Materials Structure

ENGINEERING MATERIALS and Bonding

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CHAPTER OBJECTIVES:
 Explain and discuss the atomic structure and bonding
 Understand the relationship between crystal structure of metals and its atom
arrangement
 Identify and differentiates the imperfection and defects in crystal structure

Lesson Objectives:
• At the end of the semester, students should be able to:
 Analyze and illustrate the materials’ atomic bonding and crystal structure
TOPIC CONTENT

1. Atomic structure and bonding

2. Crystal Structure of Metals which includes BCC, FCC and HCP atom arrangement

3. Imperfection and defects in crystal structure

1. ATOMIC STRUCTURE AND BONDING
1.1 Atomic structure

What is atom?
• Basic structural unit of all engineering materials
• Atoms = Nucleus (protons + neutrons) + electrons

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1. ATOMIC STRUCTURE AND BONDING
a. Valence electrons

Valence electrons are the electrons that occupy the outermost filled shell.

• These electrons are extremely important as they participate in the bonding between
atoms to form atomic and molecular aggregates.
• Most of the electrical, mechanical, chemical and thermal properties of the atoms of
solids are based on these valence electrons.
• Example: C (atomic number 6)
 1S2 2S2 2P2

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1. ATOMIC STRUCTURE AND BONDING
b. Chemical elements
• Most elements: Electron configuration not stable
Element Atomic # Electron configuration
Hydrogen 1 1s1
Helium 2 1s2 (stable)
Lithium 3 1s22s1
Beryllium 4 1s22s2
Boron 5 1s22s22p1
Carbon 1s22s22p2
6
... ...
Neon 10 1s22s22p6 (stable)
Sodium 11 1s22s22p63s1
Magnesium 12 1s22s22p63s2
Aluminum 1s22s22p63s23p1
13
... ...
Argon 18 1s22s22p63s23p6 (stable)
... ... ...
Krypton 36 1s22s22p63s23p63d104s24p6 (stable)

Adapted from Table 2.2, Callister & Rethwisch 9e.

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 1. ATOMIC STRUCTURE AND BONDING
c. Periodic Table

Adapted from Fig. 2.8, Callister & Rethwisch 9e.

Columns: Similar
Valence Structure

Electropositive elements: Electronegative elements:

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

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 1. ATOMIC STRUCTURE AND BONDING
d. Electronegativity
• Ranges from 0.9 to 4.1,
• Large values: tendency to acquire electrons.

Larger electronegativity
Smaller electronegativity
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1. ATOMIC STRUCTURE AND BONDING
1.2 Types of bonding
Ionic
bonding

ii.
Secondary
bonding
i. Primary
atomic bonds
Metallic Covalent
bonding bonding

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1. ATOMIC STRUCTURE AND BONDING
a. Primary: Ionic bonding
 Occurs between + and - ions.
 Requires electron transfer.
 Large difference in electronegativity required.
 Example: NaCl

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1. ATOMIC STRUCTURE AND BONDING
a. Primary: Ionic bonding - Examples
NaCl
MgO
CaF 2
 Occurs in compounds that are
CsCl composed of both metallic and
nonmetallic elements

Give up electrons Acquire electrons

1. ATOMIC STRUCTURE AND BONDING
a. Primary: Ionic bonding - Ionic materials properties

 are hard because particles cannot easily slide past one another.
 are good insulators because there are no free electrons or ions (unless dissolved or
melted).
 are brittle and tend to cleave rather than deform because bonds are strong.
 have high melting point because ionic bonds are relatively strong.
 Some are transparent because their electrons are not moving from atom to atom and
less likely to interact with light photons
1. ATOMIC STRUCTURE AND BONDING
b. Primary: Covalent bonding
 similar electronegativity, and hence share electrons
 bonds determined by valence – s & p orbitals dominate bonding
 Example: CH4

shared electrons
C: has 4 valence e -, H
CH from carbon atom
4
needs 4 more

H: has 1 valence e-, H C H

needs 1 more
shared electrons
Electronegativities are from hydrogen
H atoms
comparable.
Adapted from Fig. 2.10, Callister & Rethwisch 8e.
1. ATOMIC STRUCTURE AND BONDING
c. Primary: Metallic bonding
 Occurs in the solid metals and alloys.

 In solid state, atoms are packed relatively close together in a systematic pattern or
crystal structure.

 The valence electrons of metallic materials are not bound to any particular atom in
the solid and are more or less free to drift throughout the entire metal.

 Valence electrons belong to the metal as a whole, or forming a “sea of electrons”.

1. ATOMIC STRUCTURE AND BONDING
c. Primary: Metallic bonding
 Metals have low ionization energies, thus they do not have a tight hold on their valence
electrons.
 These outer electrons easily move around, as they do not "belong" to any one atom, but
are part of the whole metal crystal
1. ATOMIC STRUCTURE AND BONDING
c. Primary: Metallic bonding

 The remaining non-valence electrons and atomic nuclei form ion cores, which
possess a net positive charge equal in magnitude to the total valence electron
charge per atom.

 Metallic bonding may be strong or weak.

 The properties of metallic materials are:

i. Good ductility
ii. Good electrical conductivity
iii. Lustrous
iv. Malleable
1. ATOMIC STRUCTURE AND BONDING
c. Primary: Metallic bonding

(a) Atomic arrangement in metallic copper

crystal. Each copper atom is
coordinated with 12 other copper
atoms, producing a crystal structure
called face-centered-cubic.
(b) Two dimensional schematic diagram of
metallically bonded atoms.

The circles with the inner positive ion

cores, and the charge clouds around the
iron cores represent the dispersed
(a) (b) valence electrons.
1. ATOMIC STRUCTURE AND BONDING
ii. Secondary bonding

 Fluctuating dipoles
asymmetric electron ex: liquid H2
clouds H2 H2

+ - + - H H H H
secondary secondary
bonding bonding
1. ATOMIC STRUCTURE AND BONDING
- Summary Ceramics Large bond energy
(Ionic & covalent bonding): large Tm
large E
small α

Metals Variable bond energy

(Metallic bonding): moderate Tm
moderate E
moderate α

Polymers Directional Properties

(Covalent & Secondary): Secondary bonding dominates
small Tm
small E
large α
2. CRYSTAL STRUCTURE OF METALS
- Materials and packing
Crystalline materials:
• atoms pack in periodic, 3D arrays
• typical of:
- metals crystalline SiO2
- many ceramics
- some polymers Si Oxygen
Non-crystalline materials:
• atoms have no periodic packing
• occurs for:
- complex structures
- rapid cooling
noncrystalline SiO2 Adapted from Fig. 3.11(a, b),
"Amorphous" = Non-crystalline Callister & Rethwisch 9e.
2. CRYSTAL STRUCTURE OF METALS
- Crystalline Solids Volume
Liquid

Melting

Crystal
Temperature
Tm
Quartz crystal

Properties:
Relate to orientation and are dependent on •Single crystals
the crystal’s axes (anisotropic). •Poly-crystals

Crystals become liquids at a specific

temperature (melting point)
2. CRYSTAL STRUCTURE OF METALS
- Amorphous Solids
Volume

Softening
Liquid

Amorphous
solid
Temperature
Tm
Wax

Properties:
Identical in all directions along any axis (isotropic).

• A relatively wide temperature range for the melting point.

• Soften gradually when they are heated.
2. CRYSTAL STRUCTURE OF METALS
- Crystalline Solids
The arrangement of the atoms is called crystalline structure

Unit cell

Crystalline structure Adapted from Callister & Rethwisch 9e.

2. CRYSTAL STRUCTURE OF METALS
- Crystalline Solids
The arrangement of the atoms is called crystalline structure

Space Lattice: A three-dimensional array

of points coinciding with atoms positions.

Unit cell: smallest repetitive volume which

contains the complete lattice pattern of a
crystal.

Space Lattice Unit cell

2. CRYSTAL STRUCTURE OF METALS
- Lattice Parameter

The size and shape of unit cell is described by six

parameters, which also called as lattice parameters. They
are:

► Three edge length a,b, and c

► Three interaxial angles α, β, and γ
2. CRYSTAL STRUCTURE OF METALS
- Crystal Systems

7 different types of unit cells

(specify the lattice constants): 4 basic types of unit cells:
1. Cubic 1. Simple
2. Tetragonal 2. Body-centered
3. Orthorhombic 3. Face-centered
4. Rhombohedral 4. Base-centered
5. Hexagonal
6. Monoclinic
7. Triclinic

14 standard unit cells (Bravais)

14 Bravais
Conventional Unit Cell
2. CRYSTAL STRUCTURE OF METALS
- The Structure of Metal
Why are some metals hard and other soft?
Why some metals can withstand high temperatures, while some others not?

Structure - arrangement of atoms

Influence the behavior and structure

2. CRYSTAL STRUCTURE OF METALS
- Metallic Crystal Structures
Metals crystallize in the dense-packed structures because energy is released. (atoms come close
together & bond more tightly with each other)

Body centered Face centered Hexagonal close-

cubic (BCC) cubic (FCC) packed (HCP)
2. CRYSTAL STRUCTURE OF METALS
- Metallic Crystal Structures

a=b=c=0.287nm

The cube side of the unit cell of BCC iron at room temperature is 0.287nm. If
unit cells of pure iron are lined up side by side, in 1mm there will be:

1 unit cell 6
1mm x = 3.48 x 10 unit cells
0.287nm x 10−6 mm/nm
2. CRYSTAL STRUCTURE OF METALS
- Simple Cubic Structure (SC)
Rare due to low
packing density
(only Po has this
structure)

• Coordination Number = 6
(nearest neighbors)
 2. CRYSTAL STRUCTURE OF METALS
- Atomic Packing Factor (APF)
Volume of atoms in unit cell
APF =
Volume of unit cell

• APF for a simple cubic structure = 0.52

volume
atoms
atom
a 4 3
unit cell 1 π (0.5a)
3
APF =
a3 volume
R=0.5a

close-packed directions unit cell

Adapted from Fig. 3.24, Callister & Rethwisch 8e.
2. CRYSTAL STRUCTURE OF METALS
i. Body Centered Cubic (BCC)

Atomic-site unit cell Hard-sphere unit cell Isolated unit cell

How many atoms ?

N = 1 + (0/2) + (8/8) = 2 atoms/unit cell
2. CRYSTAL STRUCTURE OF METALS
i. Body Centered Cubic (BCC)

Prove the relation between the lattice

constant a and the atomic radius R

Prove it!
2. CRYSTAL STRUCTURE OF METALS
i. Body Centered Cubic (BCC) cont’: Atomic packing factor
APF for a body-centered cubic structure = 0.68

3a
atoms
4 π ( 3 a/4 ) 3 volume
a unit cell 2
3 atom
2a APF =
R
a3 volume
a
Close-packed directions: unit cell

length = 4𝑅𝑅 = 3a
2. CRYSTAL STRUCTURE OF METALS
ii. Face Centered Cubic (FCC)

How many atoms ?

6 8
𝑁𝑁 = 0 + +
2 8

= 4 atoms/unit cell
Atomic-site unit cell Hard-sphere unit cell Isolated unit cell
2. CRYSTAL STRUCTURE OF METALS
ii. Face Centered Cubic (FCC)

𝒂𝒂 𝟐𝟐 + 𝒂𝒂 𝟐𝟐 = 𝟐𝟐𝒂𝒂

Prove it!
2. CRYSTAL STRUCTURE OF METALS
ii. Face Centered Cubic (FCC)
• APF for a face-centered cubic structure = 0.74 maximum achievable APF

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

Unit cell contains:

6 8
2a 𝑁𝑁 = 0 + + = 4 atoms/unit cell
2 8

atoms volume
4 π ( 2a/4 ) 3
unit cell 4 atom
3
a APF =
3 volume
a
unit cell
2. CRYSTAL STRUCTURE OF METALS
iii. Hexagonal Close-Packed Structure (HCP)
• A-B-A-B... Stacking Sequence
• 3D Projection • 2D Projection

A sites Top layer

c
B sites Middle layer

A sites Bottom layer

a
.

• Coordination # = 12
6 atoms/unit cell
• APF = 0.74
eg: Cd, Mg, Ti, Zn
• c/a = Adapted from Fig. 4.3(a), Callister &
Rethwisch 9e

1.633
2. CRYSTAL STRUCTURE OF METALS
iii. Hexagonal Close-Packed Structure (HCP) cont’

How many atoms?

1 1
𝑁𝑁 = 3 + 2 x + 12 x
2 6

= 6 atoms/unit cell

Atomic-site unit cell Hard-sphere unit cell Isolated unit cell

 2. CRYSTAL STRUCTURE OF METALS
- Comparison of FCC, HCP & BCC Crystal Structures
FCC HCP
Crystal Structure BCC
(close packed) (close-packed)
Atoms are positioned Atoms are positioned at Atoms are positioned at
at each corner of the each corner of the cube each corner of the
Atom position
cube and one at the and one at the center of hexagon and 3 at the
center of the cube each cube face center of the cube
Atomic Packing Factor
𝑉𝑉𝑉𝑉𝑉𝑉𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 0.68 0.74 0.74
=
𝑉𝑉𝑉𝑉𝑉𝑉𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐
Iron, tungsten, Cadmium, zinc,
Aluminum, copper, lead,
chromium, magnesium, cobalt,
Examples: nickel, and iron (at 912-
molybdenum, zirconium, titanium,
1394oC)
vanadium beryllium
2. CRYSTAL STRUCTURE OF METALS
- Theoretical Density, 𝝆𝝆

Mass of atoms in unit cell

Density = ρ =
Total volume of unit cell

NA
ρ=
𝑉𝑉𝐶𝐶 𝑁𝑁𝐴𝐴

Where N = number of atoms/unit cell

A = atomic weight
VC = Volume of unit cell = a3 for cubic
NA = Avogadro’s number
= 6.022 x 1023 atoms/mol
2. CRYSTAL STRUCTURE OF METALS
- Theoretical Density, 𝝆𝝆 cont'
4𝑅𝑅
a= = 0.2887nm
3
.

atoms
g
unit cell
2 52.00 mol
R
a volume ρ=
3 atoms
• Ex: Cr (BCC) a 6.022 x 1023
unit cell mol
A = 52.00 g/mol
R = 0.125 nm
ρtheoretical = 7.18 g/cm3
N = 2 atoms/unit cell
ρactual = = 7.19 g/cm3
2. CRYSTAL STRUCTURE OF METALS
Graphite/
Metals/ Composites/
Ceramics/ Polymers
Alloys fibers
- Densities of Material Classes Semicond
B ased on data in Table B1, Callister
20 Platinum *GFRE, CFRE, & AFRE are Glass,
In general: 𝜌𝜌𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 > 𝜌𝜌𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 > 𝜌𝜌𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃 Gold, W
Tantalum Carbon, & Aramid Fiber-Reinforced
Epoxy composites (values based on 60%
volume fraction of aligned fibers
10 Silver, Mo in an epoxy matrix).
Cu,Ni
Steels
Why? Tin, Zinc
Zirconia
5
• Metal have: Closed-packing (metallic bond), often

ρ (g/cm3 )
Titanium
4 Al oxide
Diamond
large atomic masses 3
Aluminum
Si nitride
Glass -soda Glass fibers
Concrete
Silicon PTFE GFRE*
• Ceramics have: less dense packing, often lighter 2
Magnesium Graphite Carbon fibers
CFRE*
Silicone Aramid fibers
elements PVC
PET AFRE *
1 PC
HDPE, PS
• Polymers have: low packing density (often PP, LDPE

amorphous), lighter elements (C,H,O) 0.5

Wood
0.4
• Composites have: intermediate values
0.3
Data from Table B.1, Callister & Rethwisch, 9e.
2. CRYSTAL STRUCTURE OF METALS
- Single vs Polycrystals
• Single Crystals • Polycrystals
-Properties vary with direction: anisotropic. -Properties may/may not vary with direction.
-Example: the modulus of elasticity (E) in BCC iron: -If grains are randomly oriented: isotropic.
(Epoly iron = 210 GPa)
E (diagonal) = 273 GPa -If grains are textured, anisotropic.

Data from Table 3.3, 200 μm

Callister & Rethwisch 9e.
(Source of data is R.W.
Hertzberg, Deformation and
Fracture Mechanics of Engineering
Materials, 3rd ed., John Wiley and
Sons, 1989.)

Adapted from Fig. 6.19(b), Callister & Rethwisch 9e.

E (edge) = 125 GPa [Fig. 6.19(b) is courtesy of L.C. Smith and C. Brady, the National Bureau of Standards, Washington, DC (now the
National Institute of Standards and Technology, Gaithersburg, MD).]
2. CRYSTAL STRUCTURE OF METALS
- Polymorphism
iron system
• Two or more distinct crystal structures for the
same material (allotropy/polymorphism) liquid
1538°C
titanium BCC δ-Fe
α, β -Ti 1394°C
FCC γ-Fe

Carbon 912°C
BCC
diamond, graphite α-Fe
3. IMPERFECTION AND DEFECTS IN CRYSTAL STRUCTURE
- Imperfections in solids

The properties of materials are a function of their:

1. Bonding Structure
2. Crystal Structure
3. Imperfections (Defects)
3. IMPERFECTION AND DEFECTS IN CRYSTAL STRUCTURE
- Imperfections in solids cont’

• There is no such thing as a perfect crystal.

• What are these imperfections?
• Why are they important?

• Many of the important properties of materials are due to the presence of

imperfections.
3. IMPERFECTION AND DEFECTS IN CRYSTAL STRUCTURE
- Types of Imperfections

• Vacancy atoms
• Interstitial atoms Point defects
• Substitutional atoms

• Dislocations Line defects

• Grain Boundaries Area defects

3. IMPERFECTION AND DEFECTS IN CRYSTAL STRUCTURE
- Point Defects in Metals
• Vacancies:
-vacant atomic sites in a structure. Vacancy

Distortion of planes

• Self-Interstitials:
-"extra" atoms positioned between atomic sites.
Self-
interstitial
Distortion of planes
3. IMPERFECTION AND DEFECTS IN CRYSTAL STRUCTURE
- Point Defects in Ceramics

• Vacancies
-- vacancies exist in ceramics for both
Cation
cations and anions Interstitial
• Interstitials
Cation
-- interstitials exist for cations Vacancy
-- interstitials are not normally observed for
anions because anions are large relative
to the interstitial sites

Anion
Vacancy

Fig. 6.2, Callister & Rethwisch 9e. (From W.G. Moffatt, G.W. Pearsall, and J. Wulff, The Structure and Properties of Materials, Vol. 1,
Structure, p.78. Copyright ©1964 by John Wiley & Sons, New York. Reprinted by permission of John Wiley and Sons, Inc.)
3. IMPERFECTION AND DEFECTS IN CRYSTAL STRUCTURE
- Imperfections in Ceramics
• Ex: NaCl Na+ Cl-
• Electroneutrality (charge cation
• Substitutional cation impurity vacancy
balance) must be maintained Ca2+
when impurities are present
Na+
Na+
Ca2+
without impurity Ca2+ impurity with impurity

• Substitutional anion impurity anion vacancy

O2-

Cl- Cl-
without impurity O2- impurity with impurity
3. IMPERFECTION AND DEFECTS IN CRYSTAL STRUCTURE
- Point Defects in Polymers
Defects due in part to chain packing errors and impurities such as chain ends and side chains

Adapted from Fig. 6.8,

Callister & Rethwisch 9e ISV.
3. IMPERFECTION AND DEFECTS IN CRYSTAL STRUCTURE
- Line Defects: Dislocations
slip steps
Dislocations:
 are line defects,
 slip between crystal planes result
when dislocations move,
 produce permanent (plastic)
deformation.
3. IMPERFECTION AND DEFECTS IN CRYSTAL STRUCTURE
- Line Defects cont’: Dislocations

• Rows of unit cells that become shifted and upset the orderly arrangement.
• Types of dislocations:
 Edge
 Screw
 Mixed

• All crystalline materials contain dislocations introduced during:

 Solidification
 Plastic deformation
 As a consequence of thermal stresses resulting from rapid cooling.
3. IMPERFECTION AND DEFECTS IN CRYSTAL STRUCTURE
- Line Defects cont’: Dislocations

Types of dislocations in a single crystal: (a) edge dislocation; and (b) screw dislocation.
3. IMPERFECTION AND DEFECTS IN CRYSTAL STRUCTURE
- Line Defects cont’: Dislocations

The formation of a step on the surface of a

crystal by the motion of
(a) an edge dislocation and
(b) a screw dislocation.

Note that for an edge, the dislocation line moves

in the direction of the applied shear stress τ; for a
screw, the dislocation line motion is perpendicular
to the stress direction.

Adapted from H. W. Hayden, W. G. Moffatt, and J. Wulff, The Structure and Properties of Materials,Vol. III, Mechanical Behavior, p. 70.
3. IMPERFECTION AND DEFECTS IN CRYSTAL STRUCTURE
- Line Defects cont’: Dislocations (Movement of an Edge Dislocation)

Movement of an edge dislocation across the crystal lattice under a shear stress. Dislocations
help explain why the actual strength of metals is much lower than predicted by theory.
3. IMPERFECTION AND DEFECTS IN CRYSTAL STRUCTURE
- Imperfections in Solids

Dislocations are visible in electron micrographs

Fig. 6.12, Callister & Rethwisch 9e. (Courtesy of M. R. Plichta, Michigan Technological University.)
3. IMPERFECTION AND DEFECTS IN CRYSTAL STRUCTURE
- Area Defect

Grain Boundaries
• regions between crystals
• transition from lattice of
one region to that of the
other
• slightly disordered
• low density in grain
boundaries
– high mobility
– high diffusivity
– high chemical reactivity

Adapted from Fig. 6.14, Callister & Rethwisch 9e.

SUMMARY

• Point, Line, and Area defects exist in solids.

• The number and type of defects can be varied and controlled (e.g., temperature controls
vacancy concentration).
• Defects may be desirable or undesirable (e.g., dislocations may be good or bad, depending
on whether plastic deformation is desirable or not).