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Materials Science and Engineering I

Manolis Doxastakis
University of Houston

Fall 2013

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Outline
1

Introduction

Atomic structure and interatomic bonding

The structure of crystalline solids

Imperfections in solids

Diffusion

Mechanical properties of metals

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Introduction

Materials drive our society


Development of many technologies associated with the accessibility of suitable
materials
Stone Age ( 2.5 million BC)
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handmade tools and objects found in nature - sharpened stone,


bow and arrow, handaxe
hunting and gathering economy
mobile tribes

Bronze Age ( 3500 BC)


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copper and bronze tools, potters wheel


agriculture, cattle breeding, craft trade
farmsteads

Iron Age ( 1000 BC)


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iron tools
formation of cities

Now? (Silicon Age?,Polymer Age?)


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Introduction

What is materials science and engineering?


Structure (microscopic, macroscopic)
Property (mechanical, electrical, thermal, magnetic, optical, and
deteriorative)
Processing
Performance

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Introduction

Materials Science and Engineering

Example

Optical properties of
thin disk speciments
of aluminum oxide

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Introduction

Classification of Materials

Basic classification of solid materials


Metals
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I
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large number of free electrons


electrically conductive
thermally conductive
non-transparent to light
polished surface is mirror-like
often strong, deformable
variety of chemical reactivities, melting points

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Introduction

Classification of Materials

Basic classification of solid materials


Ceramics
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usually oxides, nitrides, carbides


usually low electrical conductivity (sometimes semiconductors)
usually poor thermal conductivity (exception:diamond)
hard and brittle

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Introduction

Classification of Materials

Basic classification of solid materials


Polymers
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usually complex organic structures


low density
usually electrically insulating (can also be conducting and
semiconducting)

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Introduction

Classification of Materials

Density

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Introduction

Classification of Materials

Stiffness

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Introduction

Classification of Materials

Strength

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Introduction

Classification of Materials

Resistance to fracture

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Introduction

Classification of Materials

Electrical conductivity

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Introduction

Classification of Materials

Advanced materials
Semiconductors
I

slight electrical conductors (trace, intentional impurities, called


dopants, drastically increase conductivity)

Composites
I

mixture of 2 or more materials from the above list (get the best of
the properties of both and/or new properties)
e.g. fiberglass (epoxy (polymer) + glass fibers)

Bio-materials
I

usually means biologically compatible materials (materials that can


be placed in the body)
can be made of any of the above materials

Nano-materials
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material composed of small particles (1 to 100 nm size) that have


properties that are different from that of the bulk material (e.g.
small Si particles emit light when current is passed through them.
Bulk Si does not)

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Introduction

Classification of Materials

All solid materials are either:


Crystalline
I

single crystal - all the atoms in object are in a periodic, coherent


arrangement. [e.g. Si wafer, Si Transmission Electron Micrograph]
polycrystalline - object composed of many single crystals with
different orientations. [e.g. poly-Si, Nb-Hf-W plate. Boundaries
between crystallites called grain boundaries]
nanocrystalline - polycrystalline, only crystallites so small (1 to 10
nm dia.) that they have different properties than larger crystallites.

Amorphous
I

atoms have no long range order. Example: glass

Composites
I

composed of combinations of crystalline and/or amorphous,


different materials. Example: steel reinforced concrete.

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Introduction

The materials selection process

The materials selection process


1

Pick Application Determine required Properties


(mechanical, electrical, thermal, magnetic, optical, deteriorative)
Properties Identify candidate Material(s)
(structure, composition)
Material Identify required Processing
(casting, vapor deposition, doping forming, joining, annealing)

Example
Electrical Resistivity of Copper:
Adding impurity atoms to
Cu increases resistivity
Deforming Cu increases
resistivity

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Atomic structure and interatomic bonding

Atomic structure - fundamental concepts

Atomic structure - fundamental concepts


atom
(electrons - 9.111031 kg, protons, neutrons - 1.671027 kg)
atomic number
= # of protons in nucleus of atom = # of electrons of neutral species
A [=] atomic mass unit = amu = 1/12 mass of 12 C
Atomic wt = wt of 6.023 x 1023 molecules or atoms
(1 amu/atom = 1 g/mol)
Models for atom
Bohr Model:
electrons orbit the
(+)-charged nucleus in discrete
orbits with quantized energy.
Too simplistic. Only works well
for principal energy levels of
H-atom
Manolis Doxastakis (University of Houston)

Wave mechanical model:


Electron wave clouds exist at discrete
energies. Electron positions can only be
described by probabilities. Solutions to
wave-mechanic equations yield
quantum numbers that describe the
energies of the electrons.
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Atomic structure and interatomic bonding

Electrons in atoms

Bohr model:

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Atomic structure and interatomic bonding

Electrons in atoms

(a) Bohr and (b) wave-mechanical model

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Atomic structure and interatomic bonding

Quantum numbers

Quantum numbers

Electrons have wavelike and particulate properties.


Electrons are in orbitals defined by a probability.
Each orbital at discrete energy level determined by quantum
numbers.
Quantum Number
n = principal (energy level-shell)
l = subsidiary (orbitals)
ml = magnetic
ms = spin

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Designation
K, L, M, N, O (1, 2, 3, etc.)
s, p, d, f (0, 1, 2, 3,. . ., n-1)
1, 3, 5, 7 (-l to +l)
1
1
2, 2

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Atomic structure and interatomic bonding

Quantum numbers

principal quantum number, n (or shell: K, L, M, . . .)


n = 1 (K)
n = 2 (L)
n = 3 (M)
n = 4 (N)

increasing distance
from nucleus
increasing orbital
energy

increasing energy
to remove electron
from atom (i.e. to form
ion )

sub-shell quantum number, l (or s, p, d, . . . orbitals)


(l = 0, 1, . . ., n-1, l = 0 s, l = 1 p, l = 2 d, l = 3 f )

magnetic sub-levels (or sub-sub-shell) quantum number, ml

(ml = 0, 1, . . . , l. Therefore 2l + 1 mag. sub-levels per sub-shell)

l=0

ml = 0

l=1

ml = 0, 1

l=2

ml = 0, 1, 2

no magnetic field
(equal energy)

px , py , px

magnetic field
(energies split)

electron spin quantum number, ms = +1/2 , -1/2, for each ml


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Atomic structure and interatomic bonding

Quantum numbers

Electron quantum number notation:


n, l, ml , (ms )
e.g. 2 1 1 (1/2)
Pauli exclusion principal: no 2 electrons in an atom can have the
same quantum numbers.
Hundss first rule: maximize the number of ml levels:

Orbitals fill from the bottom up (1s, 2s, 2p, . . .)


Highest unfilled shell called valence shell
Lower filled shells called core levels
Orbitals often hybridize, such as C 2s2 2p2 orbitals become sp3
where all 4 orbitals are equivalent. Forms tetrahedral (109
angles).
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Atomic structure and interatomic bonding

Electron configuration

Electron energy states


Electrons have discrete energy states
tend to occupy lowest available energy state

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Atomic structure and interatomic bonding

Electron configuration

Most elements: electron configuration not stable

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


Valence electrons determine all of the following properties:
Chemical, Electrical, Thermal, Optical
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Atomic structure and interatomic bonding

Electron configuration

Valence electrons those in unfilled shells


Filled shells more stable
Valence electrons are most available for bonding and tend to
control the chemical properties
Example
C (atomic number = 6)

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Atomic structure and interatomic bonding

Electron configuration

Example
Fe - atomic number = 26

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1s2 2s2 2p6 3s2 3p6 3d6 4s2

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Atomic structure and interatomic bonding

Periodic table

The Periodic Table


columns similar valence structure

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Atomic structure and interatomic bonding

Periodic table

electronegativity ranges from 0.7 to 4.0


large values tendency to acquire electrons

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Atomic structure and interatomic bonding

Atomic bonding in solids

Ionic bonding
Ionic bond

metal

donates electrons

nonmetal

accepts electrons

Dissimilar electronegativities
Example
Mg

1s2 2s2 2p6 3s2

1s2 2s2 2p4

1s2 2s2 2p6


[Ne]

MgO:

Mg

1s2 2s2 2p6


[Ne]

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Atomic structure and interatomic bonding

Atomic bonding in solids

Ionic bonding
Occurs between + and - ions (requires electron transfer)
Net charge remains zero.
All (+) ions surrounded by (-) ions and vice versa.

Example

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Atomic structure and interatomic bonding

Atomic bonding in solids

Isolated ion pair

Net force FN sum of both


attractive and repulsive
components:
FN = FA + FR
Net potential
energy EN
R
(E = Fdr F = dE
dr ):
EN = EA + ER
Z r
Z r
=
FA dr +
FR dr

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Atomic structure and interatomic bonding

Atomic bonding in solids

Isolated ion pair


Attractive energy:
A
EA =
r
z1 z2 e2
where A =
40
z1 , z2 : charges of (+) and
(-) ion (1, 2, . . .)
e : elementary charge =
1.602 1019 C
0 : permitivity of free
space = 8.85 1012 F/m

Repulsive energy:
B
ER = n
r
B: empirical constant
n: empirical constant
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Atomic structure and interatomic bonding

Atomic bonding in solids

Isolated ion pair


r0 is the equilibrium
bond length:
dEN
=0
F=
dr


d
A B
+ n
=0
dr
r r r=r0
(n+1)

Ar2
nBr0
=0
0
1
  1n
A
r0 =
nB
E0 is the minimum
potential energy:
A B
E0 = + n
r0 r0
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Atomic structure and interatomic bonding

Atomic bonding in solids

Example
Calculate the attractive force between K+ and O2 at r = 1.5 nm

F=



d
A
A
dEA
z1 z2 e2
=

= 2 F=
dr
dr
r
r
40 r2

F=

2
(1)(2)(1.6 1019 C)2
10 C
=
2.05

10

Fm
4(8.85 1012 F/m)(1.5 109 m)2

F = 2.05 1010 N

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Atomic structure and interatomic bonding

Atomic bonding in solids

Covalent bonding

2 electrons are shared in single


bonds

Example

Unlike ionic bonding, covalent


bonds are directional
With the exception of single
element solids, all bonds are a
combination of ionic and covalent.
% ionic character =
{1 exp[(0.25)(XA XB )2 )} 100

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Atomic structure and interatomic bonding

Atomic bonding in solids

Metallic Bonding
Example

Electrons are not bound to a


particular atom
Good conductors of both
electricity and heat

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Atomic structure and interatomic bonding

Atomic bonding in solids

Secondary Bonding or van der Waals


Between atoms or molecules
Permanent Dipole Bonds

Example

Polar Molecule-Induced Dipole Bonds

Fluctuating Induced Dipole Bonds

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The structure of crystalline solids

Introduction

The structure of crystalline solids


The properties of solid materials are related to how atoms pack
(carbon graphite, diamond)
Non dense random packing

Dense ordered packing

Dense, ordered packed structures tend to have lower energies.


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The structure of crystalline solids

Introduction

Materials and packing


Crystalline materials:
atoms pack in periodic, 3D
arrays
typical of:
I
I
I

Example

metals
many ceramics
some polymers

Noncrystalline materials. . .
atoms have no periodic
packing
occurs for:
I
I

complex structures
rapid cooling

Amorphous=Noncrystalline
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The structure of crystalline solids

Introduction

Unit cell
Smallest repetitive volume which contains the complete lattice
pattern of a crystal
When translated 1 unit cell distance along each edge will create
the complete crystal.

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The structure of crystalline solids

Metallic crystal structures

Metallic crystal structures


Tend to be densely packed
Reasons for dense packing:
I

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.
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The structure of crystalline solids

Metallic crystal structures

Simple cubic structure (SC)


2D:

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

Read more:
http://mathworld.wolfram.com/CirclePacking.html
http://en.wikipedia.org/wiki/Sphere_packing
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The structure of crystalline solids

Metallic crystal structures

Simple cubic structure (SC)


Coordination number=6
(# nearest neighbors)

1 Atom per unit cell (8 1/8)

Definition
Atomic Packing Factor (APF) =

Volume of atoms in unit cell


Volume of unit cell

For SC: APF = (atoms/cell) (volume/atom) / (volume/unit cell) =


= 1 43 (0.5a)3 /a3 = 0.52
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The structure of crystalline solids

Metallic crystal structures

Simple cubic structure (SC)


Coordination number=6
(# nearest neighbors)

1 Atom per unit cell (8 1/8)

Definition
Atomic Packing Factor (APF) =

Volume of atoms in unit cell


Volume of unit cell

For SC: APF = (atoms/cell) (volume/atom) / (volume/unit cell) =


= 1 34 (0.5a)3 /a3 = 0.52
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The structure of crystalline solids

Metallic crystal structures

Simple cubic structure (SC)


Coordination number=6
(# nearest neighbors)

1 Atom per unit cell (8 1/8)

Definition
Atomic Packing Factor (APF) =

Volume of atoms in unit cell


Volume of unit cell

For SC: APF = (atoms/cell) (volume/atom) / (volume/unit cell) =


= 1 34 (0.5a)3 /a3 = 0.52
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The structure of crystalline solids

Metallic crystal structures

Three crystal structures are found for most of the common metals:
face-centered cubic (FCC)
body-centered cubic (BCC)
hexagonal close-packed (HCP)

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The structure of crystalline solids

Metallic crystal structures

Face Centered Cubic Structure (FCC)

e.g. Al, Cu, Au, Pb, Ni, Pt, Ag


Coordination # = 12
4 atoms/unit cell: 6 face 1/2
+ 8 corners 1/8

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The structure of crystalline solids

Metallic crystal structures

Atomic packing factor: FCC

a2 + a2 = (4R)2 a = 2R 2

Unit cell volume Vc = a3 = 16R3 2


Volume of atoms in unit cell
Volume of unit cell

APF=4 34 R3 /(16R3 2) = 0.74


APF =

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The structure of crystalline solids

Metallic crystal structures

Body Centered Cubic Structure (BCC)

e.g.Cr, W, Fe, Tantalum, Molybdenum


Coordination # = 8
2 atoms/unit cell: 1 center + 8 corners 1/8
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The structure of crystalline solids

Metallic crystal structures

Atomic packing factor: BCC

4R =

3a

Volume of atoms in unit cell


Volume of unit cell

APF=2 34 ( 3a/4)3 /a3 = 0.68

APF =

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The structure of crystalline solids

Metallic crystal structures

Hexagonal Close-Packed Crystal Structure

e.g.Cd, Mg, Ti, Zn


Coordination # = 12
6 atoms/unit cell:
1/6 12 top and bottom
planes + 1/2 over 2 face
and 3 interior
APF=0.74
c/a = 1.633

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The structure of crystalline solids

Density computations

Density computations
A knowledge of the crystal structure permits computation of
theoretical density :
nA
=
VC NA
where
n =number of atoms associated with each unit cell
A =atomic weight
VC =volume of the unit cell
NA =Avogadros number 6.023 1023 atoms/mol
Example
Cr: A=52 g/mol, BCC, R=0.125 nm
252 g/mol

=
= 7.17g/cm3
8
3
NA (41.2510 m/ 3)

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The structure of crystalline solids

Polymorphism

polymorphism: two or more distinct crystal structures for the


same material (allotropy/polymorphism)

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The structure of crystalline solids

Crystal systems

Crystal systems

Lattice parameters: a, b, c, , ,
All crystal systems can be described by these parameters
Seven different combinations: cubic, tetragonal, hexagonal,
orthorhombic, rhombohedral, monoclinic, and triclinic
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The structure of crystalline solids

Crystal systems

Seven Crystal Systems

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The structure of crystalline solids

Crystallographic points, directions and planes

Crystallographic points or lattice points


Specify a particular point within a unit cell
Right-handed coordinate system x, y, and z (not always mutually
perpendicular)

point coordinates: q (along x), r (along y), and s (along z), are
multiples or fractions of unit cell lengths.
e.g. unit cell center:
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1 1 1
2 2 2,

corner 1 1 1
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The structure of crystalline solids

Crystallographic points, directions and planes

Crystallographic directions
Vector connecting two points q r s and q0 r0 s0 . The length q0 q,
r0 r and s0 s define the vector components
Position such that it passes through origin.
Measure length in unit cell dimensions a, b and c.
Reduce to smallest integer values u, v and w.
Enclose in brackets [u v w]. Negative - overbar.

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The structure of crystalline solids

Crystallographic points, directions and planes

For unit cells with rotational symmetry, some non-parallel


directions are equivalent. The more symmetry, the more
directions that are equivalent.
For example for cubic unit cells (FCC, BCC, SC): [100], [010], [001],

[001]
are equivalent
[100],
[010],

[1 10],
[10
1],
[01 1]
etc.
and [110], [101], [011], [110],
[101],
[011],
Families, grouped together, enclosed in brackets: < 100 > and
< 110 >.
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The structure of crystalline solids

Crystallographic points, directions and planes

Crystallographic planes

Defined with Miller indices h, j k, enclosed with ( )


To assign Miller indices to a plane:
if plane intersects origin, move the plane parallel within the unit
cell or move the origin to the corner of another unit cell.
find plane-axes intercepts in units of lattice lengths.
take recriprocals of intercepts.
divide to get smallest integers
enclose in ( ).

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The structure of crystalline solids

Crystallographic points, directions and planes

Example

Intercepts
Reciprocals
Reduction
Miller indices

a
1
1/1
1
(110)

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b
1
1/1
1

1/
0

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The structure of crystalline solids

Crystallographic points, directions and planes

Example

Intercepts
Reciprocals
Reduction
Miller indices

a
1/2
1/ 12
2
(100) equiv. to (200) ?

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1/
0

1/
0

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The structure of crystalline solids

Crystallographic points, directions and planes

Example

Intercepts
Reciprocals
Reduction
Miller indices

a
1/2
1/ 12
2
6
(634)

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b
1
1/1
1
3

c
3/4
1/ 34
4/3
4

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The structure of crystalline solids

Crystallographic points, directions and planes

Example
What if plane passes through origin?

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The structure of crystalline solids

Crystallographic points, directions and planes

Crystallographic planes
all parallel planes are
equivalent, e.g. (010) and

(010).
as with directions,
symmetry makes many
planes equivalent.
e.g. for cubic lattices (BCC,
FCC, SC) (100), (010), (001),

and (001)
are
(100),
(010),
an equivalent family of
planes, {100}
(hjk) perpendicular to [h j k]
for cubic lattices only
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The structure of crystalline solids

Crystallographic points, directions and planes

Construction of specified crystallographic plane


if no zeros, take reciprocals and construct a plane from 3 points.
If 1 zero, take other 2 reciprocals, connect them with a line and
slide the line 1 lattice unit along the zero direction. Close the
rectangle.
If 2 zeros, take other 1 reciprocal, and slide point 1 lattice unit
along the 2 zero directions. Close the rectangle.
Example

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The structure of crystalline solids

Crystallographic points, directions and planes

Atomic arrangement

Reduced-sphere FCC unit cell with (110) plane


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The structure of crystalline solids

Crystallographic points, directions and planes

Atomic arrangement

Reduced-sphere BCC unit cell with (110) plane


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The structure of crystalline solids

Crystallographic points, directions and planes

Linear and planar densities


Definition
Linear Density (LD)=

number of atoms centered on direction vector


length of direction vector

Example
Linear density of the [110] direction for FCC

LD110 = 2

+1+
4R

1
2

1
2R

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The structure of crystalline solids

Crystallographic points, directions and planes

Linear and planar densities


Definition
Planar Density (PD)=

number of atoms centered on a plane


area of plane

Example
Planar density of the (110) for FCC

PD110 =
1
4R2

1
4

+2

1
2

2R 2 4R

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The structure of crystalline solids

Crystallographic points, directions and planes

Example
Planar Density of (100) Iron
Solution: At T < 912 C iron has the BCC structure.

Radius of iron R = 0.1241 nm


1
1
Planar density = 2 =  2 = 12.1 atoms/nm2 = 1.21019 atoms/m2
a
4 3
3 R
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The structure of crystalline solids

Crystallographic points, directions and planes

Example
Planar Density of (111) Iron

 2
area= 2ah = 3a2 = 3 4 3 3 R =
Planar Density =

16 3 2
3 R

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=7

16 3 2
3 R
atoms/nm2 =0.71019

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atoms/m2

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The structure of crystalline solids

Crystallographic points, directions and planes

Example
Planar Density of (111) Iron

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The structure of crystalline solids

Close-packed crystal structures

Close-packed crystal structures


FCC

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HCP

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The structure of crystalline solids

Close-packed crystal structures

Closed-pack stacking sequences

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The structure of crystalline solids

Close-packed crystal structures

HCP
Stacking sequence: ABABABAB . . .

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The structure of crystalline solids

Close-packed crystal structures

FCC
Stacking sequence: ABCABCABCABC . . .

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The structure of crystalline solids

Crystalline and noncrystalline materials

Crystalline and noncrystalline materials


Single Crystal - recently
extremely important
I

Properties vary with


direction: anisotropic e.g.
elastic modulus, index of
refraction

Polycrystalline
I

Properties may/may not


vary with direction.
If grains are randomly
oriented: isotropic.
If grains are textured,
anisotropic.
Grain sizes typ. range from
1 nm to 2 cm

Noncrystalline solids
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The structure of crystalline solids

Determination of crystal structures

X-ray diffraction

n = 2dhkl sin
For cubic symmetry dhkl =
Manolis Doxastakis (University of Houston)

a
h2 +k2 +l2
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The structure of crystalline solids

Determination of crystal structures

X-ray diffraction

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Imperfections in solids

Imperfections in solids
There is no such thing as a perfect crystal.
Many of the important properties of materials are due to the
presence of imperfections.

Imperfection:
Chemical - foreign element - e.g. Ni in Cu, P in Si
Structural
I

0D - missing or extra atom (point defects)


F
F
F

I
I

Vacancy atoms
Interstitial atoms
Substitutional atoms

1D - dislocation
2D - grain boundary, surface

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Imperfections in solids

Point defects

Vacancies and Self-interstitials


vacant atomic sites in a structure:

extra atoms positioned between atomic sites.

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Imperfections in solids

Point defects

Vacancies and Self-interstitials

All crystalline solids contain vacancies


Equilibrium number of vacancies Nv :


Qv
Nv = N exp
kT
where:
N: total number of atomic sites
Qv : energy required for the formation of a vacancy site
T: absolute temperature
k: Boltzmanns constant (1.381023 J/atom-K)

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Imperfections in solids

Point defects

Example
Estimating vacancy concentration:
Find the equil. number of vacancies in 1 m3 of Cu at 1000 C
Given:
= 8.4 g/cm3 , ACu = 63.5 g/mol, NA = 6.02 1023 atoms/mol,
QV = 0.9 ev/atom.
NA
N =
= 8.0 1028 atoms/m3
ACu
At 1000 C (1273 K):


Qv
Nv = N exp
= 2.2 1025 vacancies/m3
kT

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Imperfections in solids

Point defects

Impurities in solids

Pure metal is not possible.


intentional or unintentional
intentional (e.g. copper in silver): alloy = solid solution
benefits:
I
I
I
I
I

increased strength
increased hardness
corrosion resistance
increased electrical conductivity (for semiconductors)
desired optical properties

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Imperfections in solids

Point defects

If impurity (B) added to host (A):


Solid solution of B in A

Solid solution and/or


Second phase:
(different composition
and/or structure)
solvent/solute terminology
solvent-major component
solute-minor component
(sometimes more or less equal concentrations)
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Imperfections in solids

Point defects

Conditions for substitutional solid solution (S.S.)


W. Hume-Rothery rule
1

r (atomic radius) < 15%

Proximity in periodic
table i.e., similar
electronegativities

Same crystal structure


for pure metals

Valency

Example
Copper and Nickel?
Carbon and Iron?
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Imperfections in solids

Point defects

Specification of composition
Definition
Weight Percent, wt%
i.e. for two components
m1
100
m1 + m2

C1 =
where mi mass of component i
Definition
Atom Percent, at%
i.e. for two components
C01 =

nm1
100
nm1 + nm2

where nm,i number of moles of component i, nm,i =


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mi
Ai
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Imperfections in solids

Point defects

Sometimes it is necessary to convert, i.e. conversion of weight percent


to atom percent for a two element alloy:
C01 =

C1 A2
100 where Ai atomic weight of i
C1 A2 + C2 A1

Proof: If total alloy mass M0 = m01 + m02 :


nm1
100 =
C01 =
nm1 + nm2
C01 =

C1 M0
100A1
C1 M0
C2 M0
100A1 + 100A2

Manolis Doxastakis (University of Houston)

m01
A1
m01
A1

100 =

CHEE 3300

m02

100

m01 =C1 M0 /100

A1

C1 A2
100
C1 A2 + C2 A1

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Imperfections in solids

Point defects

Example
Alloy is 3wt% C, 48wt% Fe, 49wt% Ni.
Calculate atom (mole) percent composition.
Assume 100g total mass:
moles C =

3g
12.01 g/mole

moles Fe =

48 g
55.85 g/mole

moles Ni =

49 g
58.69 g/mole

% moles C =

ntotal = 0.250 + 0.859 + 0.835 = 1.944


= 0.859

= 0.835

= 0.250

0.250
1.944

100 = 12.9%

% moles Fe =

0.859
1.944

100 = 44.2%

% moles Ni =

0.835
1.944

100 = 42.9%

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( check sum=100 ! )
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Imperfections in solids

Point defects

Example
Alloy has 1 g C, 2 moles Fe and 0.1 moles Ni per cm3 of alloy.
Find wt%. Given: C = 2.25 g/cm3 , Fe = 7.87 g/cm3 , Ni = 8.90 g/cm3 .
1 g of C
2 moles of Fe 55.85 g/mole =111.7 g Fe
wNi g of Ni: 0.1 moles/cm3 alloy 58.69 g/mole = 5.869 g/cm3 alloy =
Assume Va = V1 + V2 + V3 =
Va = 14.6375 +
w
5.869 = VNia

wNi
8.90

w1
1

wNi
5.869

+ w22 +

w3
3

= 14.6375 +

1g C
2.25 g/cm3

wNi
8.90

wNi
Va

111.7 g Fe
7.87 g/cm3

+ 8.90 gNi/cm3

wNi = 252 g

1
111.7
wt% C= 1+111.7+252
100 = 0.27, wt% F= 364.7
100 = 30.6,
252
wt% Ni= 364.7 100 = 69.1

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Imperfections in solids

Line defects

Line defects

One dimensional defects around which atoms are misaligned.


Edge dislocation:
I
I

extra half-plane of atoms inserted in a crystal structure


b to dislocation line

Screw dislocation:
I
I

spiral planar ramp resulting from shear deformation


b|| to dislocation line

Burgers vector, b: measure of lattice distortion

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Imperfections in solids

Line defects

Edge dislocation

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Imperfections in solids

Line defects

Screw dislocation

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Imperfections in solids

Planar defects

Planar defects
Boundaries that have two dimensions and normally separate regions
of materials that have different crystallographic orientations:
external surfaces
grain boundaries
stacking faults (e.g. for FCC metals an error in ABCABC packing
sequence :ABCABABC)
phase boundaries
twin boundaries

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Imperfections in solids

Planar defects

Grain boundaries

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Imperfections in solids

Microscopic examination

Optical microscopy
Useful up to 2000 magnification.
Polishing removes surface features (e.g., scratches)
Etching changes reflectance, depending on crystal orientation.

Other techniques: electron microscopy (transmission and scanning)


and scanning probe microscopy.
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Imperfections in solids

Microscopic examination

Scanning probe micrograph showing a (111)-type surface for silicon

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Imperfections in solids

Microscopic examination

Grain size determination


Grain size is often determined in polycrystalline materials in terms of
average grain volume, diameter or area.
Intercept Method:
Draw straight lines of same length
Count grains intersected by each line
Average grain diameter = average of line length over number of
grains intersected (divided by magnification)
ASTM: n grain size number (1-10). Magnification of 100. If N the
average number of grains per square inch at 100:
N = 2n1

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Diffusion

Introduction

Diffusion

Material transport by atomic motion


Mechanisms in solids:
Vacancy diffusion
Interstitial diffusion
Along grain boundaries

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Diffusion

Introduction

Interdiffusion
In an alloy, atoms tend to migrate from regions of high concentration
to regions of low concentration

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Diffusion

Introduction

Self-diffusion

In an elemental solid, atoms also migrate.

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Diffusion

Diffusion mechanisms

Vacancy diffusion
atoms exchange with vacancies
applies to substitutional impurities atoms
rate depends on:
I
I

number of vacancies
activation energy to exchange.

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Diffusion

Diffusion mechanisms

Interstitial diffusion

Smaller atoms can diffuse between atoms.

More rapid than vacancy diffusion

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Diffusion

Diffusion mechanisms

Example

Case Hardening:
Diffuse carbon atoms into the
host iron atoms at the surface.
Example of interstitial
diffusion is a case hardened
gear.
Result: The presence of C
atoms makes iron (steel)
harder.

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Diffusion

Steady-state diffusion

Steady-state diffusion
Definition
J = Flux =

kg
moles (or mass) diffusing
mol
=
or 2
2
(surface area)(time)
cm s
m s

Measured empirically:
Make thin film (membrane) of known surface area
Impose concentration gradient
Measure how fast atoms or molecules diffuse through the
membrane
M
1 dM
=
J=
At A dt
If the diffusion flux does not change with time, a steady-state condition
exists.
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Diffusion

Steady-state diffusion

Ficks first law - Steady state

Flux proportional to concentration gradient


dC C CB CA

=
dx
x
xB xA
Ficks first law: J = D
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dC
dx
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Diffusion

Steady-state diffusion

Example
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? Given data:
diffusion coefficient in butyl rubber: D = 110 108 cm2/s
surface concentrations: C1 = 0.44 g/cm3 , C2 = 0.02 g/cm3
Assuming linear concentration gradient:
J = D

dC
C2 C1
D
with x2 x1 =0.04 cm
dx
x2 x1

J = (110 108 cm2/s)

0.02 g/cm3 0.44 g/cm3


= 1.16 105 g/cm2 s
0.04 cm

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Diffusion

Factors that influence diffusion

Factors that influence diffusion


Diffusing species

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Diffusion

Factors that influence diffusion

Factors that influence diffusion


Temperature
Diffusion coefficient increases with increasing T


Qd
D = D0 exp
RT
where
D
D0
Qd
R
T

= diffusion coefficient (m2/s)


= pre-exponential (m2/s)
= activation energy (J/mol or eV/atom)
= gas constant (8.314 J/molK)
= absolute temperature (K)

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Diffusion

Factors that influence diffusion

Example

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Diffusion

Factors that influence diffusion

Example
At 300 C the diffusion coefficient and activation energy for Cu in Si
are:
D(300 C) = 7.8 1011 m2/s
Qd = 41.5 kJ/mol
What is the diffusion coefficient at 350 C?
T1 = 273 + 300 = 573 K,
 
Q
ln D2 = ln D0 Rd T12
 
Q
ln D1 = ln D0 Rd T11

T2 = 273 + 350 = 623 K




Qd 1
D2
1

ln
D

ln
D
=
ln
=

2
1

D1
R T2 T1

D2 = 15.7 1011 m2/s


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Diffusion

Nonsteady-state diffusion

Nonsteady-state diffusion
The concentration of diffusing species is a function of both time
and position C = C(x, t)
Time-dependent (non-steady-state) is described by Ficks second
law. In 1D:
!
J
C

C
=
=
D
t
x x
x
If D is not a function of x (1D), then:
C
2 C
=D 2
t
x
Can solve equations for a number of different boundary
conditions and geometries. Numerical methods can often be used
when analytical solution not possible.
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Diffusion

Nonsteady-state diffusion

Example
Semi-infinite slab

Boundary Conditions (B.C.):


at t = 0, C = C0 for 0 x
at t > 0, C = CS for x = 0 (const. surf. conc.)
C = C0 for x =
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Diffusion

Nonsteady-state diffusion

Example
Semi-infinite slab

x
Cx C0
= 1 erf
Cs C0
2 Dt

where erf(z)=Gaussian
error function defined by
Z z
2
2
erf(z) =
ey dy
0
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Diffusion

Nonsteady-state diffusion

x
Cx C0
= 1 erf
Cs C0
2 Dt

Example
Compute Cx /Cs at t = 100 s, x = 1 104 cm, for D = 1 108 cm2/s,
C0 = 0:

4 cm

10
Cx
= 1 erf(0.05) 1 0.05 = 0.95
= 1 erf p

Cs
2 1 108 cm2/s 100 s

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Diffusion

Nonsteady-state diffusion

For some desired, constant Cx , (Cx C0 )/(Cs C0 ) = constant


Therefore right hand side of semi-inf. Slab eq. = constant
Therefore x = constant
2 Dt

Example
Suppose you want to know how long it will take for a species to
diffuse a distance x, such that the concentration Cx is half that of the
surface concentration:
(C0 = 0):
!
!
Cx (x, t) C0 1
x
x
1
= = 1 erf
erf
=
Cs C0
2
2
2 Dt
2 Dt
from table 5.1 with interpolation, when erf(z)=0.5, z=0.48:

1
x
x Dt
2 2 Dt
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Diffusion

Nonsteady-state diffusion

Example
Cadmium (Cd) is sometimes used as p-type dopant in indium phospide
(InP), a semiconductor. Start with an InP wafer that is doped with zinc (Zn),
an n-type dopant. The Zn atom concentration throughout the wafer is
uniform and equal to 1 1018 cm3 . Now instantaneously introduce Cd vapor
on one side of the wafer and instantaneously heat the wafer to 650 C (923K)
such that the concentration of Cd at the surface is 2 1018 cm3 . Since this Cd
concentration exceeds the Zn concentration, the surface now is p-type. As
time passes, the surface Cd concentration remains fixed at 2 1018 cm3 ,
while Cd diffuses increasingly deeper into the InP wafer. The sub-surface
planar boundary separating p-type and n-type InP occurs at a depth at which
the concentration of Cd equals that of Zn (i.e. 1 1018 cm3 ). The distance
between the plane and the surface is referred to as the p-n junction depth.
Given that the diffusion coefficient of Cd in InP is 2.7 1011 cm2/s, what are
the p-n junction depths at times of 10 seconds, 20 minutes and 2 hours after
introducing Cd vapor at the surface?

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Diffusion

Nonsteady-state diffusion

Example
(cont.)
Surface concentration of Cd: Cs = 2 1018 cm3
Cs
p-n junction at concentration: 1 1018 cm3 =
2
distance given in previous example... x Dt
q
10 seconds: x = 2.7 1011 cm2/s 10 s = 1.64 105 cm
q
20 minutes: x = 2.7 1011 cm2/s 20 60 s = 1.8 104 cm
q
2 hours: x = 2.7 1011 cm2/s 2 3600 s = 4.4 104 cm

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Diffusion

Nonsteady-state diffusion

Example
A surface hardening process requires that an impurity diffuses into a work
piece. Starting with a surface concentration, Cs = 2 1019 cm3 independent
of temperature, and no impurity in the work piece initially (C0 = 0), it is
observed that 30 minutes is required at 500 C to achieve the desired result of
Cx = 1 1019 cm3 at x = 104 cm. It is further observed that the same result
can be obtained in 20 minutes at 550 C.
Assuming the usual Arrhenius temperature-activated behavior for the
diffusion coefficient a) first find Qd /R, the activation energy for diffusion
divided by the gas constant. For the manufacturing of this treated work piece
to be profitable, the diffusion step must be completed in 10 minutes b) What
temperature should be used to complete the diffusion step with the desired
result in 10 minutes?
Cx =

Cs
, x Dt
2

Manolis Doxastakis (University of Houston)

t1 = 30 min T1 = 773 K
t2 = 20 min T2 = 823 K
t3 = 10 min T3 =?K
CHEE 3300

D1 t1 = D2 t2 = D3 t3

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Diffusion

Nonsteady-state diffusion

Example
(cont.)
 Q 
d


Qd
Qd
D1 t2 D0 exp RT1
20
20
 Q =
=
=
exp

D2 t1 D0 exp d
30
RT2 RT1
30
RT2


Qd
Qd 1
1
2

= ln
= 5158.9 K
R T2 T1
3
R
 Q 
!
d
Qd
Qd
20
D3 t2 D0 exp RT3
=

=
=

exp
=2
D2 t3 D0 exp Qd
10
RT3 RT2
RT2
Qd
Qd /R
Qd
=
ln 2 T3 =
= 924 K
RT3 RT2
Qd /RT2 ln 2

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Diffusion

Nonsteady-state diffusion

Example
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 49.5h 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.
! z= x
Cx (x, t) C0 0.35 0.20
x
2 Dt
= 1 erf
erf(z) = 0.8125
=
Cs C0
1.0 0.20
2 Dt
Table z = 0.90 : erf(z) = 0.7970, z = 0.95 : erf(z) = 0.8209, interpolation:
0.8125 0.7970
z 0.90
=
z = 0.93
0.95 0.90 0.8209 0.7970
(4 103 m)2
x
x2
1h
= 2.6 1011 m2/s
= 0.93 D = 2 =
2 (49.5 h) 3600 s
4z
t
(4)(0.93)
2 Dt
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Diffusion

Nonsteady-state diffusion

Example
(cont.)
To solve for temperature we rearrange the following equation:

 

Qd 1
Qd
Qd
ln D = ln D0
T=
D = D0 exp
RT
R T
R(ln D0 ln D)
from Table 5.2, for diffusion of C in FCC Fe:
D0 = 2.3 105 m2/s, Qd = 148, 000 J/mol
T=

D=2.61011 m2/s

148, 000 J/mol

(8.314 J/molK)(ln 2.3 105 m2/s ln 2.6 1011 m2/s)


T = 1300 K = 1027 C

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Mechanical properties of metals

Concepts of stress and strain

Mechanical properties of metals


different ways to apply a load

COMPRESSION

TENSION l

 TORSIONAL

SHEAR 

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Mechanical properties of metals

Concepts of stress and strain

Tension Tests

American Society for Testing and


Materials (ASTM)

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Mechanical properties of metals

Concepts of stress and strain

Engineering stress
Shear stress

Tensile stress

lbf
N
Ft
=
or 2
A0 in2
m
=

A0 : original area before loading

Fs
A0

SI units: MPa, US units: psi


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Mechanical properties of metals

Concepts of stress and strain

Engineering strain
li l0 l
=
l0
l0
Shear strain
Lateral strain
x
L
=
= tan
L =
y
w0
=

Tensile strain

=
L0

Strain is always dimensionless


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Mechanical properties of metals

Concepts of stress and strain

Stress is usually a combination of shear and tensile. Consider the stress


on a plane inside a rod:
A0 = r20
F0 r0
= 0
cos =
F
r
Area of ellipse:
r0
A0 = r0 r0 = r0 (
)
cos
A0
=
cos
0 =

F0
F cos
= A
0
0
A
cos

0 = cos2 =

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1 + cos 2
2

0 = sin cos =

CHEE 3300

sin 2
2
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Mechanical properties of metals

Elastic deformation

Deformation
Elastic deformation (reversible)

Plastic deformation (non-reversible)

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Mechanical properties of metals

Elastic deformation

Elastic deformation
Described by the modulus of elasticity, E (or Youngs modulus)
Hookes law:

= E E =

For shear stress and strain, the shear modulus, G, is defined as:

G=

Bulk modulus K: P = K V
V0
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Mechanical properties of metals

Elastic deformation

For some materials the stress-strain curve is not linear

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Mechanical properties of metals

Elastic deformation

Slope of stress-strain plot (which is proportional to the elastic


modulus) depends on bond strength of metal


E, G

dF
dr


r=r0

modulus: ionic > metallic  van der Waals


Manolis Doxastakis (University of Houston)

CHEE 3300

Fall 2013

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Mechanical properties of metals

Elastic deformation

Anelasticity for metals


small. For polymers
significant
viscoelastic behavior

Manolis Doxastakis (University of Houston)

CHEE 3300

Fall 2013

130 / 146

Mechanical properties of metals

Elastic deformation

Example
A 500 lb pendulum is to be hung from the ceiling in the large foyer of a
Science and Technology museum. The plan is to hang it, using a 100 ft. long,
1/8 inch diameter, steel rod. How much will the rod expand (in inches) when
the pendulum is attached to it? The modulus of elasticity (aka Youngs
modulus) for steel is 3 107 psi.
=

F
=
A0

40744 psi

500 lbs
= 40744 psi = =
= 0.001358
 2
E 3 107 psi
1
16
in2
` = `0 = 100 ft 12 in/ft = 1.63 inches
r=

1
16

2.54

= 1.5875 103 m
100
mg 500 0.45359 kg 9.8 m2/s
F
=
=
=
= 2.807 108 N/m2 = 0.2807 GPa
A0
A0
(1.5875 103 m)2
0.2807 GPa
= =
= 1.356 103 ` = `0 = 1.356 103 100 12 = 1.63
E
207 GPa
Manolis Doxastakis (University of Houston)

CHEE 3300

Fall 2013

131 / 146

Mechanical properties of metals

Elastic deformation

Poissons ratio
=

y
x
=
z
z

metals 0.33
ceramics 0.25
polymers 0.40
> 0.5 density increases
< 0.5 density decreases
(voids form)
For isotropic materials:
E = 2G(1 + )
E = 3K(1 2)
Manolis Doxastakis (University of Houston)

CHEE 3300

Fall 2013

132 / 146

Mechanical properties of metals

Elastic deformation

Example
A tensile stress is to be applied along the axis of a cylindrical brass rod that
has a diameter of 10 mm (0.4in). Determine the magnitude of the load
required to produce a 2.5 103 mm (104 in.) change in diameter if the
deformation is entirely elastic ( = 0.34, E = 97 103 MPa for brass)
d 2.5 103 mm
= 2.5 104
=
d0
10 mm
2.5 104
x
z = =
= 7.35 104

0.34
= z E = (7.35 104 )(97 103 MPa = 71.3 MPa
 2
d0
=
F = A0 =
2
!2
10 103 m
6N 2
(71.3 10 /m )
= 5600 N
2
x =

Manolis Doxastakis (University of Houston)

CHEE 3300

Fall 2013

133 / 146

Mechanical properties of metals

Plastic deformation

Plastic deformation
Simple tension experiment:

Different from non-linear elastic deformation, which is reversible


Manolis Doxastakis (University of Houston)

CHEE 3300

Fall 2013

134 / 146

Mechanical properties of metals

Plastic deformation

Plastic deformation

permanent
deformation
proportional limit,
yielding
yield strength (stress
at which noticeable
plastic deformation
has occurred - 0.002)
yield point
phenomenon

Manolis Doxastakis (University of Houston)

CHEE 3300

Fall 2013

135 / 146

Mechanical properties of metals

Plastic deformation

Yield Strength, comparison

Manolis Doxastakis (University of Houston)

CHEE 3300

Fall 2013

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Mechanical properties of metals

Plastic deformation

Tensile Strength
The tensile strength (TS) is the stress at the maximum on the
engineering stress-strain curve

Manolis Doxastakis (University of Houston)

CHEE 3300

Fall 2013

137 / 146

Mechanical properties of metals

Plastic deformation

Tensile Strength, comparison

Manolis Doxastakis (University of Houston)

CHEE 3300

Fall 2013

138 / 146

Mechanical properties of metals

Plastic deformation

Example
Mechanical properties from stress-strain plot (Ex. 6.3)
1
E = slope = 22
1 = 0.00160 =
93.8 GPa
yield strength at strain offset of
0.002 250 MPa
maximum load F of cylindrical
specimen with d0 = 12.8 mm
 2
F = A0 = (450 MPa) d20 =
57, 900 N

(1500) MPa

change in length of 250mm


specimen under = 345 MPa
l = l0 = (0.06)(250 mm) =
15 mm

Manolis Doxastakis (University of Houston)

CHEE 3300

Fall 2013

139 / 146

Mechanical properties of metals

Plastic deformation

Ductility
Measure of degree of plastic deformation
Percent elongation (l0
commonly 50mm):
!
lf l0
%EL =
100
l0
Percent reduction in
area:
!
A0 Af
%RA =
100
A0
Brittle materials are approximately considered to be those having a
fracture strain of less than about 5%.
indicates degree of plastic deformation before fracture
specifies allowable deformation during fabrication
Manolis Doxastakis (University of Houston)

CHEE 3300

Fall 2013

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Mechanical properties of metals

Plastic deformation

Resilience
Ability of a material to store energy (best in elastic region)
Modulus of resilience
Z y
Ur =
d
0

Linear:
!
2y
1
1 y
Ur y y =
=
2
2 y
2E
Units: F/A=g cm s2 /cm2 =
g cm2 s2 /cm3 (energy/volume)
Resilient materials are those having high yield strenghts and low
moduli of elasticity
Toughness: measure of ability to absorb energy up to fracture
Manolis Doxastakis (University of Houston)

CHEE 3300

Fall 2013

141 / 146

Mechanical properties of metals

Plastic deformation

True stress and strain


T =

F
Ai

T = ln

li
l0

Consider stress applied in


discrete increases, such that
the length starts at l0 and
then increases slightly to l1 ,
and then to l2 , etc.:
T =

l1 l0
l0

l2 l1
l1

l2 l1
l1

+ ... =

Pi
j=1

lj lj1 li li1 0

lj1

T =

R l0
l0

dl
l

= ln

l 
i

l0

If no volume change (Ai li = A0 l0 ), T = (1 + ) T = ln(1 + )


For some metals and alloys, from plastic deformation to necking
T = KnT (strain hardening exponent n, 0.15 steels, 0.5 copper)
Manolis Doxastakis (University of Houston)

CHEE 3300

Fall 2013

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Mechanical properties of metals

Plastic deformation

Example
Cylindrical specimen of steel with original diameter d0 = 12.8 mm,
engineering fracture strength f = 460 MPa. If cross sectional diameter
at fracture is 10.7 mm:
Ductility in terms of percent reduction in area

%RA =


12.8 mm 2


10.7 mm 2

2

2
12.8 mm

100 = 30%

True stress at fracture

T =

Manolis Doxastakis (University of Houston)

f A0
F
=
= 660 MPa
Af
Af
CHEE 3300

Fall 2013

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Mechanical properties of metals

Plastic deformation

Hardness
Measure of materials resistance to localized plastic deformation. Push
a very hard ball or pyramid into the material and measure its
indentation. The smaller the indentation, the harder the material.

Manolis Doxastakis (University of Houston)

CHEE 3300

Fall 2013

144 / 146

Mechanical properties of metals

Plastic deformation

Hardness measurements

Manolis Doxastakis (University of Houston)

CHEE 3300

Fall 2013

145 / 146

Mechanical properties of metals

Plastic deformation

Rule of thumb:
TS(MPa)=3.45HB
TS(psi)=500HB

Manolis Doxastakis (University of Houston)

CHEE 3300

Fall 2013

146 / 146