CIVE 205

Introduction to Material Science

Spring 2017

Izmir University of Economics

Department of Civil Engineering

Acknowlegement: The slides are modified from Asst.Prof.Dr. Mert Yücel YARDIMCI’s work
& the book of Materials Science and Engineering by John Wiley & Sons, Inc.
 Atomic Bonding

• What promotes bonding?

• What types of bonds are there?
• How does bonding affect material
properties?
• Much of a material’s behavior can be
explained by the phenomena in this chapter
 Atomic Bonding

This is typical potential well for two interacting atoms.

The repulsion between atoms, when they are brought close to each
other, is related to the Pauli principle: when the electronic clouds
surrounding the atoms starts to overlap, the energy of the system
increases abruptly.
 Atomic Bonding

• atom – electrons – 9.11 x 10-31 kg

protons } 1.67 x 10-27 kg
neutrons
• atomic number = # of protons in nucleus of atom
= # of electrons of 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 = 1g/mol
C 12.011
H 1.008
 Atomic Bonding

• Valence electrons determine the following

properties:
1) Chemical
2) Electrical
3) Thermal
4) Optical
 Atomic Bonding
Electronic Structure
• Electrons have wavelike and particulate properties.
– This means that electrons are in orbitals defined by a
probability.
– Each orbital at discrete energy levels is determined by
quantum numbers.

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
 Atomic Bonding

Table 2.1 summarizes the maximum number of electrons that may

occupy each of the first four shells.
 Atomic Bonding
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

2p L-shell n = 2
2s

1s K-shell n = 1
Atomic Bonding
 Atomic Bonding
SURVEY OF ELEMENTS
• Most elements: Electron configuration 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 Adapted from Table 2.2,
Callister & Rethwisch 3e.
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? Valence (outer) shell usually not filled completely

 Atomic Bonding
Electron Configurations
• Valence electrons are those that occupy the outermost
shell.
• 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
 Atomic Bonding
Valance electrons
These electrons are extremely important;
• they participate in the bonding between atoms to form atomic
and molecular aggregates.
• many of the physical and chemical properties of solids are
based on these valence electrons.

The atoms, that is the states within the outermost or valence

electron shell are completely filled, are called inert (or noble) gases
are chemically unreactive chemically (stable electron
configurations). (Ne, Ar, Kr, and He)

Some atoms of the elements that have unfilled valence shells

assume stable electron configurations by gaining or losing electrons
to form charged ions.
 Atomic Bonding
• Columns: Similar Valence Structure

inert gases
give up 1e-
give up 2e-

accept 2e-
accept 1e-
give up 3e-

H He
Li Be O F Ne
Na Mg S Cl Ar
K Ca Sc Se Br Kr
Rb Sr Y Te I Xe
Cs Ba Po At Rn
Fr Ra

Electronegative elements:
Electropositive elements:
Readily acquire electrons
Readily give up electrons
to become - ions.
to become + ions.
 Atomic Bonding
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

2p L-shell n = 2
2s

1s K-shell n = 1
Atomic Bonding
 Atomic Bonding
Electronegativity
• Ranges from 0.7 to 4.0
• Large values: tendency to acquire electrons

Larger electronegativity
Smaller electronegativity Adapted from Fig. 2.7, Callister &
Rethwisch 3e. (Fig. 2.7 is adapted
As a general rule, electronegativity increases in moving from Linus Pauling, The Nature of
the Chemical Bond, 3rd edition,
from left to right and from bottom to top Copyright 1939 and 1940, 3rd
edition. Copyright 1960 by Cornell
University.
 Atomic Bonding
Bonding Energy
• Energy – minimum energy most stable
– Energy balance of attractive and repulsive terms

-
A -
B
EN = EA + ER =
r rn
Repulsive energy ER

Interatomic separation r

Net energy EN
The bonding energy for these two
atoms, E0, represents the energy that
would be required to separate these
Attractive energy EA two atoms to an infinite separation.
 Atomic Bonding
Properties From Bonding: Tm
• Bond length, r • Melting Temperature, Tm
Energy
r

• Bond energy, Eo ro
r
Energy smaller Tm

unstretched length
ro larger Tm
r
Eo = Tm is larger if Eo is larger.
“bond energy”
 Atomic Bonding
Properties From Bonding
• Coefficient of thermal expansion, a
length,Lo coeff. thermal expansion
unheated, T1
DL DL
= a (T2 -T1)
heated, T2 Lo

• a ~ symmetric at ro
Energy For a material, if Eo is smaller
unstretched length then alpha is larger (i.e. if we
ro heat up this material, it easily
r
expands)
Eo larger a
Eo smaller a
 Atomic Bonding
Primary Bonding
• Ionic
• Covalent
• Metallic

• Bonding involves the valence electrons.

• Bonding occurs due to the tendency of the atoms to assume
stable electron structures (completely filled outer shells)
 Atomic Bonding
Ionic Bonding
• 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
 Atomic Bonding
Schematic representation of ionic bonding in sodium chloride (NaCl)
 Atomic Bonding

Ionic bond – metal + nonmetal

donates accepts
electrons electrons

Dissimilar electronegativities (ex: MgO)(Mg:12, O:8)

Mg 1s2 2s2 2p6 3s2 O 1s2 2s2 2p4

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

 Atomic Bonding
Examples: Ionic Bonding
• Predominant bonding in Ceramics
NaCl
MgO
CaF 2
CsCl

Give up electrons Acquire electrons

Adapted from Fig. 2.7, Callister & Rethwisch 3e. (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.
 Atomic Bonding
Covalent Bonding
• similar electronegativity  share electrons
• bonds determined by valence – s & p orbitals dominate
bonding
• Example: polymers, SiC, CH4
shared electrons
H from carbon atom
C: has 4 valence e-,
needs 4 more
H: has 1 valence e-, H C H
needs 1 more
shared electrons
Electronegativities H from hydrogen
atoms
are comparable.

Schematic representation of covalent

bonding in CH4 (methane)
 Atomic Bonding

Covalently Bonded molecules

Many nonmetallic elemental molecules (H2, Cl2, F2)

Molecules containing dissimilar atoms, such as CH4, H2O, HNO3

and HF

Elemental solids such as diamond (carbon), silicon, and germanium

and other solid compounds composed of elements that are located
on the right-hand side of the periodic table, such as gallium arsenide
(GaAs), indium antimonide (InSb), and silicon carbide (SiC).
 Atomic Bonding

The number of Covalent Bonds...

The number of covalent bonds that is possible for a particular
atom is determined by the number of valence electrons.
For N’ valence electrons, an atom can (8-N’) covalently bond
with at most other atoms.
For example;
• One Cl (17) atom can bond to only one other atom as in the
case Cl2
• One carbon atom can bond to four other atoms as in the case
of diamond.

A unit cell for the diamond

cubic crystal structure.
 Atomic Bonding
Ionic-Covalent Mixed Bonding

 (-
( X A - X B )2 
% ioniccharacter  1 - e  x100
)
4
 
 
where XA & XB are Pauling electronegativities
Ex: MgO XMg = 1.2

XO = 3.5

 ( 3.5-1.2 ) 
2
-
% ionic character  1 - e 4  x (100%)  73.4% ionic
 
 
 Atomic Bonding
Metallic Bonding

•Metallic bonds have up to 3 valence

electrons that are not bound to a
specific atom.
•They drift throughout the metal
forming a “sea of electrons” or
“electron cloud”.
•The nonvalence electrons and nuclei
for the “ion cores”.
•The free electrons act as a “glue” to
hold the ion cores together.
•These are good conductors of heat
and charge (electricity).
 Atomic Bonding

Secondary Bonding (van der Waals)

• Interaction between dipoles; dipoles are a separation of

charge (+/-).
• Weaker forces (10kJ/mol) than primary bonding, yet these
bonds still influence physical properties.
• Secondary bonding exists in virtually all atoms and
molecules, but their presence may be obscured by primary
bonding.
 SECONDARY BONDING
(Van Der Waals Bonding, Physical Bonding)

• Fluctuating dipoles
asymmetric electron ex: liquid H 2
clouds H2 H2

+ - + - H H H H
secondary secondary
bonding bonding

• Permanent dipoles-molecule induced

secondary
-general case: + - bonding
+ -

secondary
-ex: liquid HCl H Cl bonding H Cl

-ex: polymer secondary bonding

 Atomic Bonding

Hydrogen bond is the

electrostatic attraction between
two polar groups that occurs
when a hydrogen (H) atom
covalently bond to a highly
electronegative atom such as N,
O or F experiences the
electrostatic field
 Atomic Bonding

• Bonding energies between 600 and 1500 kJ/mol (or 3 to 8 eV/atom) are considered
to be relatively large and will have correspondingly high (large) melting points.
 Summary: Bonding

Type Bond Energy Comments

Ionic Large Nondirectional (ceramics)
Coulombic force

Covalent Variable Directional

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

Metallic Variable
large-Tungsten Nondirectional (metals)
small-Mercury
Secondary smallest Directional
Van der Waals inter-chain (polymer)
inter-molecular
 Summary: Primary Bonding

Ceramics Large bond energy

(Ionic & covalent bonding): large Tm
large E

Metals Variable bond energy

(Metallic bonding): moderate Tm
moderate E

Polymers Directional Properties

(Covalent & Secondary): Secondary bonding dominates
small Tm
small E
 CRYSTAL STRUCTURES
&
PROPERTIES
ISSUES TO ADDRESS...
• How do atoms assemble into solid structures?
(for now, focus on metals)

• How does the density of a material depend on

its structure?

• When do material properties vary with the

sample (i.e., part) orientation?

Chapter 3- 1
 Classification of materials...
Solid materials may be classified according to the regularity with
which atoms or ions are arranged with respect to one another.

A crystalline material is one in which the atoms are situated in a

repeating or periodic array over large atomic distances; that is,
long-range order exists, such that upon solidification, the atoms
will position themselves in a repetitive three-dimensional pattern,
in which each atom is bonded to its nearest-neighbor atoms.

All metals, many ceramic materials, and certain polymers form

crystalline structures under normal solidification conditions. For
those that do not crystallize, this long-range atomic order is
absent; these noncrystalline or amorphous materials are discussed
briefly at the end of this chapter.
Chapter 3-
 MATERIALS AND PACKING
Crystalline materials...
• atoms pack in periodic, 3D arrays
• long range order over large
atomic distances
• typical of:-metals, -many ceramics crystalline SiO2
-some polymers and Adapted from Fig. 3.18(a),
Callister 6e.
organic molecules
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.

Chapter 3- 3
 Energy and Packing
• Non dense, random packing Energy

typical neighbor
bond length

typical neighbor r
bond energy

• Dense, ordered packing Energy

typical neighbor
bond length

typical neighbor r
bond energy

Dense, ordered packed structures tend to have lower energies.

39
Chapter 3-
Crystals – Hard Sphere Model

• Long range order – regular packing

–Atoms assumed to be hard spheres with
well defined diameters that touch
•Atoms are arranged on periodic array – or lattice
•Repetitive pattern – unit cell

Unit cell is defined by the lengths of the 3 sides

a, b, c
And angles between sides
a, , and 
Called lattice parameters
Chapter 3-
 METALLIC CRYSTALS
• tend to be densely packed.
• have several reasons for dense packing:
-Typically, only one element is present, so all atomic
radii are the same.
-Metallic bonding is not directional.
-Nearest neighbor distances tend to be small in
order to lower bond energy.

• have the simplest crystal structures.

Simple cubic structure (SC)
Face centered cubic structure (FCC)
Body centered cubic structure (BCC)

Chapter 3- 4
 SIMPLE CUBIC STRUCTURE (SC)
• Rare due to poor packing (only Po has this structure)
• Close-packed directions are cube edges.

• Coordination # = 6
1 atom/unit cell
(# nearest neighbors)

(Courtesy P.M. Anderson)

Chapter 3- 5
 ATOMIC PACKING FACTOR for SC

• APF for a simple cubic structure = 0.52

a
R=0.5a

close-packed directions
contains 8 x 1/8 =
1 atom/unit cell
Adapted from Fig. 3.19,
Callister 6e. Chapter 3- 6
 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.: aluminum, copper, gold, • Coordination # = 12

Silver, lead nickel, platinum

6 x 1/2 (face) + 8 x 1/8 (corner) Adapted from Fig. 3.1(a),

Callister 6e.
= 4 atoms/unit cell
Chapter 3- 9
(Courtesy P.M. Anderson)
 ATOMIC PACKING FACTOR: FCC
• APF for a face-centered cubic structure = 0.74

Close-packed directions (diagonal):

length = 4R = √2 a
a = 2R 2

Unit cell contains

4 atoms/unit cell
Adapted from
Fig. 3.1(a),
Callister 6e. atoms volume
4 p 3
unit cell 4 R
3 atom
APF =
volume
16 R3 2
unit cell
= 0.74 Chapter 3- 10
 FCC STACKING SEQUENCE
• ABCABC... Stacking Sequence
• 2D Projection
A
B B
C
A
A sites B B B
C C
B sites B B
C sites

• FCC Unit Cell

Chapter 3- 11
 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. – chromium, iron, molybdenum, tantalum, tungsten
• Coordination # = 8

2 atoms/unit cell
Adapted from Fig. 3.2,
Callister 6e.

(Courtesy P.M. Anderson) Chapter 3- 7

ATOMIC PACKING FACTOR for BCC
• APF for a body-centered cubic structure = 0.68

Close-packed direction - diagonal

4R
R a=
Adapted from a 3
Fig. 3.2,
Callister 6e.

Chapter 3- 8
Hexagonal Close-Packed Structure
(HCP)

49
Chapter 3-
 HEXAGONAL CLOSE-PACKED
STRUCTURE (HCP)
• ABAB... Stacking Sequence • 2D Projection
• 3D Projection

A sites

B sites

A sites
Adapted from Fig. 3.3,
Callister 6e.

• Coordination # = 12
• APF = 0.74

Chapter 3- 12
THEORETICAL DENSITY, r

Chapter 3- 14
 Theoretical Density, r
• Ex: Cr (BCC)
A (atomic weight) = 52.00 g/mol
n = 2 atoms/unit cell
R = 0.125 nm
R
a a = 4R/ 3 = 0.2887 nm

atoms
g
unit cell 2 52.00 rtheoretical = 7.18 g/cm3
mol
r= ractual = 7.19 g/cm3
a3 6.022 x 1023
volume atoms
unit cell mol 52
Chapter 3-
Crystal Systems
Lattice parameters
The unit cell geometry is
completely defined in terms of
six parameters:
Three edge lenghts:
a, b, c
Three interaxial angles:

7 crystal systems
14 crystal lattices

Chapter 3-
Crystal Systems

(To be continued)
Chapter 3-
 The fourteen
(14) types of
Bravais lattices
grouped in
seven (7)
systems.

(c) 2003 Brooks/Cole Publishing / Thomson Learning™

Chapter 3-
Characteristics of Selected Elements at 20C
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 ------ Adapted from
Table, "Charac-
Bromine Br 79.90 ------ ------ teristics of
Cadmium Cd 112.41 8.65 0.149 Selected
Elements",
Calcium Ca 40.08 1.55 0.197 inside front
Carbon C 12.011 2.25 0.071 cover,
Cesium Cs 132.91 1.87 0.265 Callister 6e.
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 ------ ------ Chapter 3- 15
 IONIC BONDING & STRUCTURE
• Charge Neutrality:
--Net charge in the
structure should
be zero.

--General form:

• Stable structures:
--maximize the # of nearest oppositely charged neighbors.

Adapted from Fig. 12.1,

Callister 6e.

Chapter 3- 15
 Coordination # and Ionic Radii
r cation
• Coordination # increases with r
anion
To form a stable structure, how many anions can
surround a cation?
r cation Coord ZnS
r anion # (zinc blende)
< 0.155 2 linear

0.155 - 0.225 3 triangular NaCl

(sodium
0.225 - 0.414 4 tetrahedral chloride)

0.414 - 0.732 6 octahedral CsCl

(cesium
chloride)
0.732 - 1.0 8 cubic

Chapter 3- 58
 Computation of Minimum Cation-Anion
Radius Ratio
• Determine minimum rcation/ranion for an octahedral site
a (C.N. = 6)
2ranion  2rcation  2a Measure the radii (blue
and yellow spheres)

a  2ranion Substitute for “a” in the

above equation

2ranion  2rcation  2 2ranion

ranion  rcation  2ranion rcation  ( 2 -1)ranion

rcation
 2 - 1  0.414
 ranion 
Chapter 3- 59
Example Problem: Predicting the Crystal
Structure of FeO
• On the basis of ionic radii, what crystal structure would you
predict for FeO?
Cation Ionic radius (nm) • Answer:
Al 3+ 0.053 rcation 0.077

Fe 2+ 0.077 ranion 0.140
Fe 3+ 0.069  0.550
Ca 2+ 0.100
based on this ratio,
-- coord # = 6 because
Anion
0.414 < 0.550 < 0.732
O2- 0.140
-- crystal structure is similar to NaCl
Cl - 0.181
F- 0.133
Chapter 3- 60
 Rock Salt Structure
Same concepts can be applied to ionic solids in general.
Example: NaCl (rock salt) structure
rNa = 0.102 nm

rCl = 0.181 nm

rNa/rCl = 0.564

 cations (Na+) prefer octahedral sites

61
Chapter 3-
 MgO and FeO
MgO and FeO also have the NaCl structure
O2- rO = 0.140 nm

Mg2+ rMg = 0.072 nm

rMg/rO = 0.514

 cations prefer octahedral sites

So each Mg2+ (or Fe2+) has 6 neighbor oxygen atoms

62
Chapter 3-