05/09/2022

ATOMIC BONDING, ARRANGEMENT

AND STRUCTURE

Dr. Deni Ferdian, M.Sc

Disclaimer: This lecture note is edited from different sources for the solely of teaching and
learning purposes. It may contain copyrighted materials from their respective owners;
therefore, apart form teaching and learning purposes, this lecture note may not be
reproduced, stored, or transmitted in any form or by any means.

THE ELECTRONIC STRUCTURE OF THE ATOM

Quantum numbers are the numbers that assign electrons in an atom to

discrete energy levels.
A quantum shell is a set of fixed energy levels to which electrons belong.
Pauli exclusion principle specifies that no more than two electrons in a
material can have the same energy. The two electrons have opposite
magnetic spins.
The valence of an atom is the number of electrons in an atom that participate
in bonding or chemical reactions.
Electronegativity describes the tendency of an atom to gain an electron.

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STRUCTURE OF ENGINEERING MATERIALS

History of Atomic Structure Model

BOHR – MODEL (1922)

orbital electrons:
n = principal
quantum number 1
n=3 2

Nucleus: Z = # protons

= 1 for hydrogen to 94 for plutonium

N = # neutrons

Atomic mass A ≈ Z + N

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© 2003 Brooks/Cole Publishing / Thomson Learning™

The atomic structure of sodium, atomic number 11, showing the electrons in the K, L,
and M quantum shells

© 2003 Brooks/Cole Publishing / Thomson Learning™

The complete set of quantum numbers for each of the 11 electrons in sodium

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STABLE ELECTRON CONFIGURATIONS

• have complete s and p subshells

• tend to be unreactive.

• Most elements: Electron configuration not stable. WHY??

ISOTOPES

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EXCITATION VS RELAXATION

THE PERIODIC TABLE

III-V semiconductor is a semiconductor that is based on group 3A and
5B elements (e.g. GaAs).
II-VI semiconductor is a semiconductor that is based on group 2B and
6B elements (e.g. CdSe).
Transition elements are the elements whose electronic configurations
are such that their inner “d” and “f” levels begin to fill up.
Electropositive element is an element whose atoms want to participate
in chemical interactions by donating electrons and are therefore highly
reactive.

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• Columns: Similar Valence Structure

Adapted
from Fig. 2.6,
Callister 6e.

Electropositive elements: Electronegative elements:

Readily give up electrons Readily acquire electrons
to become + ions. to become - ions.

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ELECTRONEGATIVITY
• Ranges from 0.7 to 4.0,
• Large values: tendency to acquire electrons.

Smaller electronegativity Larger electronegativity

Adapted from Fig. 2.7, Callister 6e. (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.

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ATOMIC BONDING

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IONIC BONDING
• Occurs between + and - ions.
• Requires electron transfer.
• Large difference in electronegativity required.
• Example: NaCl

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SALT STRUCTURE

Schematic
model
Lattice

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IONIC BOND – METAL + NONMETAL

donates accepts
electrons electrons

Dissimilar electronegativities

ex: MgO Mg 1s2 2s2 2p6 3s2 O 1s2 2s2 2p4

[Ne] 3s2

Mg2+ 1s2 2s2 2p6 O2- 1s2 2s2 2p6

[Ne] [Ne]

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EXAMPLES: IONIC BONDING

NaCl
MgO
H He
2.1 CaF2 -
Li Be O F Ne
1.0 1.5 CsCl 3.5 4.0 -
Na Mg Cl Ar
0.9 1.2 3.0 -
K Ca Ti Cr Fe Ni Zn As Br Kr
0.8 1.0 1.5 1.6 1.8 1.8 1.8 2.0 2.8 -
Rb Sr I Xe
0.8 1.0 2.5 -
Cs Ba At Rn
0.7 0.9 2.2 -
Fr Ra
0.7 0.9

Give up electrons Acquire electrons

Adapted from Fig. 2.7, Callister 6e. (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.

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COORDINATION # AND IONIC RADII

• Coordination # increases with
Issue: How many anions can you arrange around a cation?

Adapted from Fig. 12.4, Callister

6e.

Adapted from Fig. 12.2, Callister 6e.

Adapted from Fig. 12.3, Callister 6e.

Adapted from Table 12.2,
Callister 6e.

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COVALENT BONDING
• Requires shared electrons

• Example: CH4

C: has 4 valence e,
needs 4 more

H: has 1 valence e,
needs 1 more

Electronegativities
are comparable.

Adapted from Fig. 2.10, Callister 6e.

Covalent bonding requires that electrons be shared between atoms in such a way that each atom has its
outer sp orbital filled. In silicon, with a valence of four, four covalent bonds must be formed

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EXAMPLES: COVALENT BONDING

H2O
column IVA

H2 F2
C(diamond)
H He
2.1
SiC - Cl2
Li Be C O F Ne
1.0 1.5 2.5 2.0 4.0 -
Na Mg Si Cl Ar
0.9 1.2 1.8 3.0 -
K Ca Ti Cr Fe Ni Zn Ga Ge As Br Kr
0.8 1.0 1.5 1.6 1.8 1.8 1.8 1.6 1.8 2.0 2.8 -
Rb Sr Sn I Xe
0.8 1.0 1.8 2.5 -
Cs Ba Pb At Rn
0.7 0.9 1.8 2.2 -
Fr Ra
0.7 0.9 Adapted from Fig. 2.7, Callister 6e. (Fig. 2.7 is
GaAs
adapted from Linus Pauling, The Nature of the Chemical Bond, 3rd edition, Copyright 1939 and 1940, 3rd edition. Copyright 1960 by Cornell
University.

• Molecules with nonmetals

• Molecules with metals and nonmetals
• Elemental solids (RHS of Periodic Table)
• Compound solids (about column IVA)

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© 2003 Brooks/Cole Publishing / Thomson Learning™

Covalent bonds are directional. In silicon, a tetrahedral structure is formed,
with angles of 109.5° required between each covalent bond

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(a) In polyvinyl chloride (PVC),

the chlorine atoms attached to
the polymer chain have a
negative charge and the
hydrogen atoms are positively
charged. The chains are weakly
bonded by van der Waals bonds.
This additional bonding makes
PVC stiffer, (b) When a force is
applied to the polymer, the van
der Waals bonds are broken and
the chains slide past one another

© 2003 Brooks/Cole Publishing / Thomson

Learning™

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© 2003 Brooks/Cole Publishing / Thomson Learning™

METALLIC BONDING
The metallic bond forms
when atoms give up their
valence electrons, which
then form an electron sea.
The positively charged
atom cores are bonded by
mutual attraction to the
negatively charged
electrons

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© 2003 Brooks/Cole Publishing / Thomson Learning™

Figure When voltage is applied to a metal, the electrons in the electron sea can
easily move and carry a current

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SECONDARY BONDING
Arises from interaction between dipoles

• Fluctuating dipoles

Adapted from Fig. 2.13, Callister 6e.

• Permanent dipoles-molecule induced

Adapted from Fig. 2.14,

-general case: Callister 6e.

Adapted from Fig. 2.14,

-ex: liquid HCl Callister 6e.

-ex: polymer

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BONDING TYPE
Type Bond Energy Comments

Ionic Large! Nondirectional (ceramics)

Variable Directional

Covalent large-Diamond semiconductors, ceramics

small-Bismuth polymer chains)

Variable

Metallic large-Tungsten Nondirectional (metals)

small-Mercury

Directional

Secondary smallest inter-chain (polymer)

inter-molecular

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BINDING ENERGY AND INTERATOMIC SPACING

Interatomic spacing is the equilibrium spacing between the centers of

two atoms.
Binding energy is the energy required to separate two atoms from
their equilibrium spacing to an infinite distance apart.
Modulus of elasticity is the slope of the stress-strain curve in the elastic
region (E).
Yield strength is the level of stress above which a material begins to
show permanent deformation.
Coefficient of thermal expansion (CTE) is the amount by which a
material changes its dimensions when the temperature changes.

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Atoms or ions are separated

by and equilibrium spacing
that corresponds to the
minimum inter-atomic energy
for a pair of atoms or ions (or
when zero force is acting to
repel or attract the atoms or
ions)

© 2003 Brooks/Cole Publishing /

Thomson Learning™

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PROPERTIES FROM BONDING: T M

• Bond length, r • Melting Temperature, Tm

F
F

• Bond energy, Eo

Tm is larger if Eo is larger.

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PROPERTIES FROM BONDING: E

• Elastic modulus, E

Elastic modulus

F L
=E
Ao Lo

• E ~ curvature at ro
Energy

unstretched length
ro E is larger if Eo is larger.
r
smaller Elastic Modulus

larger Elastic Modulus 16

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© 2003 Brooks/Cole Publishing / Thomson Learning™

The force-distance curve for two materials, showing the relationship between
atomic bonding and the modulus of elasticity, a steep dFlda slope gives a high
modulus

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PROPERTIES FROM BONDING: A

• Coefficient of thermal expansion, a

coeff. thermal expansion

L
= a (T2-T1)
Lo

• a ~ symmetry at ro

a is larger if Eo is smaller.

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The inter-atomic energy (IAE)-separation curve for two atoms. Materials that display
a steep curve with a deep trough have low linear coefficients of thermal expansion

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SUMMARY: PRIMARY BONDS

Ceramics Large bond energy
large Tm
(Ionic & covalent bonding):
large E
small a

Metals Variable bond energy

moderate Tm
(Metallic bonding):
moderate E
moderate a

Polymers Directional Properties

(Covalent & Secondary): Secondary bonding dominates
small T
small E
large a

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LEVELS OF STRUCTURE
Level of Structure Example of Technologies

Atomic Structure Diamond – edge of

cutting tools

Atomic Arrangements: Lead-zirconium-titanate

Long-Range Order [Pb(Zrx Ti1-x )] or PZT –
(LRO) gas igniters

Atomic Arrangements: Amorphous silica - fiber

Short-Range Order optical communications
(SRO) industry

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LEVEL OF STRUCTURE: EXAMPLE OF

TECHNOLOGIES
Nanostructure Nano-sized particles of
iron oxide – ferrofluids

Microstructure Mechanical strength of

metals and alloys

Macrostructure Paints for automobiles

for corrosion resistance

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A DEEPER LOOK AT GRAIN STRUCTURE

Secondary arms
Macro-Scale:
Engine Block
~1m
Performance criteria:
•Power generated MASS TRANSPORT IN MICROSTRUCTURE FORMATION
•Efficiency
•Durability
•Cost Mesostructure:
grains
1-10 mm
Properties affected:
•High cycle fatigue
•Ductility
Microstructure:
dendrites & phases:
50-500 um
Properties affected:
•Yield strength
•Tensile strength Nano-structure:
•High/low cycle fatigue Precipitates
•Thermal growth 3-100 nm
•Ductility Properties affected:
•Yield strength Atomic Structure:
•Tensile strength 1-100 A
[D.R. Askeland and P. P. Phule, “The Science and and •Low cycle fatigue Properties affected:
Engineering of Materials”,Thomson, Brooks/Cole (USA) (2003)] •Ductility •Young’s Modulus
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•Thermal Growth

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Quartz Crystal

CRYSTAL STRUCTURE OF SOLİDS

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MATERIALS AND PACKING

Crystalline materials...
• atoms pack in periodic, 3D arrays
• typical of:
-metals
-many ceramics
-some polymers
crystalline SiO2
Adapted from Fig. 3.18(a),
LONG RANGE ORDER Callister 6e.

Noncrystalline materials...
• atoms have no periodic packing
• occurs for:
-complex structures
-rapid cooling

"Amorphous" = Noncrystalline noncrystalline SiO2

Adapted from Fig. 3.18(b),
Callister 6e.
SHORT RANGE ORDER

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METALLIC CRYSTAL STRUCTURES

How can we stack metal atoms to minimize empty space?
2-dimensions

vs.

Now stack these 2-D layers to make 3-D structures

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ROBERT HOOKE – 1660 - CANNONBALLS

“Crystal must owe its regular shape to the
packing of spherical particles”

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NIELS STEENSEN ~ 1670

observed that quartz crystals had the same
angles between corresponding faces
regardless of their size.

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CHRISTIAN HUYGENS - 1690

Studying calcite crystals made
drawings of atomic packing and
bulk shape.

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EARLY CRYSTALLOGRAPHY

René-Just Haüy (1781): cleavage of calcite

Common shape to all shards: rhombohedral
How to model this mathematically?
What is the maximum number of distinguishable shapes that will fill three
space?
Mathematically proved that there are only 7 distinct space-filling volume
elements

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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 that still retains the overall
characteristics of the entire lattice.
 Atomic radius - The apparent radius of an atom, typically calculated
from the dimensions of the unit cell, using close-packed directions
(depends upon coordination number).
 Packing factor - The fraction of space in a unit cell occupied by atoms.

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LATTICE
As explained before, a three-dimensional periodic arrangement of atoms, ions
or molecules is always present in all crystals. If each atom is represented by a
point (its centre of gravity), the arrangement is called a lattice.
The lattice of the crystal

Three-dimensional periodic A Lattice is a three dimensional arrangement

arrangement of atoms in a crystal of points in which all of the points have
identical surroundings

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CRYSTALLOGRAPHIC POINTS, DIRECTIONS, AND PLANES

It is necessary to specify a particular

point/location/atom/direction/plane in a unit cell
We need some labeling convention. Simplest way is to use a
3-D system, where every location can be expressed using
three numbers or indices.
 a, b, c and α, β, γ

α
β
y
γ
x

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POINT COORDINATES – ATOM POSİTİONS

z Point coordinates for unit cell center are
111
c
a/2, b/2, c/2 ½½½

000 y
a b Point coordinates for unit cell corner
are 111
x •
z 2c
• Translation: integer multiple of lattice
constants → identical position in
another unit cell
• •
b y
b
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CRYSTALLOGRAPHIC DIRECTIONS
z Algorithm
1. Vector repositioned (if necessary) to pass
through origin.
2. Read off projections in terms of
y unit cell dimensions a, b, and c
3. Adjust to smallest integer values
4. Enclose in square brackets, no commas
x [uvw]

ex: 1, 0, ½ => 2, 0, 1 => [ 201 ]

-1, 1, 1 => [ 111 ] where overbar represents a negative

index families of directions <uvw>

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CRYSTALLOGRAPHIC PLANES
Miller Indices: Reciprocals of the (three) axial intercepts
for a plane, cleared of fractions & common multiples. All
parallel planes have same Miller indices.

Algorithm
1. If plane passes thru origin, translate
2. Read off intercepts of plane with axes in terms of a, b, c
3. Take reciprocals of intercepts
4. Reduce to smallest integer values
5. Enclose in parentheses, no commas i.e., (hkl)

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CRYSTALLOGRAPHIC PLANES

Adapted from Fig. 3.9, Callister 7e.

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LINEAR DENSITY
Number of atoms
Linear Density of Atoms  LD =
Unit length of direction vector

[110]
ex: linear density of Al in [110]
direction
a = 0.405 nm

# atoms
2 =
a LD = 3.5 nm-1
length 2a

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AUGUST BRAVAIS
How many different ways can I put atoms into these seven crystal
systems, and get distinguishable point environments?

When I start putting

atoms in the cube, I have SC BCC FCC
three distinguishable
arrangements.

And, he proved mathematically that there are 14 distinct ways to arrange points in space.

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CRYSTAL SYSTEMS
Unit cell: smallest repetitive volume which
contains the complete lattice pattern of a crystal.

7 crystal systems

14 crystal lattices

a, b, and c are the lattice constants

Fig. 3.4, Callister

7e.

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THE CRYSTAL SYSTEMS

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SIMPLE CUBIC STRUCTURE (SC)

• Rare due to poor packing
• Close-packed directions are cube edges.

Closed packed direction is where • Coordination # = 6

the atoms touch each other (# nearest neighbors)

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BODY CENTERED CUBIC STRUCTURE (BCC)

• Close packed directions are cube diagonals.
--Note: All atoms are identical; the center atom is shaded
differently only for ease of viewing.

ex: Cr, W, Fe (a), Tantalum, Molybdenum

• Coordination # = 8

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

(Courtesy P.M. Anderson)

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ATOMIC PACKING FACTOR : SC

• APF for a simple cubic structure = 0.52

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ATOMIC PACKING FACTOR: BCC

3a
4R
a

2a
2a
R
Close-packed directions:
a
length = 4R = 3 a
atoms volume
4 3
unit cell 2  ( 3 a/4 ) atom
3
APF =
volume APF(BCC)= 0.68
a3
unit cell

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FACE CENTERED CUBIC STRUCTURE (FCC)

• Close packed directions are 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
• Coordination # = 12

Adapted from Fig. 3.1, Callister 7e.

4 atoms/unit cell: 6 face x 1/2 + 8 corners x 1/8

(Courtesy P.M. Anderson)

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ATOMIC PACKING FACTOR: FCC

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

Unit cell contains:

2a
6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell
a

atoms volume
4
unit cell 4 p ( 2a/4 )3 atom
3 maximum achievable
APF = = 0.74 APF
a3 volume
unit cell

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CHARACTERISTICS OF CUBIC LATTICES

SC BCC FCC
Unit Cell Volume a3 a3 a3
Lattice Points per cell 1 2 4

Nearest Neighbor Distance a a√3/2 a√2/2

Number of Nearest Neighbors 6 8 12

Atomic Packing Factor 0.52 0.68 0.74

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THEORETICAL DENSITY, R

Example: Copper

• crystal structure = FCC: 4 atoms/unit cell

• atomic weight = 63.55 g/mol (1 amu = 1 g/mol)
• atomic radius R = 0.128 nm (1 nm = 10 cm)
-7

Result: theoretical Cu = 8.89 g/cm3

Compare to actual: Cu = 8.94 g/cm3

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CHARACTERISTICS OF SELECTED ELEMENTS AT 20 DEG C

At. Weight Density Atomic radius
Element Symbol (amu) (g/cm3) (nm)
Aluminum Al 26.98 2.71 0.143
Argon Ar 39.95 ------ ------
Barium Ba 137.33 3.5 0.217
Beryllium Be 9.012 1.85 0.114
Boron B 10.81 2.34 ------
Bromine Br 79.90 ------ ------
Cadmium Cd 112.41 8.65 0.149
Calcium Ca 40.08 1.55 0.197
Carbon C 12.011 2.25 0.071
Cesium Cs 132.91 1.87 0.265
Chlorine Cl 35.45 ------ ------
Chromium Cr 52.00 7.19 0.125
Cobalt Co 58.93 8.9 0.125
Copper Cu 63.55 8.94 0.128
Flourine F 19.00 ------ ------
Gallium Ga 69.72 5.90 0.122
Germanium Ge 72.59 5.32 0.122
Gold Au 196.97 19.32 0.144
Helium He 4.003 ------ ------
Hydrogen H 1.008 ------ ------

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DENSITIES OF MATERIAL CLASSES

Why?
Metals have...
• close-packing
(metallic bonding)
• large atomic mass
Ceramics have...
• less dense packing
(covalent bonding)
• often lighter elements
Polymers have...
• poor packing
(often amorphous)
• lighter elements (C,H,O)
Composites have...
• intermediate values

Data from Table B1, Callister 6e.

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POLYMORPHISM & ALLOTROPY

Some materials may exist in more than one crystal structure, this is called
polymorphism.
If the material is an elemental solid, it is called allotropy. An example of
allotropy is carbon, which can exist as diamond, graphite, and amorphous
carbon.

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EXAMPLE. IRON (BCC-FCC-BCC)

“The same atoms can have more than one crystal structure”.

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AMORPHOUS MATERIALS

(c) 2003 Brooks/Cole Publishing / Thomson

Learning™

Figure 3.10 Atomic arrangements in crystalline silicon and amorphous silicon. (a)
Amorphous silicon. (b) Crystalline silicon. Note the variation in the inter-atomic
distance for amorphous silicon.

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SINGLE VS POLYCRYSTALS
• Single Crystals
Data from Table 3.3,
-Properties vary with Callister 6e.
direction: anisotropic. (Source of data is R.W.
Hertzberg, Deformation
and Fracture
-Example: the modulus Mechanics of
of elasticity (E) in BCC iron: Engineering Materials,
3rd ed., John Wiley and
Sons, 1989.)

• Polycrystals

-Properties may/may not 200 mm Adapted from Fig.

4.12(b), Callister 6e.
vary with direction. (Fig. 4.12(b) is courtesy
of L.C. Smith and C.
-If grains are randomly Brady, the National
oriented: isotropic. Bureau of Standards,
Washington, DC [now
(Epoly iron = 210 GPa) the National Institute of
Standards and
-If grains are textured, Technology,
Gaithersburg, MD].)
anisotropic.

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Single crystal
GRAIN
In one
grain,
atoms are
oriented at
the same
direction

Polycrystal

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DIFFRACTION TECHNIQUES FOR CRYSTAL

STRUCTURE ANALYSIS
 Diffraction - The constructive interference, or reinforcement, of a beam
of x-rays or electrons interacting with a material. The diffracted beam
provides useful information concerning the structure of the material.
 Bragg’s law - The relationship describing the angle at which a beam of
x-rays of a particular wavelength diffracts from crystallographic planes
of a given interplanar spacing.
 In a diffractometer a moving x-ray detector records the 2y angles at
which the beam is diffracted, giving a characteristic diffraction pattern

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X-RAYS - CRYSTAL STRUCTURE

• Incoming X-rays diffract from crystal planes.

Adapted from Fig. 3.2W,

Callister 6e.

Bragg’s
law.
• Measurement of:
Critical angles,
qc ,
for X-rays
provide
atomic spacing,
d.

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Learning
(c) 2003 Brooks/Cole Publishing / Thomson

Photograph of a XRD diffractometer. (Courtesy (a) Diagram of a diffractometer, showing powder

sample, incident and diffracted beams. (b) The
of H&M Analytical Services.) diffraction pattern obtained from a sample of
gold powder.

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