons (N)
# protons gives chemical identification of the element
# protons = atomic number (Z)
# neutrons defines isotope number
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 Atomic mass units. Atomic weight.
The atomic mass unit (amu) is often used to express atomic weight. 1 amu is
defined as 1/12 of the atomic mass of the most common isotope of carbon atom
that has 6 protons (Z=6) and six neutrons (N=6).
Mproton ≈ Mneutron = 1.66 x 10-27 kg = 1 amu.
The atomic mass of the 12C atom is 12 amu.

The atomic weight of an element = weighted average of the atomic masses of

the atoms naturally occurring isotopes. Atomic weight of carbon is 12.011 amu.
The atomic weight is often specified in mass per mole.

A mole is the amount of matter that has a mass in grams equal to the atomic
mass in amu of the atoms (A mole of carbon has a mass of 12 grams).
The number of atoms in a mole is called the Avogadro number, Nav = 6.023 ×
1023.

1 amu/atom = 1 gram/mol
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 Atomic mass units. Atomic weight.

EXAMPLE PROBLEM 2.1

Average Atomic Weight Computation for Cerium

Cerium has four naturally occurring isotopes: 0.185% of 136Ce, with an
atomic weight of 135.907 amu; 0.251% of 138Ce, with an atomic weight
of 137.906 amu; 88.450% of 140Ce, with an atomic weight of 139.905
amu; and 11.114% of 142Ce, with an atomic weight of 141.909 amu.
Calculate the average atomic weight of Ce ?

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 Atomic mass units. Atomic weight.
Solution

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 Electrons in Atoms: Bohr Atomic Model
Bohr atomic model, electrons are
assumed to revolve around the atomic
nucleus in discrete orbitals, and the
position of any particular electron is
more or less well defined in terms of
its orbital.

Figure Schematic representation of the Bohr atom.

The energies of electrons are quantized—that is, electrons are permitted to
have only specific values of energy. An electron may change energy, but in
doing so, it must make a quantum jump either to an allowed higher energy
(with the absorption of energy) or to a lower energy (with the emission of
energy). Often, it is convenient to think of these allowed electron energies as
being associated with energy levels or states.
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 Electrons in Atoms: Wave mechanical model
+ This Bohr model was eventually found to have some
significant limitations because of its inability to explain
several phenomena involving electrons.
+ A resolution was reached with a wave-
mechanical model.
+ An electron is no longer treated as a particle
moving in a discrete orbital; rather, the
position is considered to be the probability of
an electron’s being at various locations
around the nucleus.
+ In other words, the position is described by
a probability distribution or electron cloud.

Figure 2.3 Comparison of the (a) Bohr and (b) wave mechanical atom models
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in terms of electron distribution.
 Atomic Bonding in Solids
PRIMARY INTERATOMIC BONDS
+ Three different types of primary or chemical bond are found in solids—ionic,
covalent, and metallic.
+ For each type, the bonding necessarily involves the valence electrons;
furthermore, the nature of the bond depends on the electron structures of the
constituent atoms.
+ In general, each of these three types of bonding arises from the tendency of
the atoms to assume stable electron structures, like those of the inert gases, by
completely filling the outermost electron shell.

SECONDARY BONDING OR VAN DER WAALS BONDING

Secondary or physical forces and energies are also found in many solid
materials; they are weaker than the primary ones but nonetheless influence the
physical properties of some materials. The sections that follow explain the
several kinds of primary and secondary interatomic bonds.

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 PRIMARY INTERATOMIC BONDS
Ionic bonding is perhaps the easiest to describe and visualize.
+ It is always found in compounds composed of both metallic and nonmetallic
elements.
+ Atoms of a metallic element easily give up their valence electrons to the
nonmetallic atoms.
+ Sodium chloride (NaCl) is the classic ionic material.

Figure Schematic representations of (a) the formation of Na and Cl ions and

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(b) ionic bonding in sodium chloride (NaCl).
Ionic bonding

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 PRIMARY INTERATOMIC BONDS
+ A second bonding type, covalent bonding, is found in materials whose
atoms have small differences in electronegativity—that is, that lie near one
another in the periodic table.
+ For these materials, stable electron configurations are assumed by the
sharing of electrons between adjacent atoms.
+ Two covalently bonded atoms will each contribute at least one electron to
the bond, and the shared electrons may be considered to belong to both
atoms.
+ The covalent bond is directional—that is, it is between specific atoms and
may exist only in the direction between one atom and another that
participates in the electron sharing.

Figure Schematic representation of covalent bonding in a molecule of

hydrogen (H2).
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PRIMARY INTERATOMIC BONDS
Covalent bonding

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 PRIMARY INTERATOMIC BONDS
Metallic bonding, is found in metals and their alloys. In this bonding model,
these valence electrons are not bound to any particular atom in the solid and are
more or less free to drift throughout the entire metal. They may be thought of as
belonging to the metal as a whole, or forming a “sea of electrons” or an
“electron cloud.”
The remaining nonvalence electrons and atomic nuclei form what are called ion
cores, which possess a net positive charge equal in magnitude to the total
valence electron charge per atom.

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Metallic Bonding

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 SECONDARY BONDING OR VAN DER WAALS BONDING
+ Secondary bonds, or van der Waals (physical) bonds, are weak in comparison
to the primary or chemical bonds.

+ Secondary bonding exists between virtually all atoms or molecules, but its
presence may be obscured if any of the three primary bonding types is present.

+ Secondary bonding forces arise from atomic or molecular dipoles. In essence,

an electric dipole exists whenever there is some separation of positive and
negative portions of an atom or molecule. The bonding results from the
coulombic attraction between the positive end of one dipole and the negative
region of an adjacent one, as indicated in Figure.

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SECONDARY BONDING OR VAN DER WAALS BONDING

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 MIXED BONDING
It is illustrative to represent the four bonding types—ionic, covalent, metallic,
and van der Waals—on what is called a bonding tetrahedron—a three-
imensional tetrahedron with one of these “extreme” types located at each
vertex.

Figure (a) Bonding tetrahedron: Each of the four extreme (or pure) bonding types is located at
one corner of the tetrahedron; three mixed bonding types are included along tetrahedron edges.
(b) Material-type tetrahedron: correlation of each material classification (metals, ceramics,
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polymers, etc.) with its type(s) of bonding.
 Bonding Type-Material Classification Correlations

Material-type tetrahedron: correlation of each material classification (metals,

ceramics, polymers, etc.) with its type(s) of bonding. 20
 SUMMARY
Electrons in Atoms
• The two atomic models are Bohr and wave mechanical. Whereas the Bohr
model assumes electrons to be particles orbiting the nucleus in discrete paths,
in wave mechanics we consider them to be wavelike and treat electron position
in terms of a probability distribution.
• The energies of electrons are quantized—that is, only specific values of
energy are allowed.

Primary Interatomic Bonds

+ For ionic bonds, electrically charged ions are formed by the transference of
valence electrons from one atom type to another.
+ There is a sharing of valence electrons between adjacent atoms when bonding
is covalent.
+ With metallic bonding, the valence electrons form a “sea of electrons” that is
uniformly dispersed around the metal ion cores and acts as a form of glue for
them.

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 SUMMARY
Secondary Bonding or van der Waals Bonding
+ Relatively weak van der Waals bonds result from attractive forces between
electric dipoles, which may be induced or permanent.

Mixed Bonding
In addition to van der Waals bonding and the three primary bonding types,
covalent–ionic, covalent–metallic, and metallic–ionic mixed bonds exist.

Bonding Type-Material Classification Correlations

Correlations between bonding type and material class were noted:
Polymers—covalent
Metals—metallic
Ceramics—ionic/mixed ionic–covalent
Molecular solids—van der Waals
Semi-metals—mixed covalent–metallic
Intermetallics—mixed metallic–ionic

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 QUESTIONS AND PROBLEMS
Question 1: Silicon has three naturally occurring isotopes: 92.23% of
28Si, with an atomic weight of 27.9769 amu; 4.68% of 29Si, with an

atomic weight of 28.9765 amu; and 3.09% of 30Si, with an atomic weight
of 29.9738 amu. On the basis of these data, confirm that the average
atomic weight of Si is 28.0854 amu.
Question 2: Zinc has five naturally occurring isotopes: 48.63% of 64Zn, with an
atomic weight of 63.929 amu; 27.90% of 66Zn, with an atomic weight of 65.926
amu; 4.10% of 67Zn, with an atomic weight of 66.927 amu; 18.75% of 68Zn,
with an atomic weight of 67.925 amu; and 0.62% of 70Zn, with an atomic
weight of 69.925 amu. Calculate the average atomic weight of Zn.

Question 3: Indium has two naturally occurring isotopes: 113In, with an

atomic weight of 112.904 amu; and 115In, with an atomic weight of 114.904
amu. If the average atomic weight for In is 114.818 amu, calculate the fraction-
of-occurrences of these two isotopes.
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 QUESTIONS AND PROBLEMS

Question 4 (a) How many grams are there in one amu of a material?
(b) Mole, in the context of this book, is taken in units of gram-mole. On this
basis, how many atoms are there in a pound-mole of a substance?

Question 5 (a) Cite two important quantum-mechanical concepts associated

with the Bohr model of the atom.
(b) Cite two important additional refinements that resulted from the wave-
mechanical atomic model.

Question 6. Briefly cite the main differences among ionic, covalent, and
metallic bonding.

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 QUESTIONS AND PROBLEMS
Question What type(s) of bonding would be expected for brass (a copper–zinc
alloy)?
(A) Ionic bonding
(B) Metallic bonding
(C) Covalent bonding with some van der Waals bonding
(D) van der Waals bonding

Question What type(s) of bonding would be expected for rubber?

(A) Ionic bonding
(B) Metallic bonding
(C) Covalent bonding with some van der Waals bonding
(D) van der Waals bonding

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