Mid Sem PDF

CHE F243
Materials Science and Engineering

Krishna Etika
BITS Pilani Department of Chemical Engineering
B.I.T.S-Pilani, Pilani Campus
Pilani Campus
26 February 2020 2
BITS Pilani, Pilani Campus
Belated Wishes for the New Year
26 February 2020 3
Course Structure
Course No: CHE F243

Course Title: Materials Science and Engineering
Instructor-in-Charge: Krishna Etika
Tutorial Instructors: Krishna Etika / Priya Sande
Lectures: M W F 3rd Hour Tutorial : T 1st Hour
Lecture Venue : 1223 Tutorial Venue: 1223/1226
Textbook (s):
Callister's Materials Sc. & Engg, W.D. Callister & R. Balasubramaniam
(Adapted), Wiley, 2nd. ed., 2014.
26 February 2020 4
About The Course Instructor
Why am I teaching Materials Science and Engineering Course?
☼ Got my Ph.D. from Texas A&M University in Materials

(Nanomaterials to be precise!).
☼ Worked for materials/nanotechnology focused Industry (Intel
Corporation).
☼ Have been associated with the materials world for more than
17 years.
☼Taught a similar course at Texas A&M during Fall 2010.
26 February 2020 5
Course Handout
Adobe Acrobat
Document
26 February 2020 6
Why Study Materials?
Materials Used Define the Civilizations. For ex:
Stone Age
Bronze Age
Iron Age
Plastic or Silicon Age?????
 In the past, using the already available materials was the
priority .
 Now, “creating” new materials with desired “properties” is the
challenge - Needs understanding on fundamental
properties of materials.
26 February 2020 7
CHE F243
Krishna Etika
Department of Chemical Engineering
BITS Pilani
Pilani Campus
Introduction
What is a Material?
“Materials are the things that humankind uses to make
articles of necessity, utility, and/or artistic beauty”
Why should we care about Materials?
Materials drive our society
Stone Age Bronze Age Iron Age
(~2 m yr ago) (~5k yr ago) (~2 k yr ago)
Silicon Age (60 yr ago) Now? Polymer Age(???) 2

Iron Age in India
• Iron Pillar of Delhi.
• Originally located at
Udayagiri (~50 km from
Bhopal). Now at Qutub
Minar Complex
• “Forged” during Gupta
Dynasty (375-414 AD).
• Created using Forge
Welding Process.
• High Phosphor content
protects it from corrosion
CHE F243
Krishna Etika
BITS Pilani
Pilani Campus
Bombproof wall paper
http://www.popsci.com/node/42027
Guess what the wall paper is made of?

26-Feb-20
Introduction
Materials Science Materials Engineering
Investigation of Using the

“structure-property” “structure-property”
relationships relationships to design
new materials
Structure: It is the arrangement of a Property: It is the response to an external

materials internal components. stimuli e.g. how much deformation occurs
e.g. atomic structure of Au (electrons, when you apply certain load to a material.
protons) (strain)
26-Feb-20
Structure-Property Relations
Processing Structure Properties Applications

Importance of Processing
Polycrystal: Polycrystal:
Single Crystal low porosity high porosity
Exactly same chemical composition – All discs are Al2O3 (Alumina)

Different processing conditions.
26-Feb-20
Structure-Property Relations
Properties depend on structure

e.g. : hardness vs structure of steel (d)
6 00
30 mm
5 00 (c)
Hardness (BHN)
4 00 (b)
(a)
4 mm
3 00
30 mm
2 00 30 mm
100
0.01 0.1 1 10 100 1000
Cooling Rate (ºC/s)
Processing can change structure
ex: structure vs cooling rate of steel
26-Feb-20
Types of Materials
Polymers/plastics
Metals
Soft, ductile, low density
Strong, ductile,high thermal &
thermal & electrical insulators
electrical conductivity opaque, reflective.
Optically translucent or transparent.
Ceramics/Glass
Brittle, glassy, elastic
non-conducting (insulators) Composites
A hybrid material that is
formed by mixing two(or more)
individual materials (i.e.,
polymers, metals, ceramics)
26-Feb-20
Types of Materials
Advanced Materials
Materials used in high-tech applications
☼Semiconductors – Si wafer
☼Biomaterials - heart valve
☼Smart Materials– responsive polymers
☼Nanomaterials- nanotubes, graphene
26-Feb-20
The Materials Selection Process
1. Pick Application Determine required Properties
Properties: mechanical, electrical,

thermal, magnetic, optical, deteriorative.
2. Properties Identify candidate Material(s)

Material : type, structure, composition.
3. Material Identify required Processing
Processing: changes structure and overall shape

ex: casting, sintering, vapor deposition, doping
forming, joining, annealing.
26-Feb-20
Properties
• What exactly is a “Property”?
– Any response of a material to an external
stimulus
• Types of Properties:
– Mechanical
– Electrical
– Thermal
– Magnetic
– Optical
26-Feb-20
Mechanical Property
Hardness is a mechanical property.
(d)
600
30 mm
500 (c)
Hardness (BHN)
400 (b)
(a)
4 mm
300
30 mm
200 30 mm
100
0.01 0.1 1 10 100 1000
Cooling Rate (ºC/s)
BHN - Brinell hardness number
26-Feb-20
Bombproof wall paper
http://www.popsci.com/node/42027
Guess what the wall paper is made of?

26-Feb-20
Electrical Property
• Electrical Resistivity (a property) of Copper:
6
5
4
Ohm-m)
Resistivity, r
(10-8 Ohm
3
2
1
0 T (°C)
-200 -100 0
• Adding “impurity” atoms to Cu increases resistivity.

• Deforming Cu increases resistivity.
26-Feb-20
Magnetic Property
• Magnetic Storage: • Magnetic Permeability
-- Recording medium (a property) vs. Composition:
is magnetized by -- Adding 3 atomic % Si
recording head. makes Fe a better
recording medium!
Fe+3%Si
Magnetization
Fe
Magnetic Field
26-Feb-20
Property Comparison
Resistance to Fracture (mechanical)
26-Feb-20
Types of Materials
Advanced Materials
Materials used in high-tech applications
☼Semiconductors – Si wafer
☼Biomaterials - heart valve
☼Smart Materials– responsive polymers
☼Nanomaterials- nanotubes, graphene
26-Feb-20
CHE F243
Krishna Etika
BITS Pilani
Pilani Campus
Chapter 3
The Structures of Crystalline Solids
Introduction
• Crystalline Material…..
• Properties Depend on Crystal Structure…
• How to describe “crystal” structure?
• Atomic Hard Sphere Model
– In this model, the atoms actually can touch each
other.
– Lattice means 3-D array of points
– In simple cases, lattice coincides
with sphere centers
– Each lattice point has identical
surroundings (i.e., motifs)
Lattice + Basis = Crystal Structure
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Crystal Structure
A crystal is defined as a lattice with

a basis added to each lattice site. Usually the
basis consists of an atom, a group of atoms
or a molecule.
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Property Comparison
Resistance to Fracture (mechanical)
26-Feb-20
Lattice
A two-dimensional Bravais lattice can be created

as the set of integer linear combinations of two
(linear independent) vectors (called primitive
translation vectors)
2/26/2020 6
Crystal Systems
Unit cell: smallest repetitive volume which
contains the complete lattice pattern of a crystal.
More than one unit cell possible for a crystal

structure but we chose the one that highest level
of geometrical symmetry!!!
7 crystal systems
14 crystal lattices (Bravais)
a, b, and c are the lattice constants
7
Bravais Lattice
2/26/2020 8
Bravais Lattices
2/26/2020 9
Unit Cells
2/26/2020 10
CHE F243
Krishna Etika
BITS Pilani
Pilani Campus
Chapter 3
The Structures of Crystalline Solids
Introduction (Recap)
• Crystalline Material…..
• Properties Depend on Crystal Structure…
• How to describe “crystal” structure?
• Atomic Hard Sphere Model
– In this model, the atoms actually can touch each
other.
– Lattice means 3-D array of points
– In simple cases, lattice coincides
with sphere centers
– Each lattice point has identical
surroundings (i.e., motifs)
Lattice + Basis = Crystal Structure
2/26/2020 3
Crystal Structure (Recap)
A crystal is defined as a lattice with

a basis added to each lattice site. Usually the
basis consists of an atom, a group of atoms
or a molecule.
2/26/2020 4
Lattice(Recap)
• A lattice is in general defined as a discrete but
infinite regular arrangement of points (lattice
sites) in a vector space.
• Bravais Lattice: lattices which exhibit a
discrete translational symmetry.
– Translation of the whole lattice by any translation
vector given by, T leaves the lattice unchanged.
– Where, a1, a2 and a3 are called as the primitive

translational vectors.
2/26/2020 5
Crystal Systems(Recap)
Unit cell: smallest repetitive volume which
contains the complete lattice pattern of a crystal.
More than one unit cell possible for a crystal

structure but we chose the one that highest level
of geometrical symmetry!!!
7 crystal systems
14 crystal lattices (Bravais)
a, b, and c are the lattice constants
6
Crystallographic Points, Directions
and Planes
2/26/2020 7
Point Coordinates
z
111 Point coordinates for unit cell
c center are
a/2, b/2, c/2 ½½½
y
a 000 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
8
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>

9
Lattice
A two-dimensional Bravais lattice can be created

as the set of integer linear combinations of two
(linear independent) vectors (called primitive
translation vectors)
2/26/2020 6
Practice Problem
2/26/2020 11
Practice Problem 2
2/26/2020 12
Bravais Lattice
2/26/2020 8
Crystallographic Planes
Adapted from Fig. 3.10,

Callister & Rethwisch 8e.
14
Unit Cells
2/26/2020 10
z
example a b c c
1. Intercepts 1 1 
2. Reciprocals 1/1 1/1 1/
1 1 0
y
3. Reduction 1 1 0
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
16
z
example a b c
c
1. Intercepts 1/2 1 3/4 
2. Reciprocals 1/½ 1/1 1/¾
2 1 4/3  y
a  b
3. Reduction 6 3 4
x
4. Miller Indices (634)
Family of Planes {hkl}
Ex: {100} = (100), (010), (001), (100), (010), (001)
17
Crystallographic Planes (Hexagonal)
• In hexagonal unit cells the same idea is used

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),

18
Miller Vs Miller-Bravais
Miller indices indicate that these two planes are of a different family
(even though they belong to the same family). But Miller-Bravais
notations confirm that they are from the same family
19
Energy and Packing
Energy
• Non dense, random packing
typical neighbor
bond length
typical neighbor r
bond energy
Energy
• Dense, ordered packing
typical neighbor
bond length
typical neighbor r
bond energy
Dense, ordered packed structures tend to have lower energies.

2/26/2020
20
Materials and Packing
Crystalline materials...
• atoms pack in periodic, 3D arrays
• typical of: -metals
-many ceramics
-some polymers crystalline SiO2
Si Oxygen
Noncrystalline materials...
• atoms have no periodic packing
• occurs for: -complex structures
-rapid cooling
"Amorphous" = Noncrystalline noncrystalline SiO2

2/26/2020
CHE F243
Krishna Etika
BITS Pilani
Pilani Campus
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>

9
Thought for the Day
Micro-lattice
2/26/2020 3
Materials and Packing
Crystalline materials...
• atoms pack in periodic, 3D arrays
• typical of: -metals
-many ceramics
-some polymers crystalline SiO2
Si Oxygen
Noncrystalline materials...
• atoms have no periodic packing
• occurs for: -complex structures
-rapid cooling
"Amorphous" = Noncrystalline noncrystalline SiO2

2/26/2020
Chapter 4.
Structures of Crystalline Solids
2/26/2020 5
Crystal Structure of Metals
• Tend to be densely packed.
• 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.
- Electron cloud shields cores from each other
• Have the simplest crystal structures.

We will examine three such structures...
6
2/26/2020
6
Simple Cubic Structure (SC)
Rare - due to low packing density (only Po has this structure)

Close-packed directions are cube edges.
• Coordination # = 6
(# nearest neighbors)
2/26/2020
7
Practice Problem 2
2/26/2020 12
Face Centered Cubic Structure (FCC)
Atoms touch each other along 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
2/26/2020 9
Coordination Number
What is a coordination Number (C.N.) ???

It is the number of nearest neighbors
C.N ?
10
MEEN 222- Krishna Etika 10
Coordination Number
C.N ?
2/26/2020
11
Atoms/Unit Cell
How many atoms/unit cell???

SC BCC FCC
1 atoms/unit cell: 8 corners x 1/8 = SC
2 atoms/unit cell: 1 center + 8 corners x 1/8 = BCC
4 atoms/unit cell: 6 face x 1/2 + 8 corners x 1/8 = FCC

2/26/2020 12
12
Atomic Packing Factor (APF)
Volume of atoms in unit cell*

APF =
Volume of unit cell
*assume hard spheres
volume
atoms
atom
4
a unit cell 1 p (R) 3
3
R=0.5a APF =
a3 volume
close-packed directions unit cell

Relation : a= 2R
contains 8 x 1/8 =
1 atom/unit cell ???
• APF for a simple cubic structure = 0.52
2/26/2020
Atomic Packing Factor: BCC
 APF for a body-centered cubic structure = 0.68

3a
2a
R Close-packed directions:
a
Relation: 4R = 3 a
atoms
4 volume
unit cell 2 p ( R )3
3 atom
APF =
volume
a3
unit cell 14
2/26/2020
Atomic Packing Factor: FCC
• APF for a face-centered cubic structure = 0.74

maximum achievable APF
Close-packed directions:
Relation: 4R = 2a
2a
Unit cell contains:
6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell
a
Adapted from
Fig. 3.1(a),
atoms
Callister 7e.
4 volume
unit cell 4 p ( R)3
3 atom
APF =
volume
a3
2/26/2020 unit cell
15
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
length 2a
16
Linear Packing Fraction
• Linear density can also be determined from the
packing fraction: the fraction of line length in a
particular direction that passes through the atom
centers.
• For FCC [100] direction PF can be determined
as
Packing fraction =
17
• For [110] direction in FCC
18
LD from PF
• Linear density and linear packing

fraction are both related by
Packing Fraction = Linear Density x 2

radius
PF = LD x 2r
19
Metallic Crystal Structures
20
20
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
21
Hexagonal Close-Packed Structure (HCP)
• ABAB... Stacking Sequence
• 3D Projection • 2D Projection
A sites Top layer
c B sites Middle layer
A sites Bottom layer

a Adapted from Fig. 3.3(a),
• Coordination # = 12 6 atoms/unit cell
• APF = 0.74 ex: Cd, Mg, Ti, Zn
• c/a = 1.633
2/26/2020 22
CHE F243
Krishna Etika
BITS Pilani
Pilani Campus
Thought for the Day
Micro-lattice
2/26/2020 2
Chapter 4.
Recap of Lecture 5
2/26/2020 3
Simple Cubic Structure (SC)
Rare - due to low packing density (only Po has this structure)

Close-packed directions are cube edges.
(# nearest neighbors)
2/26/2020
4
Chapter 4.
2/26/2020 5
Atoms/Unit Cell
How many atoms/unit cell???

SC BCC FCC
1 atoms/unit cell: 8 corners x 1/8 = SC
2 atoms/unit cell: 1 center + 8 corners x 1/8 = BCC
4 atoms/unit cell: 6 face x 1/2 + 8 corners x 1/8 = FCC

2/26/2020 6
6
Atomic Packing Factor (APF)
Volume of atoms in unit cell*

APF =
Volume of unit cell
*assume hard spheres
volume
atoms
atom
4
a unit cell 1 p (R) 3
3
R=0.5a APF =
a3 volume
close-packed directions unit cell

Relation : a= 2R
contains 8 x 1/8 =
1 atom/unit cell ???
• APF for a simple cubic structure = 0.52
2/26/2020
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
length 2a
8
Coordination Number
What is a coordination Number (C.N.) ???

It is the number of nearest neighbors
C.N ?
10
MEEN 222- Krishna Etika 10
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
10
Hexagonal Close-Packed Structure (HCP)
• ABAB... Stacking Sequence
• 3D Projection • 2D Projection
A sites Top layer
c B sites Middle layer
A sites Bottom layer

a Adapted from Fig. 3.3(a),
• Coordination # = 12 6 atoms/unit cell
• APF = 0.74 ex: Cd, Mg, Ti, Zn
• c/a = 1.633
2/26/2020 11
Chapter 4.
Lecture 6
2/26/2020 12
Theoretical Density, r
Mass of Atoms in UnitCell

Density = r =
Total Volume of UnitCell
r = 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
13
• Ex: Cr (BCC)
A = 52.00 g/mol
R = 0.125 nm
n = 2 atoms/unit cell
R a = 4R/ 3 = 0.2887 nm
a
atoms
g
unit cell 2 52.00
mol rtheoretical = 7.18 g/cm3
r= ractual = 7.19 g/cm3

a3 6.022 x 1023
volume atoms
unit cell mol

14
Exercise Problem 4.8
• Calculate the radius of tantalum atom,

given that Ta has BCC crystal structure, a
density of 16.6 g/cm3 and an atomic
weight of 180.9 g/mol.
r = nA
VC NA
15
Exercise Problem 4.12
• Niobium has an atomic radius of 0.1430

nm and a density of 8.57 g/cm3.
Determine whether it has an FCC or BCC
crystal structure.
16
Densities of Material Classes
In general Metals/
Graphite/
Composites/
r r r Ceramics/ Polymers
metals > ceramics > polymers Alloys
Semicond
fibers
30
Why? Based on data in Table B1, Callister
Platinum *GFRE, CFRE, & AFRE are Glass,
20 Gold, W
Metals have... Tantalum Carbon, & Aramid Fiber-Reinforced
Epoxy composites (values based on
• close-packing 60% volume fraction of aligned fibers
10 Silver, Mo in an epoxy matrix).
(metallic bonding) Cu,Ni
Steels
• often large atomic masses Tin, Zinc
Zirconia
5
Ceramics have... (g/cm 3) 4
Titanium
Al oxide
Diamond
• less dense packing 3 Si nitride
Aluminum Glass -soda Glass fibers
• often lighter elements Concrete
Silicon PTFE GFRE*
2
Polymers have... Carbon fibers
r
Magnesium G raphite CFRE *

Silicone Aramid fibers
PVC
• low packing density PET
PC
AFRE *
1
(often amorphous) HDPE, PS
PP, LDPE
• lighter elements (C,H,O)
0.5
Composites have... 0.4
Wood
• intermediate values 0.3

17
Planar Density
• Planar density (PD) is simply the fraction of

the total crystallographic plane area that is
occupied by atoms (atoms are represented
by circles); the plane must pass through
an atom’s center for particular atom to be
included.
• Calculate planar density of the (100) and

(110) in BCC crystal structure.
18
Planar Density of (100) Iron
Solution: At T < 912ºC iron has the BCC structure.
2D repeat unit
(100) 4 3
a= R
3
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 nm 2 m2
R
2D repeat unit 3
19
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
ç
2 16 3 2
area = 2 ah = 3a = R
atoms 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
20
Planar Packing Fraction –
(100) BCC
21
• For [110] direction in FCC
18
Metallic Crystal Structures
20
20
Single vs Polycrystals
• Single Crystals E (diagonal) = 273 GPa

-Properties vary with
direction: anisotropic.
-Example: the modulus
of elasticity (E) in BCC iron:
E (edge) = 125 GPa
• Polycrystals
-Properties may/may not 200 mm
vary with direction.
-If grains are randomly
oriented: isotropic.
(Epoly iron = 210 GPa)
-If grains are textured,
2/26/2020
anisotropic.
Polymorphism
• Two or more distinct crystal structures for the same
material (allotropy/polymorphism)
iron system
titanium liquid
, -Ti
1538ºC
BCC -Fe
carbon
1394ºC
diamond, graphite
FCC -Fe
912ºC
BCC -Fe
25
CHE F243
Krishna Etika
BITS Pilani
Pilani Campus
Thought for the Day
Bendable Glass
Package
2/26/2020 2
Recap of Lecture 6
2/26/2020 3
Mass of Atoms in UnitCell

Density = r =
Total Volume of UnitCell
r = nA
VC NA
where n = number of atoms/unit cell

A = atomic weight
VC = Volume of unit cell = a3 for cubic
= 6.022 x 1023 atoms/mol
4
• Ex: Cr (BCC)
A = 52.00 g/mol
R = 0.125 nm
n = 2 atoms/unit cell
R a = 4R/ 3 = 0.2887 nm
a
atoms
g
unit cell 2 52.00
mol rtheoretical = 7.18 g/cm3
r= ractual = 7.19 g/cm3

a3 6.022 x 1023
volume atoms
unit cell mol

5
Planar Density
• Planar density (PD) is simply the fraction of
the total crystallographic plane area that is
occupied by atoms (atoms are represented
by circles);
• The plane must pass through an atom’s
center for particular atom to be included.
• Calculate planar density of the (100) and

(110) in BCC crystal structure.
6
Solution: At T < 912ºC iron has the BCC structure.

2D repeat unit
(100) 4 3
a= R
3
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 nm 2 m2
R
2D repeat unit 3
7
Chapter 4.
Recap of Lecture 5
2/26/2020 3
PD from Planar PF
• Planar density and Planar packing

“Planar” Packing Fraction = Planar

Density x area of atom
PF = PD x πr2
9
Crystal Structure of
Ceramics
Lecture 7
10
Ceramic Crystal Structures
Ceramic word comes from Greek word

“keramikos” which means burnt
stuff.
Ceramics are inorganic and non
metallic materials.
Ceramics are composed of at least two
elements and have more complex
crystal structures than metals
11
• Examples of Ceramics: CaF2 , MgO, NaCl,

Al2O3, SiO2, Si3N4, ZnS, SiC
- AX A, B = Cation (s)
- AMXP X = Anion
- AMBNXP
• Ceramics have inter-atomic bonding that

ranges from mostly ionic to mostly
covalent.
12
Oxide structures
– oxygen anions much larger than metal
cations
– close packed oxygen in a lattice
(usually FCC)
– cations in the holes of the oxygen
lattice
• Generally cations occupy
specific sites in ceramics in a
crystal lattice of anions
• What factors determine the
position of cations?? 13
Site Selection
Which sites will cations occupy?

1. Size of sites
– does the cation fit in the site
2. Stoichiometry
– if all of one type of site is full the
remainder have to go into other types of
sites.
3. Bond Hybridization
14
Ionic Bonding & Structure
1. Size - Stable structures:
--maximize the # of nearest oppositely charged neighbors.
- - - - - -
+ + +
- - - - - -
unstable stable stable
• Charge Neutrality:
F-
--Net charge in the Ca 2+
structure should CaF : + anions
2 cation
be zero. F-
--General form:A m Xp
m, p determined by charge neutrality
Coordination # and Ionic Radii
r
cation
• Coordination # increases with r
anion
How many anions can you arrange around a cation?
r cation Coord ZnS
r anion # (zincblende)
From Fig. 4.13
< 0.155 2 linear
0.155 - 0.225 3 triangular NaCl

(sodium
0.225 - 0.414 4 TD chloride)
From Fig. 4.11
0.414 - 0.732 6 OH CsCl

(cesium
0.732 - 1.0 8 cubic chloride)
Adapted from Table 4.3 16
Figures and table from Callister’s Materials Science and Engineering, Adapted Version.
LD from PF
• Linear density and linear packing

Packing Fraction = Linear Density x 2

radius
PF = LD x 2r
9
Example: Predicting 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,
Anion --coord # = 6
--structure = NaCl
O 2- 0.140
Cl - 0.181
F- 0.133
Site Selection II
2. Stoichiometry
– If all of one type of site is full the remainder have to
go into other types of sites.
– If for a specific ceramic each unit cell has 6
cations and the cations prefer OH sites
4 in OH
2 in TD
Note FCC unit cell has 4 OH and 8 TD sites.

Coordinates of Octahedral Sites (½ ½ ½), (½ 0 0), (0 ½ 0), ( 0 0 ½)
Tetrahedral Sites Octahedral Sites
19
Site Selection III
3. Bond Hybridization – significant covalent
bonding
– the hybrid orbitals can have impact if significant
covalent bond character present
– For example in SiC
• XSi = 1.8 and XC = 2.5
% ionic character = 100 {1 - exp[-0.25( X Si  X C )2 ]} = 11.5%
• ~ 88% covalent bonding

• both Si and C prefer sp3 hybridization
• Therefore in SiC, Si gets TD sites
20
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 prefer OH sites
21
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 OH
sites
So each oxygen has 6 neighboring Mg2+

22
AX Crystal Structures
AX–Type Crystal Structures include NaCl, CsCl, and zinc
blende
Cesium Chloride structure:
rCs  0.170
= = 0.939
rCl 0.181
 cubic sites preferred
So each Cs+ has 8 neighboring Cl-
23
AX Crystal Structures
Zinc Blende structure rZn2 0.074
= = 0.529  OH ??
rO 2 0.140
• Size arguments predict Zn2+

in OH sites,
• In observed structure Zn2+
in TD sites
• Why is Zn2+ in TD sites?
– bonding hybridization of
zinc favors TD sites
From Fig. 4.13

So each Zn
2+ has 4 neighboring O2-
Callister’s Materials Science and
Engineering, Adapted Version.
Ex: ZnO, ZnS, SiC

24
AX2 Crystal Structures
Fluorite structure
• Calcium Fluorite
(CaF2)
• cations in cubic sites
• UO2, ThO2, ZrO2,
CeO2
• antifluorite structure –
cations and anions
reversed
25
ABX3 Crystal Structures
Perovskite structure
Ex: complex oxide

BaTiO3
26
Ceramic Density Computation
Number of formula units with in the unit cell
n( AC  AA )

r=
VC N A
∑AC = Sum of atomic weights of all cations in the formula
unit
∑AA = Sum of atomic weights of all anions in the formula
unit
VC = The unit cell volume
27
Problem
• On the basis of crystal structure, compute

the theoretical density of NaCl.
rNa+ = 0.102 nm
rCl- = 0.181 nm
28
Solution
• ∑AC = A Na = 22.99 g/mol
• ∑AA = A Cl= 35.45 g/mol
• VC = (2rNa+ +2rCl- )3
How to calculate n’?
Both Na and Cl form FCC,

Hence n’ = 4
29
Silicate Ceramics
Most common elements on earth are Si & O
Si4+
O2-
crystobalite
• SiO2 (silica) structures are quartz,

crystobalite, & tridymite
• The strong Si-O bond leads to a strong, high
melting material (1710ºC)
30
Amorphous Silica
• Silica gels - amorphous SiO2

– Si4+ and O2- not in well-
ordered lattice
– Charge balanced by H+ (to
form OH-) at “dangling”
bonds
• very high surface area >
200 m2/g
– SiO2 is quite stable,
therefore unreactive
• makes good catalyst
support
Silica Glass
• Dense form of amorphous silica
– Charge imbalance corrected with “counter
cations” such as Na+
– Borosilicate glass is the pyrex glass used
in labs
• better temperature stability & less brittle than sodium
glass
32
Silicates
– Combine SiO44- tetrahedra by having them

share corners, edges, or faces
Mg2SiO4 Ca2MgSi2O7
– Cations such as Ca2+, Mg2+, & Al3+ act to

neutralize & provide ionic bonding
33
Layered Silicates
• Layered silicates (clay
silicates)
– SiO4 tetrahedra connected
together to form 2-D plane
• (Si2O5)2-
• So need cations to balance From Fig. 4.22
charge Engineering, Adapted Version.
34
Single vs Polycrystals
• Single Crystals E (diagonal) = 273 GPa

-Properties vary with
direction: anisotropic.
-Example: the modulus
of elasticity (E) in BCC iron:
E (edge) = 125 GPa
• Polycrystals
-Properties may/may not 200 mm
vary with direction.
-If grains are randomly
oriented: isotropic.
(Epoly iron = 210 GPa)
-If grains are textured,
2/26/2020
anisotropic.
Polymorphism
• Two or more distinct crystal structures for the same
material (allotropy/polymorphism)
iron system
titanium liquid
, -Ti
1538ºC
BCC -Fe
carbon
1394ºC
diamond, graphite
FCC -Fe
912ºC
BCC -Fe
25
Carbon Forms
• Carbon black – amorphous

– surface area ca. 1000
m2/g
• Diamond
– tetrahedral carbon
• hard – no good slip planes
• brittle – can cut it
– large diamonds – jewelry
– small diamonds
• often man made - used for
cutting tools and polishing
– diamond films Crystal Structure of
• hard surface coat – tools, Diamond = ZnS type
medical devices, etc.
structure
37
Carbon Forms - Graphite
• layer structure – aromatic layers
From Fig. 4.26

Callister’s Materials Science and Engineering
Adapted Version.
– weak van der Waal’s forces between layers

– planes slide easily, good lubricant
38
CHE F243
Krishna Etika
BITS Pilani
Pilani Campus
Thought for the Day
Bullet Trapping Polymers
2/26/2020 2
Crystal Structure of Ceramics
Lecture 8-9
3
Thought for the Day
Bendable Glass
Package
2/26/2020 2
Oxide structures
cations
(usually FCC)
lattice
Silicate Ceramics
Most common elements on earth are Si & O
Si4+
O2-
crystobalite
• SiO2 (silica) structures are quartz,

crystobalite, & tridymite
• The strong Si-O bond leads to a strong, high
melting material (1710ºC)
6
Amorphous Silica
• Silica gels - amorphous SiO2

– Si4+ and O2- not in well-
ordered lattice
– Charge balanced by H+ (to
form OH-) at “dangling”
bonds
• very high surface area >
200 m2/g
– SiO2 is quite stable,
therefore unreactive
• makes good catalyst
support
Silica Glass
in labs
glass
8
Silicates

Mg2SiO4 Ca2MgSi2O7

9
Layered Silicates
silicates)
• (Si2O5)2-
10
Layered Silicates
• Kaolinite clay alternates (Si2O5)2- layer with
Al2(OH)42+ layer
Note: these sheets loosely bound by van der Waal’s forces

11
Layered Silicates
• Can change the counterions

– this changes layer spacing
– the layers also allow absorption of water
• Micas KAl3Si3O10(OH)2
• Bentonite
– used to seal wells
– packaged dry
– swells 2-3 fold in H2O
– pump in to seal up well so no polluted ground
water seeps in to contaminate the water
supply.
12
Carbon Forms
• Carbon black – amorphous

– surface area ca. 1000
m2/g
• Diamond
– tetrahedral carbon
• hard – no good slip planes
• brittle – can cut it
– large diamonds – jewelry
– small diamonds
• often man made - used for
cutting tools and polishing
– diamond films Crystal Structure of
• hard surface coat – tools, Diamond = ZnS type
medical devices, etc.
structure
13
From Fig. 4.26

Adapted Version.

14
Carbon Forms –
Fullerenes and Nanotubes
• Fullerenes or carbon nanotubes
– wrap the graphite sheet by curving into ball or tube
– Buckminister fullerenes
• Like a soccer ball C60 - also C70 + others
15
Structure and Properties of
Polymers
16
Polymers
What is a polymer?
Poly mer
many repeat unit
repeat repeat repeat

unit unit unit
H H H H H H H H H H H H H H H H H H
C C C C C C C C C C C C C C C C C C
H H H H H H H Cl H Cl H Cl H CH3 H CH3 H CH3
Polyethylene (PE) Polyvinyl chloride (PVC) Polypropylene (PP)
Adapted from Fig. 14.2, Callister 7e.
17
Ancient Polymer History
• Originally natural polymers were used

– Wood – Rubber
– Cotton – Wool
– Leather – Silk
• Oldest known uses

– Rubber balls used by Incas
– Noah used pitch (a natural polymer)
for the ark
18
Site Selection
Which sites will cations occupy?

1. Size of sites
– does the cation fit in the site
2. Stoichiometry
– if all of one type of site is full the
remainder have to go into other types of
sites.
3. Bond Hybridization
14
Paraffin Compounds
20
Unsaturated Hydrocarbons
• Double & triple bonds relatively reactive –

can form new bonds
– Double bond – ethylene or ethene - CnH2n
H H
C C
H H
• 4-bonds, but only 3 atoms bound to C’s

– Triple bond – acetylene or ethyne - CnH2n-2
H C C H
21
Example: Predicting 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,
Anion --coord # = 6
--structure = NaCl
O 2- 0.140
Cl - 0.181
F- 0.133
Chemistry of Polymers
Note: polyethylene is just a long HC

- paraffin is short polyethylene
23
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 prefer OH sites
21
25
26
MOLECULAR WEIGHT
• Molecular weight, Mi: Mass of a mole of chains.
Lower M higher M
total wt of polymer
Mn 
total # of molecules
M n  x i M i
M w  w i M i
Mw is more sensitive to higher

molecular weights
27
Ceramic Density Computation
Number of formula units with in the unit cell
n( AC  AA )

r=
VC N A
∑AC = Sum of atomic weights of all cations in the formula
unit
∑AA = Sum of atomic weights of all anions in the formula
unit
VC = The unit cell volume
27
Degree of Polymerization
• Average # of repeat units in the chain

• Related to Number average Molecular
weight as
• Where m is the repeat unit molecular

weightH H H H H H H H H H H H
H C C (C C ) C C C C C C C C H ni = 6
H H H H H H H H H H H H
29
Degree of Polymerization, n
n = number of repeat units per chain
For Copolymers
Mn Mw
nn   xi ni  nw   w i ni 
m m
where m  average molecular weight of repeat unit

m  fi mi
Chain fraction mol. wt of repeat unit i
30
Problem 13.6
• Molecular weight data for some polymer are tabulated here.
Compute (a) the number-average molecular weight, and (b)
the weight-average molecular weight. (c) If it is known that
this material's degree of polymerization is 710, which one of
the polymers listed in Table 14.3 is this polymer? Why?
31
Solution
32
End to End Distance, r
33
Molecular Structures
• Covalent chain configurations and strength:
secondary
bonding
Linear Branched Cross-Linked Network
Direction of increasing strength

34
Silica Glass
in labs
glass
32
Silicates

Mg2SiO4 Ca2MgSi2O7

33
Layered Silicates
silicates)
• (Si2O5)2-
34
cis/trans Isomerism
CH3 H CH3 CH2

C C C C
CH2 CH2 CH2 H
cis trans
cis-isoprene trans-isoprene
(natural rubber) (gutta percha)
bulky groups on same bulky groups on opposite
side of chain sides of chain
38
Copolymers
two or more monomers random
polymerized together
• random – A and B randomly
vary in chain
• alternating – A and B
alternate in polymer chain alternating
• block – large blocks of A
alternate with large blocks of block
B
• graft – chains of B grafted
on to A backbone
A– B–
graft
39
Layered Silicates

• Bentonite
– packaged dry
supply.
36
What exactly is Tg ?
• There is a certain temperature(different for
each polymer) called the glass transition
temperature, or Tg for short.
• When the polymer is cooled below this
temperature, it becomes hard and brittle, like
glass.
• Some polymers are used above their glass
transition temperatures, and some are used
below.
– Polystyrene, PMMA etc below Tg
– Rubber Elastomers above their Tg
41
CHE F243
Krishna Etika
BITS Pilani
Pilani Campus
Thought for the Day
Super Hydrophobic Coatings
2/26/2020 2
Re-Cap
2/26/2020 3
Polymers
What is a polymer?
Poly mer
many repeat unit
repeat repeat repeat

unit unit unit
H H H H H H H H H H H H H H H H H H
C C C C C C C C C C C C C C C C C C
H H H H H H H Cl H Cl H Cl H CH3 H CH3 H CH3
Polyethylene (PE) Polyvinyl chloride (PVC) Polypropylene (PP)
4
MOLECULAR WEIGHT
Lower M higher M
total wt of polymer
Mn 
M n  x i M i
M w  w i M i

molecular weights
5
Degree of Polymerization
• Average # of repeat units in the chain

• Related to Number average Molecular
weight as
• Where m is the repeat unit molecular

weightH H H H H H H H H H H H
H C C (C C ) C C C C C C C C H ni = 6
H H H H H H H H H H H H
6
Crystal Structure of Ceramics
Lecture 8-9
3
secondary
bonding

8
Tacticity
Tacticity – stereoregularity of chain
H H H H H H H H
isotactic – all R groups on same side
of chain C C C C C C C C
H R H R H R H R
syndiotactic – R groups
alternate sides H H H R H H H R
C C C C C C C C
H R H H H R H H
atactic – R groups random
H H H H H R H H
C C C C C C C C
H R H R H H H R
9
Copolymers
two or more monomers random
polymerized together
• random – A and B randomly
vary in chain
• alternating – A and B
alternate in polymer chain alternating
• block – large blocks of A
alternate with large blocks of block
B
• graft – chains of B grafted
on to A backbone
A– B–
graft
10
Oxide structures
cations
(usually FCC)
lattice
What exactly is Tg ?
• There is a certain temperature(different for
each polymer) called the glass transition
temperature, or Tg for short.
• When the polymer is cooled below this
temperature, it becomes hard and brittle, like
glass.
• Some polymers are used above their glass
transition temperatures, and some are used
below.
– Polystyrene, PMMA etc below Tg
– Rubber Elastomers above their Tg
12
Lecture 10
2/26/2020 13
Question?
Do polymers exhibit both Melting and

Glass Transition Temperature?
14
Answer
• The glass transition is not the same thing as

melting.
• Melting is a transition which occurs
in crystalline polymers.
– Melting happens when the polymer chains fall out
of their crystal structures, and become a
disordered liquid.
• The glass transition is a transition which
happens to amorphous polymers
15
Tg and Tm of Various Polymers
But even crystalline polymers will have a some
amorphous portion.
16
Question?
How to we measure Tg?
17
Silicates

Mg2SiO4 Ca2MgSi2O7

9
How do we measure Tg
DSC data from a material

undergoing Tg, example:
DSC data from a material not
polymer
metal
?
19
Typical DSC data for
some polymers
What is Tc now!!!!!
20
Crystallization Temperature
• Above the glass transition temperature the
polymer chains have high mobility.
• chains have enough energy to form
ordered arrangements and undergo
crystallization.
• Crystallization is an exothermic process,
so heat is released to the surroundings.
21
Layered Silicates

• Bentonite
– packaged dry
supply.
12
Factors Affecting Tg
• Chain Flexibility: polymer with a backbone
that exhibits higher flexibility will have a
lower Tg.
23
From Fig. 4.26

Adapted Version.

14
• Cross-linking : reduces chain mobility, so
Tg will be increased.
• Plasticizers : Small molecules, typically
esters, added to the polymer increase the
chain mobility by spacing out the chains,
and so reduce Tg.
25
Polymer Crystallinity
Ex: polyethylene unit cell
• Crystals must contain

the polymer chains in
some way
– Chain folded structure
10 nm
26
Polymer Crystallinity
Polymers are rarely 100%
crystalline
• Too difficult to get all those chains
aligned crystalline
region
• % Crystallinity: % of material
that is crystalline.
-- TS and E often increase
with % crystallinity.
-- Annealing causes
crystalline regions
to grow. % crystallinity
increases. amorphous
region
27
Polymer Crystal Forms
• Single crystals – only if slow careful growth
28
• Spherulites – fast
growth – forms
lamellar (layered)
structures
Spherulite
surface
29
Spherulites – cross polarized
light transmission photomicrograph
Maltese cross
Ceiling of St. John's Co-

Cathedral, Valletta,
Malta
30
Determining %Crystallinity
• ρs = Sample Density
• ρa = density of totally amorphous polymer
• ρC = density of totally crystalline polymer
31
Problem
• (a) Compute the density of totally
crystalline polyethylene, whose
unit cell is orthorhombic and the
equivalent of two ethylene repeat
units is contained within each unit
cell.
• (b)Using the answer to part (a),

calculate the percent crystallinity
of a branched polyethylene that
has a density of 0.925 g/cm3. The
density for the totally amorphous
material is 0.870 g/cm3.
32
Solution (a)
n =2
33
Solution (b)
34
The image part with relationship ID rId3 was not found in the file.
CHE F243
Krishna Etika
BITS Pilani
Pilani Campus
Thought for the Day
Self Healing Material
2/26/2020 2
Lecture 11
Crystal Structure Determination
X-Ray Diffraction
2/26/2020
X-Ray Diffraction
• Diffraction gratings must have spacings comparable to

the wavelength of diffracted radiation.
• Can’t resolve spacings  
• Spacing is the distance between parallel planes of
atoms. 4
X-Ray Diffraction (XRD)
• Historical Perspective on XRD

• 1665: Diffraction effects observed by Italian mathematician
Francesco Maria Grimaldi
• 1868: X-rays Discovered by German Scientist Röntgen.
• 1912: Discovery of X-ray Diffraction by Crystals: von Laue
• 1912: Bragg’s Discovery
X rays are relatively short-wavelength high energy

electromagnetic radiations.
They occupy region between Gamma and UV rays
in EM spectrum
26 February 2020
5
Production of X-Rays
 X-rays are produced by the interactions between an
external beam of electrons and the electrons in the
inner shells of an atom (target)
 A high voltage (typically thousands of volts) is
maintained across these electrodes, which draws
electrons to the anode or target.
 X-rays are produced at the point of impact and radiate in all
directions
26 February 2020
6
Bulk or Commodity Polymers
24
Production of X-Rays
 X-ray radiations from the X-ray tube operated at a voltage

above threshold contains not only strong Kα line but
also the weaker Kβ lines along with continuous
spectrum.
 The X-rays are passed through a filter to removes
unwanted spectrum
 Filter is made of materials with K absorption edge
between Kα and Kβ wavelength of target material.
8
25
Interplanar Spacing
For orthogonal coordinates, sum of (direction cosines)2 = 1
26 February 2020 10
Problem
For BCC iron, compute (a) the interplanar spacing, and (b)
the diffraction angle for the (220) set of planes. The lattice
parameter for Fe is 0.2866 nm. Also, assume that
monochromatic radiation having a wavelength of 0.1790
nm is used, and the order of reflection is 1.
26 February 2020 11
d spacing formulae
26 February 2020 12
Bragg’s Law
Crystals reflect the x-rays falling on their surface. The reflection of
x-rays follow the Bragg’s law:
Bragg’s law tells us the conditions that must be met for the reflected X-
ray waves to be in phase with each other (constructive interference).
If these conditions are not met, destructive interference reduces the
reflected intensity to zero!
26 February 2020 13
MOLECULAR WEIGHT
Lower M higher M
total wt of polymer
Mn 
M n  x i M i
M w  w i M i

molecular weights
27
X-Ray Powder Diffraction Method
Powder method is used for
determination of Crystal
Structures.
A set of parallel crystal planes
making an angle  with the
incident beam will reflect if
Bragg’s condition is satisfied.
Since powder sample, different
orientations of same crystal
planes different directions of
reflection. Hence we get a cone
of reflections and not a line.
The distance between arc of
On the film, only arcs from each cone is given by S = 4R
each cone are recorded.
26 February 2020 15
X-Ray Powder Diffraction Method
XRD data from film
26 February 2020 16
Modern Diffractometer
26 February 2020 17
X-Rays to Determine Crystal
Structure
• Incoming X-rays diffract from crystal planes.
reflections must
be in phase for
a detectable signal From Fig. 4.35
Callister’s Materials
extra
distance
 Science and Engineering,
travelled   Adapted Version.
by wave “2” spacing

d between
planes
Measurement of critical X-ray

intensity n
angle, c, allows d=
(from 2 sin c
computation of planar
detector)
spacing, d.

c 18
Powder method gives the values of  for which bragg’s reflection is
allowed. [ = S/4R ]
Each ring will have one value of , but can come from different planes.
 Now, we know that,
For n =1, we get
Since,  is fixed (monochromatic X-ray beam), assume h, k, l and calculate

a for 1st ring.
 Assume different h,k,l for other rings and calculate “a” for each ring.
 If your assumption of h,k,l is correct, you will get same “a” for each. If
yes, then you have already found out the various crystal planes present and
the26lattice constant.  crystal structure determined.
February 2020 19
secondary
bonding

34
Polymers – Molecular Shape
Conformation – Molecular orientation can be

changed by rotation around the bonds
– note: no bond breaking needed
Adapted from Fig.

14.5, Callister 7e.
35
Polymers – Molecular Shape
Configurations – to change must break bonds
• Stereoisomerism
H H H H H R
C C C C or C C
H R
H R H H
A A
C C
E E
B D D B
mirror
plane
36
Solution
Assuming BCC
Hence, Lattice Constant = 3.18 A

Crystal Structure BCC
26 February 2020 23
26 February 2020 24
cis/trans Isomerism
CH3 H CH3 CH2

C C C C
CH2 CH2 CH2 H
cis trans
cis-isoprene trans-isoprene
(natural rubber) (gutta percha)
bulky groups on same bulky groups on opposite
side of chain sides of chain
38
26 February 2020 26
CHE F243
Krishna Etika
BITS Pilani
Pilani Campus
Thought for the Day
Anti-Corrosive Coating for Steel
Chemically Bonded Phosphate

Ceramics (CBPCs)
2/26/2020 2
Re-Cap
2/26/2020 3
Crystal Structure Defects
Chapter 5
26 February 2020 4
Point Defects in Alloys
Hume-Rothery Rules
Empirical rules that govern formation of solid solution by
substitution. Extensive solubility occurs when:
1. The solute and the solvent atoms do not differ by more than
15% in diameter.
2. The electronegativity difference between the elements is
small
3. The valency and the crystal structure of the elements are the
same.
4. The solubility of a metal with higher valency in a solvent of
lower valence is more compared to the reverse situation. e.g.
Zn is much more soluble in Cu than Cu in Zn.
26 February 2020 5
Alloy Compositions
Specification of composition of Alloys
m1
– weight percent C1  x 100
m1  m2
m1 = mass of component 1
n m1
– atom percent C 
'
1 x 100
n m1  n m 2
nm1 = number of moles of component 1
26 February 2020 6
Line Defects
26 February 2020 7
Re-Cap
2/26/2020 3
Dislocations
Dislocations are visible in electron micrographs
26 February 2020 9
MOLECULAR WEIGHT
Lower M higher M
total wt of polymer
Mn 
M n  x i M i
M w  w i M i

molecular weights
5
Dislocations Types
26 February 2020 11
Degree of Polymerization, n
n = number of repeat units per chain
For Copolymers
Mn Mw
nn   xi ni  nw   w i ni 
m m
where m  average molecular weight of repeat unit

m  fi mi
Chain fraction mol. wt of repeat unit i
7
Dislocation Motion
Dislocation motion leads to plastic (permanent) deformation)
26 February 2020 13
Area Defects
26 February 2020

Surface Defects
External Internal
Free surface Grain boundary

Same
Stacking fault phase
Twin boundary
Interphase Different
phases
boundary
26 February 2020 15
Free Surface
Free Surface is
Area A not similar to
bulk and is a
Broken
defect since
bonds atoms on surface
are not bonded
Area A
to other atoms
on all sides.
If bond are broken over an area A then two
free surfaces of a total area 2A is created
26 February 2020 BITS Pilani, Pilani Campus
Melting vs. Glass Transition Temp.
What factors affect Tm and Tg?
• Both Tm and Tg increase with

increasing chain stiffness
• Chain stiffness increased by
1. Bulky side groups
2. Polar groups or side
groups
3. Double bonds or aromatic
chain groups
• Regularity – effects Tm only
11
Grain Boundary
Grain Boundaries
 regions between crystals
 transition from lattice of one
region to another
Depending on orientation of
grains, it can be
1. High angle grain boundary
2. Small angle grain boundary

Stacking Faults
A stacking fault is a defect that alters the periodic

sequence of layers.
These defects may be a wrong layer inserted into the

sequence, a change of the layer sequence or a different
translation between two subsequent layers.
Twin Boundaries
26 February 2020 20
Tg and Tm of Various Polymers
But even crystalline polymers will have a some
amorphous portion.
16
Introduction
Diffusion - Mass transport by atomic motion

Mechanisms
Gases & Liquids – random (Brownian)
motion
Solids – vacancy diffusion or interstitial
diffusion

Question?
How to we measure Tg?
17
Importance of Diffusion
• Doping silicon with phosphorus for n-type semiconductors:
0.5 mm
• Process:
1. Deposit P rich
layers on surface.
magnified image of a computer chip
silicon
2. Heat it.
3. Result: Doped light regions: Si atoms
semiconductor
regions.
light regions: Al atoms

silicon
26 February 2020 24
How do we measure Tg
DSC data from a material

DSC data from a material not
polymer
metal
?
19
Self Diffusion
• Self-diffusion: In an elemental solid, atoms

also migrate.
Label some atoms After some time
C
C
A D
A
D
B
B
Any idea how to know or see

this???
26 February 2020 26
Diffusion Mechanism
Vacancy Diffusion:
• atoms exchange with vacancies
• applies to substitutional impurities atoms
• rate depends on:
--number of vacancies
--activation energy to exchange.
increasing elapsed time

26 February 2020 27
Crystallization Temperature
• Above the glass transition temperature the
polymer chains have high mobility.
• chains have enough energy to form
ordered arrangements and undergo
crystallization.
• Crystallization is an exothermic process,
so heat is released to the surroundings.
21
Factors Influencing Tg
• Chain length
22
Steady State Diffusion
Rate of diffusion independent of time
dC
Flux proportional to concentration gradient =
dx
Fick’s first law of diffusion
C1 C1
dC
C2 C2 J  D
dx
x1 x2
x
D  diffusion coefficient
dC C C2  C1
if linear  
dx x x2  x1
26 February 2020 30
• Chain Flexibility: polymer with a backbone
that exhibits higher flexibility will have a
lower Tg.
23
Solution
• Solution – assuming linear conc. gradient

glove
C1 dC C2  C1
tb 
2 J -D  D
paint
6D dx x2  x1
skin
remover
C2 Data: D = 110 x 10-8 cm2/s
x1 x2 C1 = 0.44 g/cm3
C2 = 0.02 g/cm3
x2 – x1 = 0.04 cm
-8 2 (0.02 g/cm3  0.44 g/cm3 ) g

J   (110 x 10 cm /s)  1.16 x 10-5
(0.04 cm) cm2s
26 February 2020 32
Diffusion Coefficient
• Diffusion coefficient increases with

increasing T.
 Qd 
D  Do exp  
 RT 
D = diffusion coefficient [m2/s]

Do = pre-exponential [m2/s]
Qd = activation energy [J/mol or eV/atom]
R = gas constant [8.314 J/mol-K]
T = absolute temperature [K]
26 February 2020 33
• Cross-linking : reduces chain mobility, so
Tg will be increased.
• Plasticizers : Small molecules, typically
esters, added to the polymer increase the
chain mobility by spacing out the chains,
and so reduce Tg.
25
Problem
Example: At 300ºC the diffusion coefficient and

activation energy for Cu in Si are
D(300ºC) = 7.8 x 10-11 m2/s
Qd = 41.5 kJ/mol
What is the diffusion coefficient at 350ºC?
26 February 2020 35
Solution
D transform data ln D
Temp = T 1/T
Qd 1 Qd  1
lnD2  lnD0    and lnD1  lnD0   
R  T2  R  T1 
D2 Qd  1 1
 lnD2  lnD1  ln    
D1 R  T2 T1 
26 February 2020 36
CHE F243
Krishna Etika
BITS Pilani
Pilani Campus
Thought for the Day
Electrochromic Glass
2/26/2020 2
• Spherulites – fast
growth – forms
lamellar (layered)
structures
Spherulite
surface
29
For n =1, we get

a for 1st ring.
February 2020 4
26 February 2020 5
Problem
An element, BCC or FCC, shows diffraction peaks at 2θ: 40, 58,
73, 86.8,100.4 and 114.7. Cu-Kα radiation (λD=0.1542 nm) was
used for diffraction studies. Determine:(a)Crystal structure?(b)
Lattice constant?
Hint
26 February 2020 6
Solution
Assuming BCC

26 February 2020 7
Microscopy
26 February 2020 8
Electron Microscopy
Optical Microscopy involves irradiating sample with
visible light beam.
Electron Microscopy involves irradiating sample with
electron beam.
26 February 2020 9
Response of E-Beam irradiation on specimen BITS Pilani, Pilani Campus
Electron Microscopy
Inelastic collision of Elastically scattered Transmitted
Electron Microscopy beam electron is electrons
incoming electron
results in a transfer of deflected back out of are those
energy to the the specimen, the which travel
specimen atom and a electron is termed a through the
potential expulsion of Backscattered specimen
an electron from that electron (BSE) are able to
atom as a secondary reach the
electron (SE). other end
and travel
out.
26 February 2020 10
Scanning Electron
Microscopy
http://www.technoorg.hu/news-and-events/articles/high-resolution-scanning-
electron-microscopy-1/
 A focused electron beam (2-10

keV) scans on the surface,
several types of signals are
produced and detected as a
function of position on the surface.
The space resolution can be as
high as 1 nm.
 Different type signal gives different
information:
a)Secondary electrons: surface
structure.
b)Backscattered electrons:
surface structure and average
elemental information.
c)X-rays and Auger electrons:
elemental composition with
different thickness-sensitivity. Schematic of SEM
26 February 2020 11
Scanning Electron Microscopy
http://www.technoorg.hu/news-and-events/articles/high-resolution-scanning-
electron-microscopy-1/
Principle of Image generation in SEM

26 February 2020 12
Lecture 13
26 February 2020 13
Scanning Electron Microscopy
SE: low probing volume and provide surface topography
BSE: greater probing volume and provide better contrast
(Z contrast)
The BSE yield depends on the atomic number of the specimen the
backscattered image has a so called Z-contrast. The higher the atomic
number, the larger the BSE yield is. Higher atomic number element appear
brighter.
(a) (b)
SE image (a) and BSE image (b) of the same sample area
Transmission Electron
Microscopy
The parts in a TE microscope can be
divided as follows:
i) Electron source (or called
electron gun).
ii) High voltage generator and
acceleration tube.
iii) Illumination lens system and
deflector.
iv) Specimen holder and stage.
v) Image-forming lens system.
vi) Viewing chamber and camera
chamber.
Schematic of TEM
26 February 2020 15
Transmission Electron Microscopy
Principal features of an optical microscope, a transmission
electron microscope and a scanning electron microscope,
drawn to emphasize the similarities of overall design.
SEM TEM

X-Ray Diffraction
• Diffraction gratings must have spacings comparable to

the wavelength of diffracted radiation.
• Can’t resolve spacings  
• Spacing is the distance between parallel planes of
atoms. 4
Scanning Probe Microscopy
Scanning Tunneling
Microscope Image of (111)
silicon plane
26 February 2020
Length Scales
26 February 2020 19
Comparison
26 February 2020
20
Grain Size Determination
TEM Image of a Polycrystalline Material.
How to define grain size here???
26 February 2020 21
Grain Size Determination
Intercept Method
1. Draw a straight line

2. Count number of grain
boundaries intercepting the line
–n
3. Measure the length of the line, l
Average Grain diameter , d is

defined as
26 February 2020 22
Chapter 5
26 February 2020 23
Introduction
What is a crystal defect
If we assume a perfect crystal structure containing
pure elements, then anything that deviated from
this concept or intruded in this uniform
homogeneity would be an imperfection/defect.
1. There are no perfect crystals.
2. Many material properties are improved by
the presence of imperfections and
deliberately modified (alloying and doping).
(Defects are not always bad!!!)
26 February 2020 24
Introduction
Why worry about crystal defects

It is important to know the types of defects
that exists in a crystal and the roles they play
in affecting the behavior of materials.
The properties of some materials are

profoundly influenced by the presence of
imperfections/defects.
26 February 2020 25
Types of Defects
26 February 2020 26
Point Defects
Vacancies:
-vacant atomic sites in a structure.
distortion Vacancy
of planes
Self-Interstitials:
distortion self-interstitial
of planes
Substitutional::
Substitutional solid solution.
(e.g., Cu in Ni)
26 February 2020 27
Point Defects in Ceramics
Frenkel Defect
To maintain the charge neutrality, a cation vacancy-cation interstitial
pair occur together. The cation leaves its normal position and moves to
the interstitial site.
Schottky Defect
To maintain the charge neutrality, remove 1 cation and 1 anion; this
creates 2 vacancies.
Schottky
Defect
Frenkel
Defect
26 February 2020 28
Point Defect Concentration
All crystalline solids contain vacancies

It is not possible to create such a material that is free
of these defects.
The necessity of the existence of vacancies is explained

using principles of thermodynamics
Presence of vacancies increases the entropy (i.e., the
randomness) of the crystal.
 Hence, vacancy is a thermodynamically stable (or
favored) defect.
26 February 2020 29
 The equilibrium number of vacancies (Nv) for a given

quantity of material depends on and increases with
temperature according to
T = absolute temperature in kelvin, N = total number of atomic

K = Boltzmann’s constant. sites,
The value of k is 1.38 10-23J/atom-K, Qv = Activation Energy,
or 8.62 10-5eV/atom-K,
30
26 February 2020
Problem
Calculate the equilibrium number of vacancies per cubic
meter for copper at 1000oC. The energy for vacancy formation
is 0.9 eV/atom; the atomic weight and density (at 1000 oC) for
copper are 63.5 g/mol and 8.4 g/cm3, respectively.
Given Data T = 1000oC, Qv = 0.9 ev/atom, k= 8.62 10-5 eV/

atom-K, N = ?
The whole logic here is how to find N. Any idea?

Why density and atomic weight are given???
26 February 2020 31
Solution
What exactly is N: It is the total number of atomic
sites (or atoms) remember that for copper crystal,
basis = 1 atom, which means only one atom per
atomic site.
Logic:
1 mole of copper contains = 6.023 X 1023 atoms (NA)
1 mole of copper weights = 63.5 g
In 8.4 g of copper how many atoms will be there:
(8.4/63.5) * 6.023 X 1023 atoms
That is, that many atoms will be present per cm3
26 February 2020 32
Solution
26 February 2020 33
Point Defects – Activation Energy
• We can get Qv from Nv -Q v 
= exp 
 
an experiment.  k T 
N
• Measure this... • Replot it...
Nv Nv slope
ln
N N
- Q v /k
exponential
dependence!
T
1/ T
defect concentration
26 February 2020 34
CHE F243
Krishna Etika
BITS Pilani
Pilani Campus
Thought for the Day
Mycelium – Based Materials
2/26/2020 2
Modern Diffractometer
26 February 2020 17
Chapter 5
26 February 2020 4
X-Rays to Determine Crystal
Structure
• Incoming X-rays diffract from crystal planes.
reflections must
be in phase for
a detectable signal From Fig. 4.35
Callister’s Materials
extra
distance
 Science and Engineering,
travelled   Adapted Version.
by wave “2” spacing

d between
planes
Measurement of critical X-ray

intensity n
angle, c, allows d=
(from 2 sin c
computation of planar
detector)
spacing, d.

c 18
Point Defects
Vacancies:
-vacant atomic sites in a structure.
distortion Vacancy
of planes
Self-Interstitials:
distortion self-interstitial
of planes
Substitutional::
Substitutional solid solution.
(e.g., Cu in Ni)
26 February 2020 6
 The equilibrium number of vacancies (Nv) for a given

quantity of material depends on and increases with
temperature according to
T = absolute temperature in kelvin, N = total number of atomic

K = Boltzmann’s constant. sites,
The value of k is 1.38 10-23J/atom-K, Qv = Activation Energy,
or 8.62 10-5eV/atom-K,
7
26 February 2020
For n =1, we get

a for 1st ring.
February 2020 19
Observing Point Defect Conc
• Low energy electron
microscope view of a (110)
surface of NiAl.
• Increasing T causes surface
island of atoms to grow.
• Why?
The equilibrium vacancy
conc. increases via atom
motion from the crystal Island grows/shrinks to maintain
equil. vancancy conc. in the bulk.
to the surface, where
they join the island.
26 February 2020
An Alloy is formed when two metals are mixed together given
that one metal is soluble in the other one in “solid state”.
Therefore, an alloy is a solid solution of two or more metals.
There are two types of solid solutions -
 Substitutional – Solute atoms
occupy the regular lattice sites of the
parent metal (solvent). Substitutional
solid solutions can be random (Cu-Ni)
or ordered (Cu-Au).
 Interstitial – Solute atoms occupy

the interstitial positions (Steel – C
solute atoms in Fe)
26 February 2020 10
Hume-Rothery Rules
Empirical rules that govern formation of solid solution by
substitution. Extensive solubility occurs when:
1. The solute and the solvent atoms do not differ by more than
15% in diameter.
2. The electronegativity difference between the elements is
small
3. The valency and the crystal structure of the elements are the
same.
4. The solubility of a metal with higher valency in a solvent of
lower valence is more compared to the reverse situation. e.g.
Zn is much more soluble in Cu than Cu in Zn.
26 February 2020 11
Will Cu and Ni form a Substitutional solid solution???
Crystal electroneg r (nm)

Structure
Ni FCC 1.9 0.1246
Cu FCC 1.8 0.1278

Application of Hume–Rothery rules – Solid
Solutions Element Atomic Crystal Electro- Valence
Radius Structure nega-
(nm) tivity
1. Would you predict Cu 0.1278 FCC 1.9 +2
C 0.071
more Al or Ag H 0.046
O 0.060
to dissolve in Zn? Ag 0.1445 FCC 1.9 +1
Al 0.1431 FCC 1.5 +3
Co 0.1253 HCP 1.8 +2
Cr 0.1249 BCC 1.6 +3
2. More Zn or Al Fe 0.1241 BCC 1.8 +2
Ni 0.1246 FCC 1.8 +2
in Cu? Pd 0.1376 FCC 2.2 +2
Zn 0.1332 HCP 1.6 +2
26 February 2020 13
Alloy Compositions
m1
m1  m2
n m1
'
1 x 100
n m1  n m 2
26 February 2020 14
• Frenkel Defect
--a cation is out of place.
• Shottky Defect
--a paired set of cation and anion vacancies.
Shottky
Defect:
Frenkel
Defect
QD / kT
• Equilibrium concentration of defects ~e
15
• Impurities must also satisfy charge balance = Electroneutrality
• Ex: NaCl Na + Cl -
cation
• Substitutional cation impurity vacancy
Ca 2+
Na +
Na +
Ca 2+
initial geometry Ca 2+ impurity resulting geometry
• Substitutional anion impurity

an ion vacancy
O 2-
Cl - Cl -
initial geometry O 2- impurity resulting geometry
Question
What point defects are possible for MgO as an

impurity in Al2O3? How many Mg2+ ions must be
added to form each of these defects?

Line Defects
26 February 2020 18
Line Defects
 Linear defects (Dislocations) are one-dimensional defects
that cause misalignment of nearby atoms.
 Slip between crystal planes result when dislocations
move,
 Dislocation movement produce permanent (plastic)
deformation. Schematic of Zinc (HCP):
before deformation after tensile elongation
 Types of Dislocations
Edge Dislocation slip steps
 Screw Dislocation
 Mixed Dislocation
26 February 2020 19
EDGE DISLOCATION
 extra half-plane of atoms inserted in a crystal structure; the

edge of the plane terminates within the crystal.
 Around the dislocation line there is some localized
distortion.
 b perpendicular () to dislocation line
Burgers vector, b: measure of lattice distortion

BURGERS VECTOR
Johannes Martinus BURGERS
Burger’s vector Burgers vector

Screw Dislocation
• Results from shear deformation

• b parallel () to dislocation line
26 February 2020 22
Mixed Dislocation
• Contains both edge and screw

dislocation.
26 February 2020 23
Chapter 5
26 February 2020 4
CHE F243
Krishna Etika
BITS Pilani
Pilani Campus
Thought for the Day
Radar Absorbing Materials
Microwave Absorption
2/26/2020 2
Re-Cap
2/26/2020 3
Area Defects
26 February 2020

Surface Defects
External Internal
Free surface Grain boundary

Same
Stacking fault phase
Twin boundary
Interphase Different
phases
boundary
26 February 2020 5
Dislocations
Dislocations are visible in electron micrographs
26 February 2020 9
Diffusion in Solids
Chapter 6
26 February 2020 7
Lecture 15

Interdiffusion
In an alloy, atoms tend to migrate from regions of
high concentration to regions of low concentration
Initially After some time
26 February 2020 9
Diffusion Mechanism
Vacancy Diffusion:

26 February 2020 10
Diffusion
How do we quantify the amount or rate of diffusion?
moles (or mass) diffusing mol kg

J  Flux   or
surface area time  cm2s m2s
Measured empirically
– Make thin film (membrane) of known surface area
– Impose concentration gradient
– Measure how fast atoms or molecules diffuse through the
membrane
M=
M l dM mass J  slope
J  diffused
At A dt
time
26 February 2020 11
Slip Planes
The plane on which a dislocation

moves
The plane containing both b (burgers

vector) and t (dislocation line) is called
the slip plane of a dislocation line.
26 February 2020 12

increasing T.
 Qd 
D  Do exp  
 RT 

26 February 2020 13
Dislocation Motion
Dislocation motion leads to plastic (permanent) deformation)
26 February 2020 13
Lecture 16

Non Steady State Diffusion
The concentration of diffusing species is a function

of both time and position C = C(x,t)
In this case Fick’s Second Law is used
C  C 2
D
t x 2
26 February 2020 16
Fick’s Second Law
• Copper diffuses into a bar of aluminum.
Surface conc.,
bar
Cs of Cu atoms
pre-existing conc., Co of copper atoms
Cs
B.C. at t = 0, C = Co for 0  x  
at t > 0, C = CS for x = 0 (const. surf. conc.)
26 February 2020
C = Co for x =  17
Fick’s second Law
C  x , t   Co  x 
 1  erf  
Cs  Co  2 Dt 
C(x,t) = Conc. at point x at time t CS

erf (x) = error function
C(x,t)
Co
erf(z) values are given in Table 6.1
How to Solve the Fick’s second law of diffusion for semi infinite solid?
26 February 2020 18
Problem 5.34
For an FCC single crystal, would you expect the surface
energy for a (100) plane to be greater or less than that of
(111) plane? Why?
Solution:
Planar Density is inverse proportional to the surface energy

Problem
An FCC iron-carbon alloy initially containing 0.20 wt% C is

carburized at an elevated temperature and in an
atmosphere that gives a surface carbon concentration
constant at 1.0 wt%. If after 49.5 h the concentration of
carbon is 0.35 wt% at a position 4.0 mm below the surface,
determine the temperature at which the treatment was
carried out.
26 February 2020 20
Solution
C ( x , t )  Co  x 
Solution (cont.):  1  erf  
Cs  Co  2 Dt 
– t = 49.5 h x = 4 x 10-3 m
– Cx = 0.35 wt% Cs = 1.0 wt%
– Co = 0.20 wt%
C( x, t )  Co 0.35  0.20  x 
  1  erf    1  erf ( z )
Cs  Co 1.0  0.20  2 Dt 
 erf(z) = 0.8125
26 February 2020 21
Solution
We must now determine from Table 5.1 the value of z for which the
error function is 0.8125. An interpolation is necessary as follows
z erf(z) z  0.90 0.8125  0.7970


0.95  0.90 0.8209  0.7970
0.90 0.7970
z 0.8125 z  0.93
0.95 0.8209
Now solve for D x x2

z D
2 Dt 4 z 2t
 x2  3 2
( 4 x 10 m) 1h
D      2.6 x 10 11 m2 /s
 4z 2t  ( 4)(0.93)2 ( 49.5 h) 3600 s
 
26 February 2020 22
Solution
To solve for the temperature at Qd
which D has above value, we T 
use a rearranged form of R(lnDo  lnD )
Equation (6.9a);
from Table 6.2, for diffusion of C in FCC Fe

Do = 2.3 x 10-5 m2/s Qd = 148,000 J/mol
 148,000 J/mol
T 
(8.314 J/mol - K)(ln 2.3 x10 5 m2 /s  ln 2.6 x10 11 m2 /s)
T = 1300K = 1027°C
26 February 2020 23
Solution to Ficks 2nd Law
26 February 2020 24
Solution of Ficks 2nd Law
But,
We need to solve this Equation

Introduction
Diffusion - Mass transport by atomic motion

Mechanisms
Gases & Liquids – random (Brownian)
motion
Solids – vacancy diffusion or interstitial
diffusion

First and Second Boundary Condition

26 February 2020 28
CHE F243
Krishna Etika
BITS Pilani
Pilani Campus

Recap
2/26/2020 2
Diffusion
How do we quantify the amount or rate of diffusion?
moles (or mass) diffusing mol kg

J  Flux   or
surface area time  cm2s m2s
Measured empirically
– Make thin film (membrane) of known surface area
– Impose concentration gradient
– Measure how fast atoms or molecules diffuse through the
membrane
M=
M l dM mass J  slope
J  diffused
At A dt
time
26 February 2020 29
•The concentration of diffusing species is a function of
both time and position C = C(x,t)
• In this case Fick’s Second Law is used

•
C  C 2
D
t x 2
4
26 February 2020
Chemical Protective Cloathing
Methylene chloride is a common ingredient of paint removers.

Besides being an irritant, it also may be absorbed through
skin. When using this paint remover, protective gloves
should be worn.
If butyl rubber gloves (0.04 cm thick) are used, what is the
diffusive flux of methylene chloride through the glove?
Data:
– diffusion coefficient in butyl rubber:
D = 110 x10-8 cm2/s
– surface concentrations: C1 = 0.44 g/cm3
C2 = 0.02 g/cm3
26 February 2020 31
Thought for the Day
Indestructible Coatings
2/26/2020 6
Diffusion in Polymers
Diffusion mechanism : analogous to

interstitial diffusion in metals.
diffusive movements occur through small
voids between polymer chains
Rates of diffusion are greater through

amorphous regions than through
crystalline regions.
26 February 2020 7
Modified Fick’s First Law is applicable
where, PM = permeability coefficient

J = diffusion flux of gas through the membrane.
[(cm3STP/(cm2-s)]
Δx = Thickness of Membrane
ΔP = Pressure gradient
For small molecules (O2, CO2, N2),
PM= D*S
D = Diffusion coefficient (D)
S = Solubility of the diffusing species in the polymer
26 February 2020 8

increasing T.
 Qd 
D  Do exp  
 RT 

26 February 2020 33
Mechanical Behavior of Materials
Chapter 9
2/26/2020 10
Why study of Mechanical Properties
• We all know that things break.
• Study mechanical properties to better
understand why and how things break.
• Analyze the properties of materials to assess
strength, ductility, and fatigue under
different conditions.
• Understanding how different factors affects
materials helps engineers estimate how long
things will last and identify early signs of
impending failure.
Why Study Mechanical Properties
• A familiar example is the number of kilometers

tires are expected to last.
• Would you develop at 60000 k.m. tire or 20000
k.m tire?
• The material used to construct a 60,000 k.m.
tire might cost more, but it is a good
investment unless it costs more than three
times the 20,000 k.m tire.

Solution
D transform data ln D
Temp = T 1/T
Qd 1 Qd  1
lnD2  lnD0    and lnD1  lnD0   
R  T2  R  T1 
D2 Qd  1 1
 lnD2  lnD1  ln    
D1 R  T2 T1 
26 February 2020 36
Common States of Stress
• Simple tension: cable
F F
A o = cross sectional
area (when unloaded)
F
s s s
Ao
• Torsion (a form of shear): drive shaft
M Fs Ao
Ac t
Fs
t 
M Ao
2R 14
COMMON STRESS STATES
• Simple compression:
Ao
Canyon Bridge, Los Alamos, NM

(photo courtesy P.M. Anderson)
F Note: compressive
Balanced Rock, Arches s structure member
National Park
(photo courtesy P.M. Anderson)
Ao (s < 0 here).
15
OTHER COMMON STRESS STATES
• Bi-axial tension: • Hydrostatic compression:
Pressurized tank Fish under water
16
Thought for the Day
Electrochromic Glass
2/26/2020 2
Poisson’s Ratio
• Define as ratio of Lateral to Longitudinal Strain

 L

metals:  ~ 0.33
ceramics: ~0.25
polymers: ~0.40
Can Poisson’s Ratio be Negative for any materials??

18
Negative Poisson’s Ratio Material
Auxetics are structures or materials that have a negative Poisson's

ratio. This occurs due to their particular internal structure and the
way this deforms when the sample is uniaxially loaded
19
Linear Elastic Behavior
• Modulus of Elasticity, E: (also known as Young's modulus)
s
• Hooke's Law: E F
s=E 1 
Units: Linear-
E: [GPa] or [psi] elastic
F
simple
tension
test
10
26 February 2020 5
Relation between Young and Bulk Modulus
What is εx for this cube subjected
to stress in the x,y and z
directions?
22
2/26/2020
Volumetric Strain Vs Linear Strain
Let a cuboid of material having initial sides of Length x, y and z.
If under some load system, the sides changes in length by dx, dy,
and dz then the new volume ( x + dx ) ( y + dy ) ( z +dz )
New volume = xyz + yzdx + xzdy + xydz

Original volume = xyz
Change in volume = yzdx +xzdy + xydz
Volumetric strain = ( yzdx +xzdy + xydz ) / xyz = εx+ ε y+ ε z
Neglecting the products of epsilon's since the strains are

sufficiently small.
23
2/26/2020
Solution
Assuming BCC

26 February 2020 7
CHE F243
Krishna Etika
Pilani Campus
Thought of the Day
Tuning Shape Tunes Mechanical
Properties
2
Recap
3
2/26/2020
Chapter 9
2/26/2020 4
Engineering Stress
• Tensile stress, s: • Shear stress, t:
Ft Ft F
Area, A
Area, A Fs
Fs
Ft Ft Fs
s t Ft
Ao Ao F
original area
before loading Stress has units:
N/m2 or lb/in2

Common States of Stress
• Simple tension: cable
F F
A o = cross sectional
area (when unloaded)
F
s s s
Ao
• Torsion (a form of shear): drive shaft
M Fs Ao
Ac t
Fs
t 
M Ao
2R 6
Engineering Strain
• Tensile strain: • Lateral strain:
/2
L
  wo
Lo L 
Lo wo
/2
• Shear strain: L/2 L/2 Strain is always
dimensionless.
/2
 = tan 
/2 -
/2 /2
Poisson’s Ratio
• Define as ratio of Lateral to Longitudinal Strain

 L

metals:  ~ 0.33
ceramics: ~0.25
polymers: ~0.40
Can Poisson’s Ratio be Negative for any materials??

8
Other Elastic Properties
• Elastic Shear modulus, t M
G:
G
1  simple
t=G torsion
test
M
• Elastic Bulk modulus, P P
K:
V V P P
P= K
- Vo Pressure test:
Vo -K Initial vol =Vo.
1 Vol change = V
• Special relations for isotropic materials:
E E
G K
2(1  ) 3(1  2)
Lecture 18
10
Deformation
• Material deforms under external stress (force/area).
• Deformation: Change in shape or size of a material
under the application of an external stress.
Deformation
Temporary Permanent
Elastic Anelastic Plastic Viscoelastic

Fully recoverable, Fully recoverable, Not recoverable, Elastic + Plastic,
Time independent. Time dependent. Time independent. Time dependent.
Elastic Deformation
1. Initial 2. Small load 3. Unload
bonds
stretch
return to
initial

Stress- Strain Diagram Strain-time Diagram
F 
F
s Linear- F Linear-
elastic elastic
Elastic means reversible!
Non-Linear- Non-Linear-
elastic elastic
 t
Plastic Deformation
bonds
stretch planes
& planes still
shear sheared
Elastic+Plastic
s
tensile stress, at larger stress
elastic + plasticplastic
F Elastic
initially
permanent (plastic)
after load is removed
Plastic means permanent! 

engineering strain,
p
plastic strain

Anelastic Deformation
Recoverable deformation that occurs as a function of
time is called Anelastic deformation.
Relaxation process occurring inside the material leads to
time dependence. t = Relaxation timer
Stress Stress
t<<tr
ttr x = 1- exp[-t/tr]
x= fraction of the
completed relaxation
process.
t>>tr
Strain Strain
Relaxation time is defined as the time required for 63% completion of the
relaxation process
Viscoelastic Deformation
• In viscoelastic deformation, both elastic and plastic
deformation occur simultaneously.

Problem
A tensile stress is to be applied along the long

axis of a cylindrical brass rod that has a
diameter of 10mm. Determine the magnitude
of the load required to produce a 2.5x10-3 mm
change in diameter if the deformation is
considered elastic.
16
Stress Strain Testing
• Typical tensile specimen
load cell
• Typical tensile
specimen test machine
extensometer
moving cross head
gauge(portion of sample with

=
lengthreduced cross section)
• Other types of tests:

--compression: brittle
materials (e.g., concrete)
--torsion: cylindrical tubes,
shafts.
Stress Strain Diagram - Metals
TS We can
determine
various
engineering
parameters
stress
related to
mechanical
performance of a
Typical response of a metal material from its
stress-strain
diagram.
strain
True Stress-Strain Diagram
σT=KϵTn n= Strain hardening exponent
Relation between true to engineering stress and strain

σT= σ(1+ϵ) ϵT= ln(1+ϵ) 19
Yeild Strength (sy)
• Stress at which noticeable plastic
deformation has occurred.
tensile stress, s
sy
When p = 0.002
engineering strain, 
 p = 0.002
Yeild Strength (sy)
• Some steels exhibit Yield point phenomena
two yield points exists
Why this happens?

•Due to the presence of Carbon as
solute in mild steels.
•Pins the dislocation till upper yield
point.
21
Yield Strength Comparison
s y(ceramics)
>> s y(metals)
>> s y(polymers)
Room T values

Tensile Strength, TS
The maximum possible engineering stress that an material can
experience. Stress corresponding to the highest point in the stress-
strain diagram.
TS
engineering
stress
Typical response of a metal
strain
Introduction
What is a crystal defect
If we assume a perfect crystal structure containing
pure elements, then anything that deviated from
this concept or intruded in this uniform
homogeneity would be an imperfection/defect.
1. There are no perfect crystals.
2. Many material properties are improved by
the presence of imperfections and
deliberately modified (alloying and doping).
(Defects are not always bad!!!)
26 February 2020 24
CHE F243
Krishna Etika
Pilani Campus
Thought of the Day
Themochromic Paint
2
Recap
3
2/26/2020
Chapter 9
2/26/2020 4
Stress Strain Testing
• Typical tensile specimen
load cell
• Typical tensile
specimen test machine
extensometer
moving cross head
gauge(portion of sample with

=
lengthreduced cross section)
• Other types of tests:

--compression: brittle
materials (e.g., concrete)
--torsion: cylindrical tubes,
shafts.
Stress Strain Diagram - Metals
TS We can
determine
various
engineering
parameters
stress
related to
mechanical
performance of a
Typical response of a metal material from its
stress-strain
diagram.
strain
True Stress-Strain Diagram
σT=KϵTn n= Strain hardening exponent
Relation between true to engineering stress and strain

σT= σ(1+ϵ) ϵT= ln(1+ϵ) 7
Yeild Strength (y)
• Stress at which noticeable plastic
deformation has occurred.
tensile stress, 
y
When p = 0.002
engineering strain, 
 p = 0.002
Tensile Strength, TS
The maximum possible engineering stress that an material can
experience. Stress corresponding to the highest point in the stress-
strain diagram.
TS
engineering
stress
strain
CHE F243
Krishna Etika
BITS Pilani
Pilani Campus
Lecture 19
11
2/26/2020
Ductility
• It can defined as the plastic strain at failure.
• measured by % Area reduction or % Elongation
smaller %EL
Engineering (brittle if %EL<5%)
tensile
A
stress,  larger %EL Lo o Af Lf
(ductile if
%EL>5%)
Engineering tensile strain, 

• Another ductility measure:
L f  Lo Ao  A f
%EL  x100 %AR  x100
Lo Ao
Problem
• A cylindrical specimen of steel having an
original diameter of 12.8 mm (0.505 in.) is
tensile tested to fracture and found to have an
engineering fracture strength of 460 MPa
(67,000 psi). If its cross-sectional diameter at
fracture is 10.7 mm (0.422 in.), determine:
(a) Ductility (b) The true stress at fracture
13
Problem
14
Question?
• Why in the engineering stress strain diagram,

the engineering stress decreases after tensile
strength is reached? Why?
TS
engineering
stress
strain
15
Question
• Do tensile and compression test yeild similar

results?
16
Chapter 5
26 February 2020 4
Toughness
• It can be defined as the energy required to
break a unit volume of the material.
• It is equal to the area under the stress strain
diagram.

Toughness
• Another definition of Toughness is: Amount of
energy absorbed by the material to
“plastically” deform.
• In reality, toughness is the area under the true

stress-strain curve, however, engineers use
area under the engineering stress-strain curve
till fracture as a measure.
19
Toughness
Toughness
20
Lecture 14

Hardness
Hardness is a measure of how resistant solid matter is to various
kinds of permanent shape change when a compressive force is
applied
Large hardness values mean that material has :

-- more resistance to plastic deformation or cracking in
compression.
--better wear properties.
apply known forcemeasure size
e.g., (1 to 1000g) of indent after
10mm sphere removing load
Smaller indents
D d mean larger
hardness.
Brinell Hardness Test
23
Other Hardness Tests
24
CHE F243
Krishna Etika
Pilani Campus
Will Cu and Ni form a Substitutional solid solution???
Crystal electroneg r (nm)

Structure
Ni FCC 1.9 0.1246
Cu FCC 1.8 0.1278

Recap
3
2/26/2020
Alloy Compositions
m1
m1  m2
n m1
'
1 x 100
n m1  n m 2
26 February 2020 14
Lecture 19
5
2/26/2020
Ductility
• It can defined as the plastic strain at failure.
• measured by % Area reduction or % Elongation
smaller %EL
Engineering (brittle if %EL<5%)
tensile
A
stress,  larger %EL Lo o Af Lf
(ductile if
%EL>5%)
Engineering tensile strain, 

• Another ductility measure:
L f  Lo Ao  A f
%EL  x100 %AR  x100
Lo Ao
Question
• Do tensile and compression test yield similar

results?
7
Elastic Strain Recovery or Strain Hardening
8
Toughness
• It can be defined as the energy required to
break a unit volume of the material.
• It is equal to the area under the stress strain
diagram.

Resilience
• Ability of a material to store energy
– Energy stored in elastic region
y
Ur   d
0
If we assume a linear stress-

strain curve this simplifies to
1
U r @ y  y
2
10
EDGE DISLOCATION
 extra half-plane of atoms inserted in a crystal structure; the

edge of the plane terminates within the crystal.
 Around the dislocation line there is some localized
distortion.
 b perpendicular () to dislocation line
Burgers vector, b: measure of lattice distortion

Chapter 11
Failure in Materials
12
Fracture
Type of failure where the material breaks due to stress,
at temperatures below the melting point.
Fracture takes place in two stages:
(i) initial formation of crack and
(ii) spreading of crack.
Depending upon the type of materials, the applied
load, state of stress and temperature metals have
different types of fracture.
Types of fracture in materials
 Brittle Fracture
 Ductile Fracture
Ductile Fracture
-slow propagation of crack with considerable
plastic deformation.
There are three successive events involved in
a ductile fracture.
– Necking:The specimen begins necking and
minute cavities form in the necked region.
– Crack Formation: small micro cracks are formed

at the centre of the specimen due to the
combination of dislocations.
– Crack growth: Finally these cracks grow out

ward to the surface of the specimen
Ductile Fracture

Mixed Dislocation
• Contains both edge and screw

dislocation.
26 February 2020 23
Brittle Vs Ductile Fracture
A. Very ductile: soft metals

(e.g. Pb, Au) at room T,
polymers, glasses at high T
B. Moderately ductile
fracture
typical for metals
A. Brittle fracture: ceramics,
cold metals,
• Ductile Ductile: A B Brittle:
C
fracture is usually warning before No
desirable! fracture warning

Ductile Vs Brittle Fracture
cup-and-cone fracture brittle fracture
18
Ductile Vs Brittle Fracture
Brittle Fracture Ductile Fracture
19
Principles of Fracture Mechanics
• The measure fracture strength for most brittle
materials are significantly lower than the
predicted values.
• This is attributed to the presence of

microscopic flaws or “Cracks” on the surface
and within the body of the material.
20
Flaws are Stress Concentrators!
1/ 2 t = radius of curvature
a  o = applied stress
 m  2o    K t o m = stress at crack tip
 t  Kt = Stress Concentration Factor
21
Fracture Toughness
A property that is a measure of a materials
resistance to brittle fracture when a crack is present.
Kc = Yc a
Y = 1.1
Kc = Fracture toughness, MPa√(m)

Y = dimensionless parameter depends on crack geometry
and manner of loading.
Y=1
σC= critical stress for crack propagation
22
Re-Cap
2/26/2020 3
Let’s Review
• What is the difference between Stress
Concentration factor (Kt) and Fracture
Toughness (KIc)
• If a material has low value of KIc, what does it
mean?
• Which one will have lower Klc values? Metals
or ceramics?
24
K1C comparison
25
CHE F243
Krishna Etika
Pilani Campus
Thought of the Day
LIGHT TRANSMITTING CONCRETE
2
Diffusion Mechanism
Vacancy Diffusion:

26 February 2020 10
Chapter 11
Failure in Materials
4
Fracture
Type of failure where the material breaks due to stress,
at temperatures below the melting point.
Fracture takes place in two stages:
(i) initial formation of crack and
(ii) spreading of crack.
Depending upon the type of materials, the applied
load, state of stress and temperature metals have
different types of fracture.
Types of fracture in materials
 Brittle Fracture
 Ductile Fracture
Brittle Vs Ductile Fracture
A. Very ductile: soft metals

(e.g. Pb, Au) at room T,
polymers, glasses at high T
B. Moderately ductile
fracture
typical for metals
A. Brittle fracture: ceramics,
cold metals,
• Ductile Ductile: A B Brittle:
C
fracture is usually warning before No
desirable! fracture warning

Principles of Fracture Mechanics
• The measure fracture strength for most brittle
materials are significantly lower than the
predicted values.
• This is attributed to the presence of

microscopic flaws or “Cracks” on the surface
and within the body of the material.
7
Flaws are Stress Concentrators!
1/ 2 t = radius of curvature
a  so = applied stress
s m  2so    K t so sm = stress at crack tip
 t  Kt = Stress Concentration Factor
8
The concentration of diffusing species is a function

of both time and position C = C(x,t)
In this case Fick’s Second Law is used
C  C 2
D
t x 2
26 February 2020 16
Modes of Crack Propagation
• Mode I: (a)
• KIc is the “plane strain” fracture toughness
• Mode I type of loading is the most common
10
K1C comparison
11
Lecture 21-22
12
2/26/2020
Error Function
26 February 2020 19
Solution
Kc = Ysc a
What is the missing in the problem???
14
Solution Hint
• Y is specific to the crack geometry. It differs from
crack to crack.
• Only if plate have semi-infinite width with edge
crack, we get this Y = 1.1
• Only if we have plate of infinite width with Y = 1

through thickness crack
15
Solution
1st Determine the Y parameter applicable for this case
Plug the Y parameter in the 2nd case and find K1c
Compare K1c in both cases and comment 16

Solution
To solve for the temperature at Qd
which D has above value, we T 
use a rearranged form of R(lnDo  lnD )
Equation (6.9a);
from Table 6.2, for diffusion of C in FCC Fe

Do = 2.3 x 10-5 m2/s Qd = 148,000 J/mol
 148,000 J/mol
T 
(8.314 J/mol - K)(ln 2.3 x10 5 m2 /s  ln 2.6 x10 11 m2 /s)
T = 1300K = 1027°C
26 February 2020 23
IZOT TESTING VIDEO
18
Impact Testing Results Vs Temp
More Shiny or grainy surface More fibrous or dull surface

Possible Brittle Fracture Possible ductile Fracture 19
Ductile to Brittle Transition
• Increasing temperature...
--increases %EL and K1c
• Ductile-to-Brittle Transition Temperature (DBTT)...
FCC metals (e.g., Cu, Ni)
Impact Energy
BCC metals (e.g., iron at T < 914°C)

polymers
Brittle More Ductile
High strength materials
Temperature
Ductile-to-brittle
transition temperature 20
Stay Above The DBTT!
Titanic
• Problem: Used a type of steel with a DBTT ~ Room temp.

21
Fatigue
• Under fluctuating / cyclic

stresses, failure can occur at
lower loads than under a
static load.
Cyclic Stress Cycle

• 90% of all failures of metallic
structures (bridges, aircraft, Stress amplitude
machine components, etc.) S = (smax - smin) / 2
Mean Stress
• Fatigue failure is brittle-like – s m= (smax + smin) / 2
– even in normally ductile
Stress Ratio
materials. Thus sudden and
catastrophic! R = smin/ smax
Fatigue: S-N Curve
Plotted between S (stress) vs. N (number of
cycles to failure)
Most alloys: S decreases
with N.
Fatigue strength: Stress at
which fracture occurs after
specified number of cycles
(e.g. 107)
Fatigue life: Number of
cycles to fail at specified
stress level
Fatigue S-N Curve Ferrous Alloys
Fatigue limit/Endurance :
demonstrated by some Fe
and Ti (i.e., ferrous)alloys)
S—N curve becomes

horizontal at large N
Defined as Stress amplitude
below which the material
never fails, no matter how
large the number of cycles
is
Problem
A 15.2 mm (0.60 in.) diameter cylindrical rod

fabricated from a 2014-T6 aluminum alloy
(Figure 11.34) is subjected to a repeated
tension compression load cycling along its
axis. Compute the maximum and minimum
loads that will be applied to yield a fatigue life
of 1x108cycles. The data were taken for a
mean stress of 35 MPa (5000 psi).
25
CHE F243
Krishna Etika
BITS Pilani
Pilani Campus

Creep
Time-dependent deformation due to constant load
at high temperature
1. Instantaneous deformation, mainly Stages of creep
elastic.
2. Primary/transient creep. Slope of
strain vs. time decreases with time:
strain-hardening
3. Secondary/steady-state creep. Rate
of straining constant: work-
hardening and recovery.
4. Tertiary. Rapidly accelerating strain
rate up to failure: formation of
internal cracks, voids, necking, etc. Creep Curve
Creep
28
Creep: Stress and Temperature effects
Creep in metals becomes important at Temp > 0.4 Tm
With increasing stress or temperature:

 The instantaneous strain increases
 The steady-state creep rate increases
 The time to rupture decreases

Creep Testing
Furnace
30
Steady State Diffusion
Rate of diffusion independent of time

dC
Flux proportional to concentration gradient =
dx
Fick’s first law of diffusion
C1 C1
dC
C2 C2 J  D
dx
x1 x2
x
D  diffusion coefficient
dC C C2  C1
if linear  
dx x x2  x1
26 February 2020 3
Stress and Temp Effects
Empirical relationships have been developed in which
the steady-state creep rate as a function of stress and
temperature is expressed
when the influence of temperature is included
where K2 and Qc are constants; Qc is termed the

activation energy for creep
32
Creep Test Data
33
Fick’s second Law
C  x , t   Co  x 
 1  erf  
Cs  Co  2 Dt 
C(x,t) = Conc. at point x at time t CS

erf (z) = error function
2 z C(x,t)

y 2
 e dy
 0
Co
erf(z) values are given in Table 6.1
Take Home Assignment:

Solve the Fick’s second law of diffusion for semi5 infinite solid
26 February 2020
BITSPilani,
BITS Pilani,Pilani
PilaniCampus
Campus
Solution
• If we know the steady state creep rate, then one

can determine the stress using a standard chart
shown below.
• How to determine the steady state creep rate?

• Steady state creep = Total creep – (Inst +
primary) Creep
35
Solution
• Figure 11.31 in your text book is incorrect for

this problem. Use the figure below as the
correct figure
36
Diffusion mechanism : analogous to

interstitial diffusion in metals.
diffusive movements occur through small
voids between polymer chains
Rates of diffusion are greater through

amorphous regions than through
crystalline regions.
26 February 2020 7
Larson Miller Parameter
• The rupture lifetime of a given material measured

at a specific stress levels will vary with temperature
such that Larson Millers Parameter remains
constant.
T (C + log tr) Larson Miller Parameter
38
Stress Vs L-M Parameter
39
Problem 11.D4
Consider an S-590 iron component (Figure
11.32) that is subjected to a stress of 55 MPa. At
what temperature will the rupture lifetime be
200 h?
Solution: Read L-M parameter for the specified

stress level.
Use L-M definition to calculate the

Temperature
40
Reading Assignment
Fracture in Polymers
Chapter 14.5-14.9
41
Why study of Mechanical Properties
• We all know that things break.
• Study mechanical properties to better
understand why and how things break.
• Analyze the properties of materials to assess
strength, ductility, and fatigue under
different conditions.
• Understanding how different factors affects
materials helps engineers estimate how long
things will last and identify early signs of
impending failure.

Mid Sem PDF

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CHE F243

Materials Science and Engineering

Course No: CHE F243

☼ Got my Ph.D. from Texas A&M University in Materials

(~2 m yr ago) (~5k yr ago) (~2 k yr ago)

Silicon Age (60 yr ago) Now? Polymer Age(???) 2

Guess what the wall paper is made of?

Materials Science and Engineering

Materials Science Materials Engineering

Investigation of Using the

Structure: It is the arrangement of a Property: It is the response to an external

Processing Structure Properties Applications

Exactly same chemical composition – All discs are Al2O3 (Alumina)

Properties depend on structure

Properties: mechanical, electrical,

2. Properties Identify candidate Material(s)

Processing: changes structure and overall shape

BHN - Brinell hardness number

Guess what the wall paper is made of?

• Adding “impurity” atoms to Cu increases resistivity.

Resistance to Fracture (mechanical)

A crystal is defined as a lattice with

Resistance to Fracture (mechanical)

A two-dimensional Bravais lattice can be created

More than one unit cell possible for a crystal

a, b, and c are the lattice constants

A crystal is defined as a lattice with

– Where, a1, a2 and a3 are called as the primitive

More than one unit cell possible for a crystal

a, b, and c are the lattice constants

1. Vector repositioned (if necessary) to pass

ex: 1, 0, ½ => 2, 0, 1 => [ 201 ]

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

families of directions <uvw>

A two-dimensional Bravais lattice can be created

Adapted from Fig. 3.10,

Family of Planes {hkl}

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

• In hexagonal unit cells the same idea is used

4. Miller-Bravais Indices (1011) a1

Adapted from Fig. 3.8(b),

Dense, ordered packed structures tend to have lower energies.

"Amorphous" = Noncrystalline noncrystalline SiO2

1. Vector repositioned (if necessary) to pass

ex: 1, 0, ½ => 2, 0, 1 => [ 201 ]

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

families of directions <uvw>

"Amorphous" = Noncrystalline noncrystalline SiO2

-Typically, only one element is present, so all atomic radii

• Have the simplest crystal structures.

Rare - due to low packing density (only Po has this structure)

Atoms touch each other along face diagonals.

What is a coordination Number (C.N.) ???

How many atoms/unit cell???

1 atoms/unit cell: 8 corners x 1/8 = SC

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

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

Volume of atoms in unit cell*

close-packed directions unit cell

 APF for a body-centered cubic structure = 0.68

• APF for a face-centered cubic structure = 0.74

• For [110] direction in FCC

• Linear density and linear packing