GE 201/203

Introduction to Materials Science and

Engineering
Lecture 4: Bonding and Intro to Crystal Structures
13/08/2019
Types of Bonds
 Primary Bonding (Chemical)

 Ionic (transfer of valence electrons)

 Covalent (sharing valence electrons, directional)

 Metallic (delocalization of valence electrons)

 Secondary or van der Waals Bonding (Physical)

 Dipole – Dipole

 H-bonding

 Fluctuating Induced Dipole Bonds

 Polar Molecule-Induced Dipole Bonds

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Secondary Bonding – van der Waals Bonds
 weaker bonds comparing to primary or chemical bonds
 exist between virtually all atoms and molecules
 arise from atomic or molecular dipoles, coulombic interactions between + & -.
Fluctuting Induced Dipole (H2, Cl2)
Permanent Dipole
Polar Molecule-Induced Dipole (HCl)

H-bond
Special case of vdW
H-N, H-O, H-F

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Bonding
Generally
Increasing
Bond Strength
Primary / Chemical
Strong Bond strength is
somewhat
correlated with the
melting temp.

Secondary /
Van der Waals
Weak

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Bonding – The Big Picture
Generally Increasing Bond Strength

Metallic Covalent Ionic

spheres are atoms spheres are ions
spheres are atoms

C (Graphite) C (Diamond)
Al, Cu, Ag, Au … Silicon NaCl, KCl, FeO
Strong covalent bonding within graphite
sheets. Weaker secondary bonding
between sheets.

C-H and O-H bonds within CH4 and H2O molecules are covalent.
Fe, Na, W …
Bonding between these molecules would be vdW (secondary) CsCl
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bonds, such as in solid methane and ice.
Bonding – Directionality and Constraints
Generally Increasing Geometric Requirements / Constraints

Metallic Covalent Ionic

Non-directional attraction
promotes ductility and high density.
Directionally-dependent attraction
dictated by orbital shape promotes
lower ductility and lower density.
Non-directional bonds.
A charge registry in the solid-state
hinders displacement / shifting of
ions to arbitrary positions, severely
limiting ductility.

Al, Cu, Ag, Au … C (Graphite)

NaCl, FeO, …

Fe, Na, W … C (Diamond) 6

Silicon CsCl
 Mixed Bonding
A bond can have mixed character depending on the difference in electronegativity between atoms of
interest.

Sn, Si, Bi, etc.

Cu, Ag, Fe

CuZr, CuZr2
Al2O3, TiN

We’re not talking about the simultaneous presence of multiple, “pure”, bonding schemes here.
We’re talking about a particular bond having characteristics of multiple bond types, such as partly covalent & partly ionic.
There is a continuum between the extreme bond types. 7
Bonding – Summary
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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Hierarchy: How does it look?

If you were to were to write a book what would be the hierarchy?

Letters The hierarchical structures guide our

Sentence construction of the final product
Paragraphs
Pages
Sub-atomic
Chapters
particles
Volume
Atoms Book
Unit Cells
Crystals
Microstructure
Components
Unit Cell

Unit cell:
(Lattice cell)
Smallest structural unit
that describes the whole
crystal structure.

Callister WD, Retwisch DG, “Fundamentals of Materials Science and Engineering”, 2011, 9th Ed. (Figure 3.1) 10
Unit Cell Atomic
Hard Sphere
Model

Reduced Sphere
Unit Cell

An aggregate of As an easy and simple way of representation we use

many atoms cubes or similar geometrical tools to represent a unit cell.

Callister WD, Retwisch DG, “Fundamentals of Materials Science and Engineering”, 2011, 9th Ed. (Figure 3.1) 11
What is a crystal

Crystal = Lattice + Basis

Recollect our
discussion of
hierarchy?

Identify this crystal structure

Identify this crystal structure

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Arranging apples

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Arranging apples

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How do crystals know the “right arrangement”

What is so special about

these structures? Why do
they form the way they
do?

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Crystal Structures of Metals

Do you observe any

trends?

Can you explain any of the

trends?

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