Materials 

for applications to 
MEMS
Paola Rivolo
e‐mail: paola.rivolo@polito.it

1
 Reference Textbooks

• Materials Science and Engineering: An Introduction
William D. Callister (J. Wiley and Sons)
• Foundations of Materials Science and Engineering
William F. Smith and Javad Hashemi (McGraw‐Hill)
• Solid State Chemistry and its Applications
Anthony R. West (J. Wiley and Sons)

2
 Materials Science and Engineering
• A branch of science & engineering that deals with the inter‐play between 
structure, properties and processing of materials

Properties
“Materials Science” “Materials Engineering”

Structure Processing

• Materials Science: investigates relationship between materials’ structure & 
properties: How do the arrangement of a materials components (e.g. atoms, etc.) 
influence its properties (e.g. does it conduct electrons or not)?

• Materials Engineering: The discipline of designing or engineering the 
structure of a material to produce a predetermined set of properties 
based on established structure‐property correlation.

Systematic study, not trial & error
3
 Materials Science and Engineering

Performance
(or Properties to Cost ratio)

Materials Engineering

Structure Synthesis and

Processing

Properties

Materials Science

4
 Materials Science and Engineering
• Processing/Structure/Properties/Performance
– They are interrelated as follow:

Processing Structure Properties Performance

• However, how processing influences the structure is critical

• Why? This will influence the material properties, which of
course affect its performance!

5
 Materials Science and Engineering

• Casting • Extrusion
• Forging
Processing • Calcinating
• Stamping Texturing, Temperature, • Sintering
• Layer-by-layer growth Time, Transformations
(nanotechnology)

Properties
characterization MatSE Physical behavior
Crystal structure Response to environment
Defects
Microstructure
• Mechanical (e.g., stress-strain)
• Microscopy: Optical, transmission • Thermal
electron, scanning tunneling • Electrical
• X-ray, neutron, e- diffraction • Magnetic
• Spectroscopy • Optical
• Corrosive
• Deteriorative characteristics 6
 Units of Length

1 cm*  10–2 m  0.01 m

1 mm  10–3 m  0.001 m
1 micron (μm)  10–6 m  0.000001 m
1 nanometer (nm)  10–9 m  0.000000001 m
1 Angstrom (Å)  10–10 m  0.0000000001 m

*nota bene: cm are not typically used.

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 Structure 

Properties
“Materials Science” “Materials Engineering”

Structure Processing

• Electronic level (subatomic)
• Atomic (molecular level, chemical composition)
• Crystal (arrangement of atoms or ions with one another)
• Microstructure (can study with microscopes)
• Macrostructure (can see with naked eye)

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 Structure...has many dimensions...

Structural feature Dimension (m)

atomic bonding < 10 -10

missing/extra atoms 10 -10

crystals (ordered atoms) 10 -8 -10 -1
second phase particles 10 -8 -10 -4
crystal texturing
> 10 -6

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How to have a look….. (characterization) 

<0.1 nm 1-10 nm 1-100 m >100 m

UHV-STM HRTEM, STEM Optical and Magnifying
Electron glasses or
AFM, XRD
Microscopes Naked Eye

10
Multiple Length Scales Critical in Engineering

In Askeland and Phule’s book, from J. Allison and W. Donlon (Ford Motor Company)
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A short History of Materials Science

“CONTROL” of materials
– Stone Age – naturally occurring materials
• Special rocks, skins, wood
– Bronze Age
• Casting and forging
– Iron Age
• High Temperature furnaces
– Steel Age
• High Strength Alloys
– Non‐Ferrous and Polymer Age
• Aluminum, Titanium and Nickel (superalloys) –
aerospace
• Silicon – Information 
• Plastics and Composites – food preservation, 
housing, aerospace and higher speeds
– Exotic Materials Age?
• Nano‐Material and bio‐Materials – they are coming 
and then …

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 A Multidisciplinary Approach
Macroscopic versus microscopic
• Engineers typically are interested in macroscopic properties (e.g. heat capacities,
viscosity, fracture strength, etc.)
• Scientists often describe things in microscopic terms (e.g. bond strength, orbital
theory, etc.)
• However, recent trends tend to mix both approaches: Engineers and Scientists
both look at micro and macroscopic properties and try to understand the
connection between them

13
Periodic Table of Elements
From http://64.224.111.143/handbook/periodic/

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Physical Classification of Materials by State

Gases

Liquids and Gases: Play a major role in heat transfer (e.g, radiator), hydraulic and 
pneumatic systems, lubrication 15
 Solid (Condensed) State: Generality

• At the solid state, particles (atoms, ions, molecules) are 10 times

closer each other than gases.
• They are characterized by higher density, are incompressible, they
have an own shape and volume
• They are not able to diffuse, also if slow diffusion phenomena happen
when two solids are put into contact
• Solids Kinetic Energy is only vibrational (no rotational and translational
components): only vibrations with respect to an equilibrium position
(characterized by an Energy minimum) are allowed
• Vibration entity depends on Temperature and nature and force of
interactions established among particles.
• Properties of solids can be explained for each case taking into account
interaction and different bonds force (depending on species chemical
nature) among particles

16
 Solid (Condensed) State: Generality
• Solids can be amorphous (low- order) or crystalline (high-order):
 amorphous materials do not have a specific Melting Point at a defined
Temperature. The starting temperature of melting is defined as Softening
Point
crystalline materials are characterized by a specific Melting Temperature
or Point, that is the temperature at which the transition from the solid
state to the liquid state starts, under a constant external pressure
The Temperature interval at which the complete process takes place is
about 1-2 °C.
Considering that in the crystalline state atoms are highly ordered and
placed at repeatable positions, bonds to be broken during melting have the
same energy  restricted melting Temperature interval
 Single crystal solids have properties (hardness, exfoliation, electrical
conductivity, refractive index) variable depending on the considered
crystalline direction  anisotropy exception for highly symmetric crystals
 Polycrystalline solids: crystals are oriented in all direction  isotropy

17
 Seven Major Classes of Materials ‐ 1
• Some of these have descriptive subclasses.
• Classes have overlap, so some materials fit into more than one class
Classification according to the way the atoms are bound together – 4 classes:

• Metals
• Iron and Steel
• Alloys and Superalloys (e.g. aerospace applications)
• Intermetallic Compounds (high-T structural materials)
Ex.: Aluminum, Copper, Titanium, many others

• Ceramics
• Structural Ceramics (high-temperature load bearing: Alumina, Zirconia)
• Refractories (corrosion-resistant, insulating: Bricks)
• Whitewares (e.g. porcelains)
• Glass
• Electrical Ceramics (capacitors, insulators, transducers, etc.: SiN, SiC)
• Chemically Bonded Ceramics (e.g. cement and concrete)

• Electronic Materials (Semiconductors)

• Silicon and Germanium
• III-V Compounds (e.g. GaAs)
• Photonic materials (solid-state lasers, LEDs) 18
 • Polymers
Seven Major Classes of Materials ‐ 2
• Plastics
• Liquid crystals
• Adhesives
Ex: Plastics, Wood, Cotton (rayon, nylon), “glue”
A variant or combinationof the previous four:
• Composites
• Particulate composites (small particles embedded in a different material, Metal
Matrix Composites)
• Laminate composites (golf club shafts, tennis rackets, Damaskus swords)
• Fiber reinforced composites (e.g. fiberglass or glass fibers reinforced
Polymers,Carbon Fiber-reinforced polymers)

• Smart (Functional) Materials and Advanced Materials

• Shape Memory Alloys (NiTi)
• Piezoeffect (PZT)
• Magnetostriction (Terfenol-D –Terbium-Dysprosium-Iron)
• Sensors-Actuators
• Elements of IC, Magnetic Storage, LCDs, Fiberoptics, thin fillms, MEMS, NEMS

• Biomaterials (really using previous 5, but bio-mimetic)

• Man-made proteins (cytoskeletal protein rods or “artificial bacterium”)
• Biosensors (Au-nanoparticles stabilized by encoded DNA for anthrax detection) 19
• Drug-delivery colloids (polymer based)
Functional classification of Materials ‐ 1

20
Functional classification of Materials – 2

21
22
23
Elements occurring in semiconductors

24
25
 Atomic Structure and Bonding

ISSUES TO ADDRESS...
• What promotes bonding?

• What types of bonds are there?

• What properties are inferred from bonding?

26
 Atomic Structure: fundamental concepts
Atoms are composed of electrons, protons, and neutrons. Electron and protons are negative
and positive charges of the same magnitude, 1.6 × 10‐19 Coulombs.
The mass of the electron is negligible with respect to those of the proton and the neutron,
which form the nucleus of the atom.
The unit of mass is an atomic mass unit (amu) = 1.66 × 10‐27 kg, and equals 1/12 the mass of a
carbon atom. The Carbon nucleus has Z=6, and A=6, where Z is the number of protons, and A
the number of neutrons. Neutrons and protons have very similar masses, roughly equal to 1
amu. A neutral atom has the same number of electrons and protons, Z.
A mole is the amount of matter that has a mass in grams equal to the atomic mass in amu of the
atoms. Thus, 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.
Calculating n, the number of atoms per cm3 in a piece of material of density d (g/cm3).
n = Nav × d / M
where M is the atomic mass in amu (grams per mol). Thus, for graphite (carbon) with a density d
= 1.8 g/cm3, M =12, we get 6 × 1023 atoms/mol × 1.8 g/cm3 / 12 g/mol) = 9 × 1022 C/cm3.
For a molecular solid like ice, one uses the molecular mass, M(H2O) = 18. With a density of 1
g/cm3, one obtains n = 3.3 × 1022 H2O/cm3. Note that since the water molecule contains 3
atoms, this is equivalent to 9.9 × 1022 atoms/cm3.
Most solids have atomic densities around 6 × 1022 atoms/cm3. The cube root of that number
gives the number of atoms per centimeter: about 39 x 106. The mean distance between atoms is
the inverse of that: 0.25 nm  2,5 Å. This is an important number that gives the scale of atomic
27
structures in solids.
 Atomic Models
• Towards the end of 19th century physicists realized Newtonian physics 
has serious difficulty in explaining many phenomena involving 
electrons => quantum mechanics
– Bohr atomic model
• Electrons assume very well defined orbits around the nucleus (protons + 
neutrons)
• Electrons in each shell orbit assumes the same energy level
– Electrons are assumed to revolve around the nucleus in discrete orbitals
– Severe issues when considering events involving electrons such as emission 
spectra and photoelectrons…)
– Wave mechanical model
• Electrons exhibit both wavelike and particlelike characteristics
• Electrons in an atom or molecule are permitted to have only specific values of 
energy, energy is quantized…
• Electrons do not move in circular orbits but in “fuzzy” orbits. At any given 
time we can only talk about the probability of finding an electron at a radius 
from the orbit.
• Every electron is characterized by four quantum numbers. The size, shape, 
spatial orientation of an electrons probability density are specified by these 
numbers
 Atomic Structure: Electrons in Atoms
The forces in the atom are repulsions between electrons and attraction
between electrons and protons.
Electrons form a cloud around the nucleus Radius ~ 0.05 – 1nm.
Picture looks like a mini planetary system.
But Quantum Mechanics says this analogy is not correct

orbital electrons:
n = principal
quantum number 1 BOHR Atomic Model
n=3 2 Adapted from Fig. 2.1,
Callister 6e.

Nucleus:

29
 Beyond Bohr’s Model

In 1924 de Broglie : dual character of electrons

In 1927 Heisenberg : uncertainity, it is not possible to measure simultaneously

both the momentum (or velocity) and the position of a microscopic particle
with absolute accuracy.

Schrodinger, math expression for the behavior of an electron around an

atom
 Atomic Structure:  Adapted from Fig. 2.3,
Callister 6e.
Electrons in Atoms
Wave Mechanical Model:

Electrons “orbits” are 'fuzzy‘

Can only discuss probability of finding
it at some distance from the nucleus.
Only certain “orbits” or shells
are allowed.
Shells identified by principal quantum
number n, n related to size of radius
(and energy) n = 1, smallest; n = 2,
3 .. are larger. (distance of electrons
from the nucleus)
Second quantum number l = s,p,d,f,
defines subshells: shape of electron
subshell)
Third and fourth quantum numbers ml
and ms characterize states within
subshells. 31
 Quantum Numbers (I)
• A product of Schrodinger’s Equation
– n, l , ml , ms
• n principal quantum number, distance of an 
electron from the nucleus
• l subshell, describes the shape of the subshell
• ml number of energy states in a subshell
• ms spin moment 
• Pauli’s exclusion principle: only one 
electron can have a given set of four 
quantum numbers
Quantum Numbers (II)

l ml ms = ±½
 Quantum Numbers (III)
Electrons fill quantum levels in order of increasing
energy ( only n and l make significant differences
in energy configurations).

1s, 2s, 2p, 3s,3p,4s,3d,4p,5s,4d,5p,6s,4f,5d,….

When all electrons are at the lowest possible

energy levels => ground state

Excited states do exist such as in glow discharges

etc…

Valence electrons occupy the outermost filled shell.

Valence electrons are responsible for all bonding !
Atomic Structure: Electron energy states
Electrons...
• have discrete energy states
• tend to occupy lowest available energy state.
Increasing energy

4p
n=4 3d
4s
n=3 3p
3s
n=2 2p
2s
n=1 1s Adapted from Fig. 2.5,
Callister 6e.

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Atomic Structure: Stable electron configuration
Stable electron configurations...
• have complete s and p subshells
• tend to be unreactive.

Z Element Configuration
2 He 1s2 Adapted from Table 2.2,
10 Ne 1s22s 22p6 Callister 6e.

18 Ar 1s2 2s22p63s23p6
36 Kr 1s2 2s22p63s23p63d10 4s24p6

(inert and noble gases) 

36
 Atomic Structure: 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 22s 1
Beryllium 4 1s 22s 2
Boron 5 1s 22s 22p 1 Adapted from Table 2.2,
1s 22s 22p 2 Callister 6e.
Carbon 6
... ...
Neon 10 1s 22s 22p 6 (stable)
Sodium 11 1s 22s 22p 63s 1
Magnesium 12 1s 22s 22p 63s 2
Aluminum 13 1s 22s 22p 63s 23p 1
... ...
Argon 18 1s 22s 22p 63s 23p 6 (stable)
... ... ...
Krypton 36 1s 22s 22p 63s 23p 63d 10 4s 24 6 (stable)

• Why? Valence (outer) shell usually not filled completely.

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 The Periodic Table
• Columns: Similar Valence Structure

inert gases
give up 1e
give up 2e

accept 2e
accept 1e
give up 3e
Metal

Nonmetal
H He
Li Be Intermediate Ne
O F
Na Mg Adapted
S Cl Ar
from Fig. 2.6,
K Ca Sc Se Br Kr Callister 6e.

Rb Sr Y Te I Xe
Cs Ba Po At Rn
Fr Ra

Electropositive elements: Electronegative elements:

Readily give up electrons Readily acquire electrons
to become + ions. to become - ions.
38
 The Periodic Table: Electronegativity
• Ranges from 0.7 to 4.0,
• Large values: tendency to acquire electrons.
• Atoms with electronegativity differences higher than 1.7 form
Ionic Bonds; lower than 1.7, form polar Covalent Bonds.
H He
2.1 -
Li Be F Ne
1.0 1.5 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

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.
39
Bonding Forces and Energies

FN=FA+FB

40
 Bonding Forces and Energies
Typical dependence of potential Energy as function of interatomic separation
of two atoms (it varies from material to material, in shape and magnitude)
Repulsion occurs when they are brought close together
Related to Pauli principle
(As electron clouds overlap energy increases)

repulsion
Equilibrium Spacing
Potential Energy, E

Attractive part: at large distances

(Depends on type of bonding)

0
attraction E0: minimum of potential 
r0 energy= energy required to 
separate atoms = bonding 
equilibrium energy 41
 Types of Chemical Bonding

Primary Bonding: e- are transferred or shared

Strong (100-1500 KJ/mol or 1-10 eV/atom)

 Ionic: Example - Na+Cl

Strong Coulomb interaction between
a positive atom (lost an electron, Na+) and
a negative atom (an extra electron, Cl-)

 Covalent: electrons shared between the atoms.

Example - H2

 Metallic:
Atoms lose some electrons from valence band
Those electrons are shared by all the material
42
 Types of Chemical Bonding

Secondary Bonding or Van der Waals Bonding:

no e- transferred or shared
Interaction of ions/molecular dipoles
Weak (< 10 KJ/mol or < 1 eV/atom)

 Fluctuating Induced Dipole (inert gases, H2, Cl2…)

 Polar Molecule- induced dipole bonds (polar molecule, HCl on
non-polar molecules)

 Permanent dipoles (polar molecules - H2O, HCl...)

43
 Ionic Bonding
Electron transfer from electropositive metal atoms to electronegative 
nonmetal atoms form ions which attract each other by coulombic forces:

• 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 44
Interatomic Interaction  Energy in Ionic Bond

n is a constant, approximatively equal to 8 45

 Strength of a Ionic Bond

1. The strength of an ionic bond is determined by the 
charges of the ions and the distance between them.
2. The larger the charges and the smaller the ions the 
stronger the bonds will be
3. Bond strength then is proportional to
Q1 x Q 2
r2
r2
Where Q1 and Q2 represent ion charges and r is the 
sum of the ionic radii.
46
 Ionic Bonding
• Electron transfer reduces energy of the
system
• Na shrinks and Cl expands

Ionic bonds: very strong, nondirectional bonds

In real solids, ionic bonding is usually combined with covalent bonding. In this
case, the fractional ionic bonding is defined as %ionic = 100 × [1 – exp(-0.25
(XA – XB)2], where XA and XB are the electronegativities of the two atoms, A
and B, forming the bond. 47
 Examples: Ionic Bonding
• Predominant bonding in Ceramics
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.
48
 Covalent Bonding
• Requires shared electrons
• Example: CH4
shared electrons
H from carbon atom
C: has 4 valence e, CH4
needs 4 more
H: has 1 valence e, H C H
needs 1 more
shared electrons
Electronegativities H from hydrogen
are comparable. atoms

Adapted from Fig. 2.10, Callister 6e.

The covalent bond is directional: it is between specific atoms and may exist
only in the direction between one atom and another that partecipates in the
electron sharing
In covalent bonding, electrons are shared between the molecules, to saturate the valence. 
The simplest example is the H2 molecule, where the electrons spend more time in between 
49
the nuclei than outside, thus producing bonding. 
 Covalent Bonding: Electron Sharing
Under special circumstances, the s and p orbitals combine forming
hybrid spn orbitals where n indicates the number of p orbitals
involved which may have value of 1, 2, 3. Elements of 3A,4A,5A
groups.
Hybridization: quantum mechanical interaction of the electronic
wave functions of the atoms such that s and p or s and d atomic
orbitals can combine to become equivalent and permit a number of
directional covalent bonds between atom pairs.
Examples:   sp3,   sp2,  sp, sd5,  etc.
Electrons in covalent solids are localized to the covalent bond.
They can’t shift within the crystal: covalent solids are insulators with 
high melting points.
Carbon
50
Ibrids sp3

Spatial Geometry
Bond angle: 109,5°

51 51
Ethane: 2 sp3  orbitals overlapping  σ bonds

52 52
Ibrids sp2 : ethylene
 σ + π bonds: double bond

Planar trigonal Carbon

Bond Angle: 120°

Ethylene

53 53
Ibrids sp : acethylene
 σ + π + π bond : triple bond
Bond Axis

Bond Angle: 180°

Acethylene

54
 Covalent Bonding

Example: Carbon Zc = 6 (1S2 2S2 2P2)

N’ = 4, 8 - N’ = 4  can form up to four covalent
bonds
ethylene molecule:

polyethylene molecule:

ethylene mer

55
 Covalent Bonding

2-D schematic of the “spaghetti-like”

structure
of solid polyethylene

Diamond:
(each C atom has four
covalent bonds with four
other carbon atoms)

56
 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 GaAs

• Molecules with nonmetals

• Molecules with metals and nonmetals
• Elemental solids
• Compound solids (about column IVA) 57
 Metallic Bonding
In metals, the atoms are ionized, loosing some electrons from the valence
band.
Those electrons form a electron sea, which binds the charged nuclei in place

• Arises from a sea of donated valence electrons

(1, 2, or 3 from each atom).
• Non- directional character
• Bonds may be weak or strong
• Energies range
from 68 kJ/mol for Mercury to 850
kJ/mol for Tungsten
• Remaining non valence electrons and
atomic nuclei form what are called ion
cores, which posses a net positive charge
equal in magnitude to the total valence
electron charge per atom
Adapted from Fig. 2.11, Callister 6e.

58
• Primary bond for metals and their alloys
 Secondary Bonding
Arises from interaction between dipoles
• Fluctuating dipoles (the weaker)
Electrically simmetric molecules with an istantaneous distorsion of this electrical
symmetry
ex: liquid H2
H2 H2

H H H H
secondary
bonding

Adapted from Fig. 2.13, Callister 6e.

Since the electrons may be on one side of the atom or the other, a dipole is formed: the +
nucleus at the center, and the electron outside. Since the electron moves, the dipole
fluctuates. This fluctuation in a molecule A produces a fluctuating electric field that is felt by
the electrons of an adjacent molecule B. Molecule B then polarizes so that its outer electrons
are on the side of the molecule A closest to the + side (or opposite to the – side) of the 59
dipole
in A. This bond is called van der Waals bonding.
 Secondary Bonding
secon
-ex: polymer dary
bond
in g

• Dipoles - polar molecule induced

_ _ _
+ + +
• Permanent dipoles (the strongest)
Due to asymmetry of positive and negative regions
Strongest among secondary bonds.
Adapted from Fig. 2.14,
secondary
-general case: + - bonding
+ - Callister 6e.

secondary Adapted from Fig. 2.14,

-ex: liquid HCl H Cl bonding H Cl Callister 6e.
60
 Secondary Bonding
• Hydrogen Bonding The Crystal Structures of Ice

“Hydrogen bond” – secondary bond formed

between two permanent dipoles in
adjacent water molecules.
MOLECULAR SOLID
Others: CO2, alcools, chetons, noble gases:
61
covalent bonds and intermolecular forces
 Mixed Bonding
The chemical bonding of atoms or ions can involve more than one type of
primary bonding:
2
• Ionic‐covalent: %ionic = 100 × [1 – e(‐0.25 (XA – XB) ]
According to Linus Pauling definition.
Many semiconducting compounds: GaAs (III‐V) and ZnSe (II‐VI): GaAs less
ionic character than ZnSe

• Metallic‐Covalent: Transition Metals, involving s, p, d bonding orbitals 

high melting points. IVA group, from top to bottom, increasing of metallic
charachter. Tin and lead are primary metallic bonded.

• Metallic‐Ionic: for intermetallic compounds, when there is a significant

difference in electronegativity in the elements forming the compounds,
may be a significant amount of electron transfer  ionic bonding: higher
for NaZn13, lower for Al9Co3 and Fe5Zn21

62
 Summary of Bonds and related properties
• Melting Temperature, Tm
• Elastic modulus, E • Coefficient of thermal expansion, 
Ceramics Large bond energy
(Ionic & covalent bonding): large Tm
large E
small 

Metals Variable bond energy

(Metallic bonding): moderate Tm
moderate E
moderate 

Polymers Directional Properties

(Covalent & Secondary): Secondary bonding dominates
small T
secon
dary
bond
small E
in g large 
63
Solid Structure

65
 ENERGY AND PACKING
• Non dense, random packing Energy

typical neighbor
bond length

typical neighbor r
bond energy

• Dense, regular packing Energy

typical neighbor
bond length

typical neighbor r
bond energy

Dense, regular-packed structures tend to have

lower energy.
66
 Crystalline Structure
• Allotropy: the property according which an element can exist in different crystalline
structure which have different chemical and physical properties: rombic and monocline
Sulfur; graphite, diamond and fullerene Carbon; black, white, red Phosphorus (it can
crystallize according to all seven crystalline systems).
 Monotropy: when only one STABLE crystalline form exists at every Pressure-
Temperature value and it cannot transform from the one to the other:
IRREVERSIBILITY
 Enantiotropy: when different stable crystalline forms exist and can transform
from the one to the other at specific Pressure/Temperature : REVERSIBILITY
• Polymorphism: substances can crystallize in several forms characterized by different
physico-chemical properties according to crystallization conditions. Transformation
from a crystalline phase to the other is slow, because the destruction of a crystalline
lattice in order to form the other is required
E.g.: TiO2 crystallize in tetragonal form (anatase and rutile) and in a rombohedric form
(brookite)
• Isomorphism: several substances exist as similar crystals (similar lattice parameters)
They can form solid solution:
 Perfect or complete Isomorphism: when the two isomorphs are mixable at any
ratio
 Imperfect or incomplete Isomorphism: when some defined ratio only are
allowed
67
Allotropy/Polymorphism some examples
• Two or more distinct crystal structures for the same 
material (allotropy/polymorphism)
iron system
titanium
liquid
, ‐Ti
1538ºC
BCC -Fe
carbon
diamond, graphite  1394ºC
FCC -Fe
912ºC
BCC -Fe

68
 Single vs Polycrystals
• Single Crystal
 The periodic and repeated arrangement is perfect or extends
throughout the entirety of the specimen without interruption.
 All unit cells interlock in the same way and have the same
orientation. Natural or synthetic. Difficulty for growth:
environment must be carefully controlled.
• Polycrystalline materials
 Collection of small crystals or grains.
 Initially small crystals or nuclei form at various positions.
 Random crystallographic orientations: the small grains grow by
the successive addition from the surrounding of atoms to the
structure of each.
 The extremities of adjacent grains impinge on one another as the
solidification process approaches completion.
 Crystallographic orientation varies from grain to grain
 Atomic mismatch within the region where two grains meet 70

grain boundary
 Single vs Polycrystals
• Single Crystals
-Properties vary with
direction: anisotropic.
-Example: the modulus
of elasticity (E) in BCC iron:
E (edge) = 125 GPa
• Polycrystals
-Properties may/may not
vary with direction.
-If grains are randomly
oriented: isotropic.
(Epoly iron = 210 GPa)
-If grains are textured,
anisotropic.
E (diagonal) = 273 GPa
Data from Table 3.3,
Callister 6e.
(Source of data is
R.W. Hertzberg,
Deformation and
Fracture Mechanics of
Engineering Materials,
3rd ed., John Wiley
and Sons, 1989.)
200 m Adapted from Fig.
4.12(b), Callister 6e.
(Fig. 4.12(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].)
71
Polycrystals Growth

72
 Polycrystals
• Most engineering materials are polycrystals.

Adapted from Fig. K,

color inset pages of
Callister 6e.
(Fig. K is courtesy of
Paul E. Danielson,
Teledyne Wah Chang
Albany)
1 mm

• Nb-Hf-W plate with an electron beam weld.

• Each "grain" is a single crystal.
• If crystals are randomly oriented,
overall component properties are not directional.
• Crystal sizes typ. range from 1 nm to 2 cm
(i.e., from a few to millions of atomic layers).
73
Seven Crystalline 
Systems (Unit cell)
• A unit cell is chosen to represent
the symmetry of the crystal
structure, wherein all the atom
positions in the crystal may be
generated by translations of the
unit cell integral distances along
each of its edges  building block
• Cell parameters: a, b, c = the three
edges length;    = the three
interaxial angles
• Seven different possible
combinations of the six
parameters  Seven crystals
systems

74
Fig. 3.4, Callister & Rethwisch 8e.
 14 Bravais lattices
 When the crystal systems are combined with the various possible lattice centerings, we arrive at the
Bravais lattices.
 Bravais lattice (the only 14 unique lattices possible in three dimensions)  an infinite array of points that
appears the same from any lattice point.
The 14 Bravais Lattices
• Simple Cubic
• Body Centered Cubic
• Face Centered Cubic
• Simple Tetragonal
• Centered Tetragonal
• Simple Orthorhombic
• Base Centered Orthorombic
• Body Centered Orthorhombic
• Face Centered Orthorhombic
• Simple Monoclinic
• Centered Monoclinic
• Triclinic
• Trigonal
75
• Hexagonal
76
77
 Point Coordinates
z
111 Point coordinates for unit cell 
c center are
a/2, b/2, c/2       ½ ½ ½

000
y
a b
Point coordinates for unit cell 
x  corner are 111
z 2c

Translation: integer multiple of 
  lattice constants  identical 
b y position in another unit cell 
b
78
 Crystallographic Directions
z Algorithm
1. Vector repositioned (if necessary) to pass
through origin.
2. Read off projections in terms of
unit cell dimensions a, b, and c
y 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>
Several nonparallel directions with different indices are equivalent,
79
that is the spacing of atoms along each direction is the same
 HCP Crystallographic Directions
z
Algorithm
1. Vector repositioned (if necessary) to pass
through origin.
2. Read off projections in terms of unit
a2 cell dimensions a1, a2, a3
3. Adjust to smallest integer values
- 4. Enclose in square brackets, no commas
a3
[uvtw] a
a1
2
Adapted from Fig. 3.7(a), Callister 
5e
a2 -a3
2
a3
a1
2
dashed red lines indicate
projections onto a1 and a2 axes a1
80
 HCP Crystallographic Directions
• Hexagonal Crystals
– 4 parameter Miller‐Bravais lattice coordinates are 
related to the direction indices (i.e., u'v'w') as follows.

z
[ u ' v ' w ' ]  [ uvtw ]

1
u  ( 2 u ' ‐ v ')
3
a2 1
v  ( 2 v ' ‐ u ')
3
‐
a3 t  ‐ (u + v )
a1
w  w '
Adapted from Fig. 3.7(a), Callister 5e.

81
 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
a
2
LD   3.5 nm 1
Adapted from
Fig. 3.1(a), length 2a
Callister & Rethwisch 
8e.

82
83
 Crystallographic Planes

Adapted from Fig. 3.10, Callister & 
Rethwisch 8e.
84
 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. Read off intercepts of plane with axes in  
terms of a, b, c
2. Take reciprocals of intercepts (A plane that parallels has 
an infinite intercept  0 index)
3. Reduce to smallest integer values
4. Enclose in parentheses, no  
commas i.e., (hkl)

85
 Crystallographic Planes
z
example a b c
1. Intercepts 1         1         c
2. Reciprocals 1/1      1/1     1/
1         1        0
3. Reduction 1         1        0 y
a b
4. Miller Indices (110)
x
z
example a b c
1. Intercepts 1/2         c
2. Reciprocals 1/½     1/ 1/
2        0         0
3. Reduction 2        0         0
y
4. Miller Indices (100) a b
x
86
 Crystallographic Planes
z
example a         b        c
1/2      1       3/4
c
1. Intercepts 
2. Reciprocals 1/½     1/1     1/¾
2 1      4/3  y

3. Reduction 6 3        4 a b

4. Miller Indices (634) x

Family of Planes {hkl}

Ex:   {100} = (100), (010), (001), (100), (010), (001)

87
MILLER Indeces for some important  
planes in a cubic crystal

89
 Crystallographic Planes (HCP)
• In hexagonal unit cells the same idea is used
• Four index‐scheme (hkil)
• Where i = ‐(h + k) z

example a1 a2 a3    c
1. Intercepts 1         -1 1
2. Reciprocals 1      1/ -1 1
1        0  -1 1 a2

3. Reduction 1        0 -1 1
a3

4. Miller-Bravais Indices (1011) a1

Adapted from Fig. 3.8(b), 
Callister & Rethwisch 8e.

90
 Planar Density of (100) Iron
Solution: At T < 912ºC iron has the BCC structure.
2D repeat unit

(100) 4 3
a R
3

Adapted from Fig. 3.2(c), Callister & Rethwisch 8e. Radius of iron R = 0.1241 nm

atoms
2D repeat unit 1
1 atoms atoms
Planar Density = =  =  12.1 = 1.2 x 10 19
2
area a2 4 3 nm2 m2
R
2D repeat unit 3
91
 Planar Density of (111) Iron
Solution (cont): (111) plane 1 atom in plane/ unit surface cell

2a atoms in plane
atoms above plane
atoms below plane

3
h a
2
2
 4 3  16 3 2
area  2 ah  3 a  3 
2
R   R
atoms  3  3
2D repeat unit 1
Planar Density = =  atoms =  atoms
7.0 0.70 x 1019
area 16 3 nm2 m2
R2
2D repeat unit 3
92
 MILLER INDECES‐SUMMARY

Points a, b, and c as units

Directions
Planes

Points  point coordinates, example: P [[ 2 1 0 ]]

Planes: (100)

Directions: lines through origin, example: [111]

Families of directions <111>

A group of equivalent (parallel) planes: 100

93
 METALS
• Properties of metals
– High number of delocalized electrons
– What does this mean?  ‐‐ The electrons (outer valence e‐’s of the 
various atoms) are not bound to particular atoms
– Impact delocalization has on properties:
– Good conductors of heat and electricity
– Opaque to visible light
– High density

– Atoms arranged in a regular repeating structure
– Mechanically they are strong, yet deformable
– Shiny appearance
– Malleable or ductile
– Resistant to fracture tough
94
 METALS
• Thus, metals can be formed and machined easily, and are usually long-lasting materials.

• They do not react easily with other elements, however, metals such as Fe and Al do form
compounds readily (such as ores) so they must be processed to extract base metals.

• One of the main drawbacks is that metals do react with chemicals in the environment, such as
iron-oxide (rust).

• Many metals do not have high melting points, making them useless for many applications.
Applications
• Electrical wiring
• Structures: buildings, bridges, etc.
• Automobiles: body, chassis (car internal framework), springs, engine block, etc.
• Airplanes: engine components, fuselage, landing gear assembly, etc.
• Trains: rails, engine components, body, wheels
• Machine tools: drill bits, hammers, screwdrivers, saw blades, etc.
• Shape memory materials: eye glasses
• Magnets
• Catalysts
Examples
• Pure metal elements (Cu, Fe, Zn, Ag,Au, Pt, Al, etc.)
• Alloys (Cu-Sn=bronze, Cu-Zn=brass, Fe-C=steel, Pb-Sn=solder, NiTinol) 95
• Intermetallic compounds (e.g. Ni3Al)
 Alloys
Small amounts of a another
element added to a metal can
change its overall properties.
For example, adding a small
amount of carbon to iron, will
significantly increase its hardness
and strength forming steel.
1) Substitutional or 2) Interstitial
position

1) Because the atoms are considered to be positive spheres in a

sea of electrons , any similar sized sphere can fit right in without
too much trouble.
2) Even dissimilar sized (i.e. even smaller H atoms) can fit into the
spaces between atoms. 96
 Intermetallic compounds
• Intermetallics: compounds formed by 2 metals which have a distinctive chemical formula or
a defined stoichiometry (fixed ratio of involved atoms)
• Mixture of metallic‐ionic or metallic‐covalent bond

97
 Semimetals or Metalloids  Semiconductors

The electrons in semimetals are much less mobile than in 
metals, hence they are semiconductors
98
 CERAMICS
• Properties of Ceramics
– “Between” metallic and nonmetallic compounds
• Oxides, nitrides, and carbides
• Except for glasses, atoms are regularly arranged
• These materials are typically insulators of heat and electricity
• Some transparent (Single crystals are transparent)
• Stronger than metals
• Low resistance to fracture: low toughness or brittle 
• Mechanically – ceramics are hard but brittle
• Low ductility or malleability: low plasticity 
• High melting point 
• More resistant to high temperature and harsh environments ‐
corrosion resistant ‐(e.g. pH) than metals (e.g. Alumina 
(Al2O3) and Silica (SiO2, Quartz)
99
• Chemically inert
 CERAMICS
Applications
• Electrical insulators
• Abrasives
• Thermal insulation and coatings
• Windows, television screens, optical fibers (glass)
• Corrosion resistant applications
• Electrical devices: capacitors, varistors, transducers, etc.
• Highways and roads (concrete)
• Biocompatible coatings (fusion to bone)
• Self-lubricating bearings
• Magnetic materials (audio/video tapes, hard disks, etc.)
• Optical waveguides
• Night-vision

Examples
• Simple oxides (SiO2, Al2O3, Fe2O3, MgO)
• Mixed-metal oxides (SrTiO3, MgAl2O4, YBa2Cu3O7-x, having vacancy defects.)
• Nitrides (Si3N4, AlN, GaN, BN, and TiN, which are used for hard coatings.)

100
101
 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.

• assuming hard sphere,
each sphere represent s an ion core

102
 METALLIC CRYSTALS

We will look at four such structures: 

SC = simple cubic
FCC = face-centered cubic
HCP = hexagonal close-packed
BCC = body-centered cubic 103
 SIMPLE CUBIC STRUCTURE (SC) and 
Coordination number
• Rare due to poor packing (only Po has this structure)
• For metals, each atom has the same number of nearest
neighbor or touching atoms
• Bulk Coordination number=
the number of atoms touching the given atom
• Close-packed directions are cube edges

• Coordination # = 6
(# nearest neighbors)

(Courtesy P.M. Anderson) 104

 SIMPLE CUBIC STRUCTURE (SC) and atomic 
packing factor
Volume of atoms in unit cell*
APF =
Volume of unit cell
*assume hard spheres

• APF for a simple cubic structure = 0.52

volume
atoms atom
a 4
unit cell 1 (0.5a)3
3
R=0.5a APF =
a3 volume
close-packed directions
unit cell
contains 8 x 1/8 =
1 atom/unit cell • APF is the the fraction of solid
Adapted from Fig. 3.19,
Callister 6e.
sphere volume in a unit cell 105
 FACE CENTERED CUBIC STRUCTURE (FCC)
• Atoms touch each other along face diagonals.
• 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(a),

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

(Courtesy P.M. Anderson)

106
 FACE CENTERED CUBIC STRUCTURE (FCC)
• APF for a face-centered cubic structure = 0.74

Close‐packed directions: 
length = 4R = 2 a
Unit cell contains:
6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell
a
Adapted from
Fig. 3.1(a),
Callister 6e. atoms volume
4
unit cell 4 ( 2a/4)3
3 atom
APF =
3 volume
a
unit cell
107
108
 FCC Stacking Sequence
•  ABCABC... Stacking Sequence
•  2D Projection

B B
C
A
A sites B B B
C C
B sites B B
C sites

A
•  FCC Unit Cell B
C

109
 BODY CENTERED CUBIC STRUCTURE (BCC)
•  Atoms touch each other along cube diagonals.
• 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 (), Tantalum, Molybdenum • Coordination # = 8

2 atoms/unit cell:  1 center + 8 corners x 1/8 Adapted from Fig. 3.2,

Callister 6e.
(Courtesy P.M. Anderson)
110
 BODY CENTERED CUBIC STRUCTURE (BCC)
• APF for a body-centered cubic structure = 0.68

Close‐packed directions:
length = 4R = 3 a
Unit cell contains:
1 + 8 x 1/8
= 2 atoms/unit cell
R
Adapted from a 3a
Fig. 3.2,
Callister 6e.
atoms volume
4 a
unit cell 2 ( 3a/4)3
3 atom
APF = 2a
volume
a3
unit cell 111
HEXAGONAL 
CLOSE‐PACKED STRUCTURE (HCP)

112
HEXAGONAL 
CLOSE‐PACKED STRUCTURE (HCP)

• ABAB... Stacking Sequence

• 3D Projection • 2D Projection
A sites Top layer
c B sites
Middle layer
A sites
a Bottom layer
Adapted from Fig. 3.3,
Callister 6e.

• Coordination # = 12
The same of cubic FCC
• APF = 0.74

ex: Cd, Mg, Ti, Zn • c/a = 1.633 113

 THEORETICAL DENSITY, 

Mass of Atomsin Unit Cell

Density =  =
Total Volume of Unit Cell

 = nA
VC NA

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

114
 Chromium: THEORETICAL DENSITY, 

• Ex: Cr (BCC)  
A = 52.00 g/mol
R = 0.125 nm
n = 2 atoms/unit cell
R
Adapted from  a a = 4R/ 3 = 0.2887 nm
Fig. 3.2(a), Callister & 
Rethwisch 3e.
atoms
g
unit cell 2 52.00
mol theoretical = 7.18 g/cm3

 =  actual = 7.19 g/cm3
a 3 6.022 x 1023
volume atoms

unit cell mol
115
 Characteristics of Selected Elements at 20°C
At. Weight Density Crystal Atomic radius
Element Symbol (amu) (g/cm3) Structure (nm)
Aluminum Al 26.98 2.71 FCC 0.143
Argon Ar 39.95 ------ ------ ------
Barium Ba 137.33 3.5 BCC 0.217
Beryllium Be 9.012 1.85 HCP 0.114
Boron B 10.81 2.34 Rhomb ------ Adapted from
Table, "Charac-
Bromine Br 79.90 ------ ------ ------ teristics of
Cadmium Cd 112.41 8.65 HCP 0.149 Selected
Calcium Ca 40.08 1.55 FCC 0.197 Elements",
inside front
Carbon C 12.011 2.25 Hex 0.071 cover,
Cesium Cs 132.91 1.87 BCC 0.265 Callister 6e.
Chlorine Cl 35.45 ------ ------ ------
Chromium Cr 52.00 7.19 BCC 0.125
Cobalt Co 58.93 8.9 HCP 0.125
Copper Cu 63.55 8.94 FCC 0.128
Flourine F 19.00 ------ ------ ------
Gallium Ga 69.72 5.90 Ortho. 0.122
Germanium Ge 72.59 5.32 Dia. cubic 0.122
Gold Au 196.97 19.32 FCC 0.144
Helium He 4.003 ------ ------ ------
Hydrogen H 1.008 ------ ------ ------ 116
 CERAMIC CRYSTALS
• Bonding:
--Mostly ionic, some covalent.
--% ionic character increases with difference in
electronegativity.
• Large vs small ionic bond character:
H
2.1
CaF2: large He
-
Li C F
1.0
Be
1.5 SiC: small 2.5 4.0
Ne
-
Na Mg Si Cl Ar
0.9 1.2 1.8 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 Table of Electronegativities
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. 117
118
High Covalent Character: Bond Hybridization
Bond Hybridization is possible when there is significant 
covalent bonding
– hybrid electron orbitals form
– For example for SiC
• XSi = 1.8  and   XC = 2.5

% ionic character  100 {1 - exp[-0.25( X Si  X C )2 ]}  11.5%

• ~ 89% covalent bonding
• Both Si and C prefer sp3 hybridization
• Therefore, for SiC, Si atoms occupy tetrahedral sites

119
Ceramic Crystal Structure

120
 Factors that Determine Ceramic 
Crystal Structure
1. Relative sizes of ions – Formation of stable structures:
--maximize the # of oppositely charged ion neighbors.
- - - - - -
+ + +
Adapted from Fig. 3.4,
Callister & Rethwisch 3e.
- - - - - -
unstable stable stable
2. Maintenance of
Charge Neutrality : F-
CaF 2 : Ca 2+ +
--Net charge in ceramic
cation anions
should be zero.
--Reflected in chemical F-
formula:
A m Xp
121
m, p values to achieve charge neutrality
 COORDINATION # AND IONIC RADII
rcation
• Coordination # increases with r
anion
To form a stable structure, how many anions can you
arrange around a cation?
r cation Coord  ZnS 
r anion # (zinc blende)
Adapted from Fig. 12.4,
< 0.155  2  linear Callister 6e.

0.155 ‐ 0.225  3  triangular NaCl

(sodium 
0.225 ‐ 0.414 4 tetrahedral chloride)
Adapted from Fig. 12.2,
Callister 6e.

0.414 ‐ 0.732  6 octahedral CsCl

(cesium 
0.732 ‐ 1.0 8 cubic chloride)
Adapted from Fig. 12.3,
Adapted from Table Callister 6e.
12.2, Callister 6e.
122
EX:  PREDICTING STRUCTURE OF FeO
• On the basis of ionic radii, what crystal structure
would you predict for FeO?
Cation Ionic radius (nm) • Answer:
Al3+ 0.053 r cation 0.077
Fe2+ 0.077 
r anion 0.140
Fe3+ 0.069
 0.550
Ca2+ 0.100
based on this ratio,
--coord # = 6
Anion
--0.414 < 0.550 < 0.732
O2- 0.140 --structure = NaCl
Cl- 0.181
F-
Data from Table 12.3,
0.133 Callister 6e.
123
 AmXp STRUCTURES: AX
• Compounds: Often have similar close-packed structures.
• Structure of NaCl • Structure of CsCl
NO BCC (2  elements)

rCs  0.170
Fig. 13.2, Callister 6e.   0.939
rCl 0.181
 Since 0.732 < 0.939 < 1.0,
Coordination # = 6 cubic sites preferred C#=8
Anions Face-Centered + ‐
So each Cs has 8 neighbor Cl
124
125
 AmXp STRUCTURES: AX2
r cation 0.100
• Consider CaF2 :   0.8
r anion 0.133

• Fluorite structure: UO2, ThO2, ZrO2, CeO2

• Based on this ratio, coord # = 8 and structure = CsCl.

• Difference is that only half the center cube positions are
occupied by the cations.

• #Ca2+ ions = 1/2 # F- ions.

Adapted from Fig. 12.5,

Callister 6e. 126
 AmBnXp: ABX3 Crystal Structures

• Three compositional
variables, A, B and X

• A and B = two types of

cations
• X = Oxygen or an Alogen

• Perovskite structure
Adapted from Fig. 3.9, 

Ex: complex oxide Callister & Rethwisch 3e.

BaTiO3
128
 A CERAMIC:  Perovskite ‐
an Inorganic Chameleon 

• CaTiO3 - dielectric • NaxWO3 - mixed conductor;

electrochromic
• BaTiO3 - ferroelectric
• SrCeO3 - H - protonic conductor
• Pb(Mg1/3Nb2/3)O3 - relaxor
ferroelectric • RECoO3-x - mixed conductor
• Pb(Zr1-xTix)O3 - piezoelectric • (Li0.5-3xLa0.5+x)TiO3 - lithium ion
conductor
• (Ba1-xLax)TiO3 - semiconductor
• LaMnO3-x - Giant magneto-
• (Y1/3Ba2/3)CuO3-x (YBCO)-
resistance and ionic conductors
superconductor

129
 Example: SrTiO3
ABO3 e.g. KNbO3 In SrTiO3, Ti-O = a/2 = 1.955 Å
SrTiO3
Sr-O = a2/2 = 2.765 Å
LaMnO3

SrTiO3 cubic, a = 3.91 Å CN of A=12, CN of B=6

OR

• Not traditional close packing - mixed cation/anion 130

 SrTiO3 vs BaTiO3

In SrTiO3, Ti-O ~ 1.95 Å a typical

bond length for Ti-O; stable as a cubic
structure

larger

In BaTiO3, Ti-O is stretched, > 2.0 Å Too long for

a stable structure.
Ti displaces off its central position towards one
oxygen
 square pyramidal coordination
 Cubic structure only above 120°C
131
 This creates a net dipole moment :

Below 120°C, TiO6 octahedron is

distorted, due to Ti displacement
Cell structure distorted from cubic to
tetrahedral
Displacement by 5-10% Ti-O bond length

Aligned dipole orientations ferroelectric

Random dipole orientations paraelectric

Under an applied electric field, dipole orientations can be reversed, i.e. the structure
is polarisable
Dipoles tend to be ‘frozen in’ at room temperature; as increase temperature, thermal
vibrations increase the polarisability, but enhance the disorder of domains

Below 120°C, BaTiO3 is ferroelectric with aligned dipoles

Partial substitution of Ba with Sr, ex: Ba0.92Sr0.08TiO3  cell volume decrease and
phase transition T decrease 132
Tc is Ferrolectric Curie Temperature (T of ferrolectric-paraelectric phase transitions)
YBa2Cu3O7- :
Perovskite
Superconductors
YBa2Cu3O7-
Perovskite?
called YBCO

Oxygen Deficient
Triple Perovskite
Crosses mark absent
oxygens

133
MgAl2O4 : Spinel (garnet) strucuture
Cubic closed‐ packed structure

134
135
Density Computations for Ceramics

Number of formula units/unit cell

n(AC  AA )

VC N A
Avogadro’s number
Volume of unit cell

AC = sum of atomic weights of all cations in formula unit

AA = sum of atomic weights of all anions in formula unit

136
 Crystalline and Amorphous Silicates

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

Si Oxygen
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.

137
 Ceramics: other Oxide structures
– oxygen anions larger than metal cations
– close packed oxygen in a lattice (usually FCC)
– cations fit into interstitial sites among oxygen ions

Silicates

138
139
 GLASS STRUCTURE
• Basic Unit: • Glass is amorphous
4- • Amorphous structure
Si04 tetrahedron occurs by adding impurities
Si4+ (Na+,Mg2+,Ca2+, Al3+)
O2-
• Impurities:
interfere with formation of
crystalline structure.

• Quartz is crystalline Na+

SiO2:
Si4+
O2-

(soda glass)
Adapted from Fig. 12.11,
Callister, 6e.

140
Other glass structures: B2O3, GeO2
141
142
 Allotropic Forms of Carbon
Diamond
– tetrahedral bonding of 
carbon
• hardest material known
• very high thermal conductivity
– large single crystals – gem 
stones
– small crystals – used to 
grind/cut other materials 
– diamond thin films
• hard surface coatings – used 
Adapted from Fig. 3.16, 
for cutting tools, medical  Callister & Rethwisch 3e.
devices, etc.
Diamond cubic structure Zinc blend like, similar to Group IVA elements 
143
 Allotropic Forms of Carbon
Graphite
– layered structure – parallel hexagonal arrays of carbon 
atoms 

Adapted from Fig. 
3.17, Callister & 
Rethwisch 3e.

– weak van der Waals forces between layers
– planes slide easily over one another ‐‐ good lubricant
– Conductivity parallel to planes  
144
 Allotropic Forms of Carbon
Fullerenes and Nanotubes
• Fullerenes – spherical cluster of 60 carbon atoms, C60
– Like a soccer ball  ‐ crystalline solid
• Carbon nanotubes – sheet of graphite rolled into a tube
– Ends capped with fullerene hemispheres

Adapted from Figs. 
3.18 & 3.19, Callister 
& Rethwisch 3e.

145
146
 Types of Imperfections in Solids

Many of the important properties of materials are due to the 
presence of imperfections.   

•  Vacancy atoms
•  Interstitial atoms Point defects
•  Substitutional atoms

•  Dislocations Line defects

•  Grain Boundaries Area defects
147
•  Vacancies:
Point Defects in Metals
‐vacant atomic sites in a structure.

Vacancy
distortion 
of planes

•  Self‐Interstitials:
‐"extra" atoms positioned between atomic sites.

self‐
interstitial
distortion 
of planes

148
 Equilibrium Concentration:
Point Defects
• The presence of vacancies increase the entropy of the crystal
• Equilibrium concentration varies with temperature!

No. of defects Activation energy

Nv Q v 
No. of potential   exp  
defect sites N  k T 
Temperature
Boltzmann's constant
(1.38 x 10 ‐23 J/atom‐K) 
(8.62 x 10 ‐5 eV/atom‐K)

Each lattice site 
is a potential  Activation energy is the energy required to form a Vacancy
Ratio=10‐4  for metals below the Melting Temperature
vacancy site
149
 Measuring Activation Energy
•  We can get Qv from Nv Q v 
an experiment. = exp 
 
N  k T 
•  Measure this... •  Replot it...

Nv Nv slope
ln
N N
‐ Q v /k
exponential 
dependence!
T
1/ T
defect concentration
150
 Observing Equilibrium Vacancy Conc.
•  Low energy electron
microscope view of
a (110) surface of NiAl.
•  Increasing temperature 
causes surface island of
atoms to grow.
•  Why? The equil. vacancy
conc. increases via atom
motion from the crystal
to the surface, where  Reprinted with permission from Nature (K.F. McCarty, J.A. 
they join the island. Nobel, and N.C. Bartelt, "Vacancies in
Solids and the Stability of Surface Morphology",
Nature, Vol. 412, pp. 622‐625 (2001).  Image is
Island grows/shrinks to maintain  5.75 m by 5.75 m.)  Copyright (2001) Macmillan Publishers, 
equil. vancancy conc. in the bulk. Ltd.

152
 Imperfections in Metals (i)
Two outcomes if impurity (B) added to host (A):
•  Solid solution of B in A (i.e., random dist. of point defects)

OR

Substitutional solid soln. Interstitial solid soln.

(e.g., Cu in Ni) (e.g., C in Fe)
•  Solid solution of B in A plus particles of a new
phase (usually for a larger amount of B)
Second phase particle
‐‐ different composition
‐‐ often different structure.

153
 Imperfections in Metals (ii)
Conditions for substitutional solid solution (S.S.)
• W. Hume – Rothery rule
– 1.  r (atomic radius) < 15%, if not: lattice distorption and a new 
phase formation
– 2.  Proximity in periodic table 
• i.e., similar electronegativities, if not formation of intermetallic compounds
– 3.  Same crystal structure for pure metals
– 4.  Valency
• All else being equal, a metal will have a greater tendency to dissolve a 
metal of higher valency than one of lower valency
Conditions for interstitial solid solution (S.S.)
– 1.  atomic diameter of impurity has to be smaller than the one of 
host atoms
– 2. maximum allowable concentraton less than 10% (C in Fe=2%) 154
 Impurities in Metals
• Specification of composition
m1
– weight percent C1  x 100
m1  m2
m1 = mass of component 1

n m1
– atom percent C 
'
x 100
n m1  n m 2
1

nm1 = number of moles of component 1

156
 DEFECTS IN CERAMIC STRUCTURES
• Frenkel Defect
--a cation is out of place (migration closed to another cation).
• Shottky Defect
--a paired set of cation and anion vacancies.

Shottky
Defect: Adapted from Fig. 13.20,
Callister 5e. (Fig. 13.20 is from
W.G. Moffatt, G.W. Pearsall,
and J. Wulff, The Structure and
Properties of Materials, Vol. 1,
Structure, John Wiley and
Sons, Inc., p. 78.) See Fig.
Frenkel 12.21, Callister 6e.
Defect

• Equilibrium concentration of defects ~ eQD / kT

• Elettroneutrality has to be preserved, if not NONSTOICHIOMETRY = common
in Iron Oxide (Fe2+/Fe3+)
157
 IMPURITIES in Ceramics
• Impurities must also satisfy charge balance
• Ex: NaCl Na+ Cl-
cation
• Substitutional cation impurity vacancy
Ca2+
Na+
Na+
Ca2+
initial geometry Ca2+ impurity resulting geometry

• Substitutional anion impurity

anion vacancy
O2-

Cl- Cl-
initial geometry O2- impurity resulting geometry
158
 Imperfections in Solids

Linear Defects (Dislocations)
– Are one‐dimensional defects around which atoms are misaligned
• Edge dislocation:
– extra half‐plane of atoms inserted in a crystal structure
– b perpendicular () to dislocation line
• Screw dislocation:
– spiral planar ramp resulting from shear deformation
– b parallel () to dislocation line

Burger’s vector, b: measure of lattice distortion (define magnitude and direction 
of the distortion)

Dislocations in crystalline materials are introduced by plastic deformation, as a 
resutl of thermal stresses due to rapid cooling for example
159
 Imperfections in Solids
Edge Dislocation

Fig. 4.3, Callister & Rethwisch 8e.

160
 Imperfections in Solids

Screw Dislocation (shear stress is applied)

Screw Dislocation

b
Dislocation
line
Burgers vector b (b)
(a)
Adapted from Fig. 4.4, Callister & Rethwisch 8e.

161
 Edge, Screw, and Mixed Dislocations
Mixed

Edge

Adapted from Fig. 4.5, Callister & Rethwisch 8e.
Screw

162
 Imperfections in Solids
Dislocations are visible in electron micrographs

Titanium 
alloy: dark 
lines are 
linear 
dislocation

Fig. 4.6, Callister & Rethwisch 8e.
165
 Imperfections in Solids

• Solidification‐ result of casting of molten material
– 2 steps
• Nuclei form 
• Nuclei grow to form crystals – grain structure
• Start with a molten material – all liquid

nuclei crystals growing grain structure

liquid Adapted from Fig. 4.14(b), Callister & Rethwisch 8e.
• Crystals grow until they meet each other

167
 Polycrystalline Materials

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. 4.7, Callister 
& Rethwisch 8e.
168
 Solidification
Grains can be ‐ equiaxed   (roughly same size in all directions)
‐ columnar   (elongated grains)
~ 8 cm

heat 
flow

Shell of
Columnar in equiaxed grains
area with less due to rapid
undercooling cooling (greater
Adapted from Fig. 5.17,  T) near wall
Callister & Rethwisch 3e.

Grain Refiner - added to make smaller, more uniform, equiaxed grains.

169
 Planar Defects in Solids
• One case is a twin boundary (plane)
– Essentially a reflection of atom positions across the twin 
plane. Caused by applied mechanical shear forces, 
deformation due to annealing treatments

Adapted from Fig. 4.9, 
Callister & Rethwisch 8e.

• Stacking faults
– For FCC metals an error in ABCABC packing sequence
– Ex:  ABCABABC
170
Defects and Surfaces

171
171
Defects and Surfaces

172
Defects and Surfaces

173
173
Steps

174
174
Domain walls

175
175
Domain walls

176
176
Dislocations

177
177
 Dislocations

Dislocation are ubiquitous in

heteroepitaxial system

178
 Catalysts and Surface Defects
• A catalyst increases the 
rate of a chemical reaction 
without being consumed
• Active sites on catalysts are  Fig. 4.10, Callister & Rethwisch 8e.

normally surface defects

Single crystals of 
(Ce0.5Zr0.5)O2
used in an automotive 
catalytic converter
Fig. 4.11, Callister & Rethwisch 8e.
179
 SEMICONDUCTORS
• Properties of Semiconductors
– Made primarily from metalloids
– Regular arrangement of atoms (crystals, but not, e.g., solar
cell amorphous Si)
– Extremely controlled chemical purity
– Materials with electrical properties intermediate of a metal
(good conductor) and a ceramic (good insulator):
Adjustable conductivity of electricity
– Opaque to visible light
– Shiny appearance
– Some have good plasticity, but others are fairly brittle
– Some have an electrical response to light
– Silicon is the essential example – computer chips
• Key to use of semiconductors is the extremely precise control of
dopant atoms that are used to manipulate the conducting properties 180
 SEMICONDUCTORS

• Applications and Examples

– Computer CPUs
– Electrical components (transistors, diodes, etc.)
– Solid-state lasers
– Light-emitting diodes (LEDs)
– Flat panel displays
– Solar cells
– Radiation detectors
– Microelectromechanical devices (MEMS)
– Examples: Si, Ge, GaAs, and InSb

181
 POLYMERS
• Properties of Polymers
– Plastics and rubber materials
• Macromolecules – generally formed from carbon and hydrogen
(HYDROCARBONS), nitrogen, oxygen (chon systems or molecules)
• there are polymers that contain metals
• Usually have low density
• Low melting temperature.
• Some are crystals, many are amorphous
• Many have high plasticity.
• A few have good elasticity.
• Can be extremely flexible, deformable, low strength
• Not stable at high temperatures typically
• Soft, ductile, low strength, low density
• thermal & electrical insulators
• Optically translucent or transparent.
• Good corrosion resistance
182
• Low resistance to heat
 POLYMERS

Examples: polyethylene, *
H2
C *
H2
C
H
N
H
N R' *
C * *
polystyrene, polyamide H2 n
CH
n
* R
n
(Nylon®) O O

• Polymers are attractive because they are usually lightweight

and inexpensive to make, and usually very easy to process,
either in molds, as sheets, or as coatings.

• Most are very resistant to the environment.

• They are poor conductors of heat and electricity, and tend to

be easy to bend, which makes them very useful as insulation
for electrical wires.
183
 POLYMERS
• Two main types of polymers are thermosets and
thermoplastics
– Thermoplastics are long-chain polymers that slide easily past one
another when heated, hence, they tend to be easy to form, bend, and
break.

– Thermosets are cross-linked polymers that form 3-D networks, hence

are strong and rigid.

184
 POLYMERS
• Applications and Examples
– Adhesives and glues
– Containers
– Moldable products (computer casings, telephone
handsets, disposable razors)
– Clothing and upholstery material (vinyls, polyesters,
nylon)
– Water-resistant coatings (latex)
– Biodegradable products (corn-starch packing “peanuts”)
– Biomaterials (organic/inorganic intefaces)
– Liquid crystals
– Low-friction materials (teflon)  prosthesys
– Synthetic oils and greases
– Gaskets and O-rings (rubber)
185
– Soaps and surfactants
 COMPOSITES

• Properties of Composites
– Exactly what it sounds like: a new material that consists of more
than one component
• Fiberglass – glass fibers embedded in a polymeric matrix
• Idea – get desirable features of each material component
• Complicated though – does not always work out as well as you’d like
• Composed of two or more different materials (e.g., metal/ceramic,
polymer/polymer, etc.)
• Properties depend on amount and distribution of each type of material.
• Collective properties more desirable than possible with any individual
material.

186
 COMPOSITES

– Applications and Examples

• Sports equipment (golf club shafts, tennis rackets,
bicycle frames)
• Aerospace materials
• Thermal insulation
• Concrete
• "Smart" materials (sensing and responding)
• Brake materials
– Examples
• Fiberglass (glass fibers in a polymer)
• Space shuttle heat shields (interwoven ceramic fibers)
• Paints (ceramic particles in latex)
• Tank armor (ceramic particles in metal)

187
 BIOMATERIALS

• Properties of Biomaterials
– Use of the above materials in life science applications
 Key point: the material must not lead to an
adverse physiological reaction
 Hip implants are the big success story here

– Organic (not polymers only) and biological molecules

188
 Summary table

http://www.virginia.edu 189
190