Introduction To Materials Science, Chapter 4, Imperfections in solids

CHAPTER 4

Addis Ababa institute of technology, School. of Mechanical and Industrial Engineering1

 Introduction To Materials Science, Chapter 4, Imperfections in solids

Addis Ababa institute of technology, School. of Mechanical and Industrial Engineering

 Introduction To Materials Science, Chapter 4, Imperfections in solids

• Example
• Draw the following planes and directions
in the case of a FCC structure: (112),
(001) and (101).

Addis Ababa institute of technology, School. of Mechanical and Industrial Engineering

 Introduction To Materials Science, Chapter 4, Imperfections in solids

• Example 2 Draw the planes (020), (120)

and (220) in a FCC structure.

Addis Ababa institute of technology, School. of Mechanical and Industrial Engineering

 Introduction To Materials Science, Chapter 4, Imperfections in solids

• Example 3 Draw the planes and directions

of FCC structures (321), (102), (201) and
(111).

Addis Ababa institute of technology, School. of Mechanical and Industrial Engineering

 Introduction To Materials Science, Chapter 4, Imperfections in solids

• Example 4 In a cubic unit cell, find the

angle between normals to the planes (111)
and (121).
• Solution Since the given crystal is cubic, the
normals to the planes (111) and (121) are
the directions [111] and [121] respectively.
If q ϴ be the angle between the normals,
then

Addis Ababa institute of technology, School. of Mechanical and Industrial Engineering

 Introduction To Materials Science, Chapter 4, Imperfections in solids

• Determine the linear atomic density in the

[110] and [111] directions of copper crystal
lattice. Lattice constant of copper is 3.61 10–
10
m

Addis Ababa institute of technology, School. of Mechanical and Industrial Engineering

 Introduction To Materials Science, Chapter 4, Imperfections in solids

• Example 5 Calculate the planar atomic

densities of planes (100), (110) and (111) in
FCC unit cell and apply your result for lead
(FCC form)

Addis Ababa institute of technology, School. of Mechanical and Industrial Engineering

 Introduction To Materials Science, Chapter 4, Imperfections in solids

1. What are the indices for the two planes

drawn in the following sketch?
2. Calculate the radius of a vanadium
atom, given that V has a BCC crystal
structure, a density of 5.96 g/cm 3, and
an atomic weight of 50.9 g/mol
3. Determine the planer density for (110)
plane of V.

.0.2nm

Addis Ababa institute of technology, School. of Mechanical and Industrial Engineering9

 Introduction To Materials Science, Chapter 4, Imperfections in solids

Chapter Outline
“Crystals are like people, it is the defects in them
which tend to make them interesting!” - Colin
Humphreys.

• Defects in Solids
 0D, Point defects
 vacancies
 interstitials
 impurities, weight and atomic composition
 1D, Dislocations
 edge
 screw
 2D, Grain boundaries
 tilt
 twist
 3D, Bulk or Volume defects
 Atomic vibrations

Addis Ababa institute of technology, School. of Mechanical and Industrial Engineering

1
 Introduction To Materials Science, Chapter 4, Imperfections in solids

Defects – Introduction (I)

Real crystals are never perfect, there are always

defects

Schematic drawing of a poly-crystal with many defects

by Helmut Föll, University of Kiel, Germany.

Addis Ababa institute of technology, School. of Mechanical and Industrial Engineering

11
 Introduction To Materials Science, Chapter 4, Imperfections in solids

Defects – Introduction (II)

Defects have a profound impact on the

macroscopic properties of materials

Bonding
+
Structure Properties
+

Defects

Addis Ababa institute of technology, School. of Mechanical and Industrial Engineering

1
 Introduction To Materials Science, Chapter 4, Imperfections in solids

Defects – Introduction (III)

Processing determines the defects

Composition

Bonding Crystal Structure

Thermomechanical
Processing

defect introduction and manipulation

Microstructure

Addis Ababa institute of technology, School. of Mechanical and Industrial Engineering

1
 Introduction To Materials Science, Chapter 4, Imperfections in solids

Types of Defects

Four categories
depending on their dimension

 0D, Point defects:

atoms missing or in irregular places in the lattice
(vacancies, interstitials, impurities)

 1D, Linear defects:

groups of atoms in irregular positions (e.g. screw
and edge dislocations)

 2D, Planar defects:

interfaces between homogeneous regions of the
material (grain boundaries, external surfaces)

 3D, Volume defects:

extended defects (pores, cracks)

Addis Ababa institute of technology, School. of Mechanical and Industrial Engineering

1
 Introduction To Materials Science, Chapter 4, Imperfections in solids

Point defects: vacancies &

interstitials

Self-interstitials
Vacancy

Vacancy - lattice position that is vacant

because atom is missing.
Interstitial - atom that occupies a place
outside the normal lattice position. May be
same type of atom (self interstitial) or an
impurity interstitial.
Addis Ababa institute of technology, School. of Mechanical and Industrial Engineering
1
 Introduction To Materials Science, Chapter 4, Imperfections in solids

How many vacancies?

Equilibrium number of vacancies is
due to thermal vibrations

N v  N s exp 
Qv 
k T 
 B 

Ns = number of regular lattice sites

kB = Boltzmann constant
Qv = energy to form a vacant lattice site in a
perfect crystal
T = temperature in Kelvin (note, not in oC or oF).

Room temperature in copper: one vacancy per 1015

atoms. Just below the melting point: one vacancy for
every 10,000 atoms.

Above lower bound to number of vacancies.

Additional (non-equilibrium) vacancies introduced
in growth process or treatment
(plastic deformation, quenching,
etc.)
Addis Ababa institute of technology, School. of Mechanical and Industrial Engineering
1
 Introduction To Materials Science, Chapter 4, Imperfections in solids

1. Calculate the equilibrium number

of vacancies per cubic meter for
copper at 1000C. The energy for
vacancy formation is 0.9 eV/atom;
the atomic weight and density (at
10000C) for copper are 63.5 g/mol
and 8.4 g/cm3, respectively.
2. Calculate the number of vacancies
per cubic meter in iron at
850C.The energy for vacancy
formation is 1.08 eV/atom.
Furthermore, the density and
atomic weight for Fe are 7.65g/cm3
(at 850ºC) and 55.85 g/mol,
respectively.

Addis Ababa institute of technology, School. of Mechanical and Industrial Engineering

1
 Introduction To Materials Science, Chapter 4, Imperfections in solids

Estimate number of vacancies in Cu at room T

N v  N s exp  v 
Q
 k BT 

kB = 1.38  10-23 J/atom-K = 8.62  10-5 eV/atom-K

T = 27o C + 273 = 300 K.

kBT = 300 K  8.62  10-5 eV/K =
0.026 eV
Qv = 0.9 eV/atom

Ns = NA/Acu
NA = 6.023  1023 atoms/mol
 = 8.4 g/cm3
Acu = 63.5 g/mol
6.023 10 23 atoms 
mol 
  8.4 g 
3
cm 
Ns   8  10 22 atoms
63.5 g cm 3
mol

atoms   0.9 eV atom 

N v  8 10 22
exp 
cm 3
 0.026 eV atom 

Addis Ababa institute of technology, School. of Mechanical and Industrial Engineering

1
 Introduction To Materials Science, Chapter 4, Imperfections in solids

Point defects: self-interstitials, impurities

(1) vacancies
1
(2) self-interstitial
3
(3)interstitial impurity
(4,5)substitutional
4
impurities

Arrows  local
5 stress introduced
by defect

Self-interstitials
Large distortions in surrounding lattice
 Energy of self-interstitial formation is
~ 3 x larger than for vacancies (Qi ~ 3Qv)
 equilibrium concentration of self-
interstitials is very low(< 1/ cm3 at 300K)
Addis Ababa institute of technology, School. of Mechanical and Industrial Engineering
1
 Introduction To Materials Science, Chapter 4, Imperfections in solids

Impurities
Impurities  atoms which differ from host

 All real solids are impure. Very pure

metals 99.9999%
- one impurity per 106 atoms
 May be intentional or unintentional
Carbon in small amounts in iron makes
steel. It is stronger.
Boron in silicon change its electrical
properties.

 Alloys - deliberate mixtures of metals

Sterling silver is 92.5% silver – 7.5%
copper alloy.
Stronger than pure silver.

Addis Ababa institute of technology, School. of Mechanical and Industrial Engineering

2
 Introduction To Materials Science, Chapter 4, Imperfections in solids
How Are Impurities Contained in Alloy?
Solid solutions
Host (Solvent or Matrix) dissolves minor
component (Solute).
Ability to dissolve is called Solubility.
 Solvent: element in greater amount
 Solute: element present in lesser amount
 Solid Solution:
homogeneous
maintain crystal structure
randomly dispersed impurities
(substitutional or interstitial)

OR

Substitutional solid
Interstitial solid
soln. (e.g., Cu in Ni)
soln. (e.g., C in Fe)
Addis Ababa institute of technology, School. of Mechanical and Industrial Engineering
2
 Introduction To Materials Science, Chapter 4, Imperfections in solids

Second Phase
As solute atoms added: new compounds
or structures form or solute forms local
precipitates
Solid solution of B in A plus particles of a new
phase (usually for a larger amount of B)

Second phase particle

--different composition
--often different structure.
Whether addition of impurities results in a solid
solution or second phase depends nature of
impurities, concentration, temperature and
pressure

Addis Ababa institute of technology, School. of Mechanical and Industrial Engineering

2
 Introduction To Materials Science, Chapter 4, Imperfections in solids

Conditions for substitutional solid

solution (S.S.)
• Hume – Rothery rules
– 1. r (atomic radius) < 15%
– 2. Proximity in periodic table
• i.e., similar electronegativities
– 3. Same crystal structure for pure
metals
– 4. Valency equality
• All else being equal, a metal will have
a greater tendency to dissolve a metal
of higher valency than one of lower
valency (it provides more electrons to
the “cloud”)

Addis Ababa institute of technology, School. of Mechanical and Industrial Engineering

2
 Introduction To Materials Science, Chapter 4, Imperfections in solids

Application of Hume–Rothery rules – Solid

Solutions
1. More Zn or Al in Cu?
Surely Zn since size is closer thus causing lower
distortion (4% vs 12%)
2. Would you predict more Al or Ag to dissolve in Zn?
More Al because size is closer and val. Is higher – but
not too much because of structural differences – FCC
in HCP

Addis Ababa institute of technology, School. of Mechanical and Industrial Engineering

2
 Introduction To Materials Science, Chapter 4, Imperfections in solids

Random, substitution solid solution can occur

in Ionic Crystalline materials as well.
Eg. Here of NiO in MgO.
• The O2− arrangement is unaffected.
• The Substitution occurs among Ni2+
and Mg2+ ions.

Addis Ababa institute of technology, School. of Mechanical and Industrial Engineering

 Introduction To Materials Science, Chapter 4, Imperfections in solids

A substitution solid solution of Al2O3 in MgO

is not as simple as the case of NiO in MgO.
The requirement of charge neutrality in the
overall compound permits only two Al3+ ions
to fill every three Mg2+ vacant sites, leaving
one Mg2+ vacancy.

Addis Ababa institute of technology, School. of Mechanical and Industrial Engineering

 Introduction To Materials Science, Chapter 4, Imperfections in solids

Interstitial Solid Solutions

Carbon interstitial
atom in BCC iron

Interstitial solid solution of C in BCC Fe ( phase).

C small enough to fit (some strain in BCC lattice).

Factors for high solubility:
 FCC, BCC, HCP: void space between
host (matrix) atoms relatively small
 atomic radius of solute should be
significantly less than solvent
 Max. concentration  10%,
(2% for C-Fe)
Addis Ababa institute of technology, School. of Mechanical and Industrial Engineering
2
 Introduction To Materials Science, Chapter 4, Imperfections in solids

Composition / Concentration
 Weight Percent (wt %)

Weight of one element relative to total alloy weight

2 components: concentration of element 1 in wt. %

m1
C1   100
m1  m 2
 atom percent (at %):
useful in understanding material at atomic level

Number of moles (atoms) of one element relative to

total number of moles (atoms) in alloy.

2 component: concentration of element 1 in at. %:

n m1
C '
1  100
n m1  n m 2

nm1= number density = m’1/A1 (m’1 = weight in

grams of 1, A1 is atomic weight of element 1)
Addis Ababa institute of technology, School. of Mechanical and Industrial Engineering
2
 Introduction To Materials Science, Chapter 4, Imperfections in solids

Composition Conversions
Weight % to Atomic %:
C1A 2
C '
1 100
C1A 2  C 2 A1

C 2 A1
C '
2 100
C1A 2  C 2 A1

Atomic % to Weight %:

C1' A1
C1  ' 100
C1A1  C 2 A 2
'

C '2 A 2
C2  ' 100
C1A1  C 2 A 2
'

Textbook, pp. 71-74

Addis Ababa institute of technology, School. of Mechanical and Industrial Engineering

2
 Introduction To Materials Science, Chapter 4, Imperfections in solids

Wt. % and At. % -- An example

Addis Ababa institute of technology, School. of Mechanical and Industrial Engineering

 Introduction To Materials Science, Chapter 4, Imperfections in solids

Defects in Ceramic Structures

• Frenkel Defect
--a cation is out of place.
• Shottky Defect
--a paired set of cation and anion vacancies.

Shottky
Defect:

Frenkel
Defect

Equilibrium concentration QD / kT

of defects ~e
Addis Ababa institute of technology, School. of Mechanical and Industrial Engineering
 Introduction To Materials Science, Chapter 4, Imperfections in solids

Line Defects
Are called Dislocations:
And:
• slip between crystal planes result when
dislocations move,
• this motion produces permanent (plastic)
deformation.
Schematic of Zinc (HCP):
• before deformation • after tensile elongation

slip steps which are the

physical evidence of
large numbers of
dislocations slipping
along the close packed
plane {0001}

Addis Ababa institute of technology, School. of Mechanical and Industrial Engineering

3
 Introduction To Materials Science, Chapter 4, Imperfections in solids

Dislocations = Linear Defects

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

Addis Ababa institute of technology, School. of Mechanical and Industrial Engineering

3
 Introduction To Materials Science, Chapter 4, Imperfections in solids

Definition of the Burgers

vector, b, relative to an edge
dislocation.
(a) In the perfect crystal, an
m× n atomic step loop
closes at the starting point.
(b) (b) In the region of a
dislocation, the same loop
does not close, and the
closure vector (b)
represents the magnitude
of the structural defect.
For the edge dislocation,
the Burgers vector is
perpendicular to the
dislocation line.

Addis Ababa institute of technology, School. of Mechanical and Industrial Engineering

3
 Introduction To Materials Science, Chapter 4, Imperfections in solids

Screw dislocation. The spiral stacking of

crystal planes leads to the Burgers vector
being parallel to the dislocation line.

Addis Ababa institute of technology, School. of Mechanical and Industrial Engineering

3
 Introduction To Materials Science, Chapter 4, Imperfections in solids

Mixed dislocation. This dislocation has both

edge and screw character with a single Burgers
vector consistent with the pure edge and pure
screw regions.

Addis Ababa institute of technology, School. of Mechanical and Industrial Engineering

3
 Introduction To Materials Science, Chapter 4, Imperfections in solids

Interfacial Defects

External Surfaces
Surface atoms  unsatisfied bonds
 higher energies than bulk atoms
 Surface energy,  (J/m2)

• Surface areas try to minimize (e.g. liquid drop)

• Solid surfaces can “reconstruct” to satisfy
atomic bonds at surfaces.

Grain Boundaries
Polycrystalline: many small crystals or grains.
Grains have different crystallographic orientation.
Mismatches where grains meet.
1. Surfaces and interfaces are reactive
2. Impurities tend to segregate there.
3. Extra energy associated with interfaces
 larger grains tend to grow by diffusion of atoms
at expense of smaller grains, minimizing energy.
Addis Ababa institute of technology, School. of Mechanical and Industrial Engineering
3
 Introduction To Materials Science, Chapter 4, Imperfections in solids

High and Low Angle Grain Boundaries

Misalignments of atomic planes between grains 
Distinguish low and high angle grain boundaries

Addis Ababa institute of technology, School. of Mechanical and Industrial Engineering

3
 Introduction To Materials Science, Chapter 4, Imperfections in solids

Tilt and Twist Grain Boundaries

Tilt boundary  Low angle grain boundary: an
array of aligned edge dislocations (like joining two
wedges)

Transmission electron microscope

image of a small angle tilt
boundary in Si. The red lines
mark the edge dislocations, the
blue lines indicate the tilt angle

Twist boundary - boundary region consisting of

arrays of screw dislocations (like joining two
halves of a cube and twist an angle around the
cross section normal)
Addis Ababa institute of technology, School. of Mechanical and Industrial Engineering
3
 Introduction To Materials Science, Chapter 4, Imperfections in solids

Bulk or Volume Defects

 Pores: affect optical, thermal, mechanical
properties
 Cracks: affect mechanical properties
 Foreign inclusions: affect electrical,
mechanical, optical properties

Cluster of microcracks in a
melanin granule irradiated
by a short laser pulse.
Computer simulation by L.
V. Zhigilei and B. J.
Garrison.

Addis Ababa institute of technology, School. of Mechanical and Industrial Engineering

4
 Introduction To Materials Science, Chapter 4, Imperfections in solids

Atomic Vibrations

 Heat causes atoms to vibrate

 Vibration amplitude increases with

temperature

 Melting occurs when vibrations are

sufficient to rupture bonds

 Vibrational frequency ~ 1013 Hz

 Average atomic energy due to

thermal excitation is of order kT
Addis Ababa institute of technology, School. of Mechanical and Industrial Engineering
4
 Introduction To Materials Science, Chapter 4, Imperfections in solids

Summary
• Point, Line, Surface and Volumetric defects
exist in solids.
• The number and type of defects can be
varied and controlled
– T controls vacancy conc.
– amount of plastic deformation controls # of
dislocations
– Weight of charge materials determine
concentration of substitutional or interstitial
point ‘defects’
• Defects affect material properties (e.g.,
grain boundaries control crystal slip).
• Defects may be desirable or undesirable
– e.g., dislocations may be good or bad,
depending on whether plastic deformation is
desirable or not.
– Inclusions can be intention for alloy
development

Addis Ababa institute of technology, School. of Mechanical and Industrial Engineering

 Introduction To Materials Science, Chapter 4, Imperfections in solids

Which of these elements would you expect

to form the following with nickel:
a. A substitutional solid solution having
complete solubility
b. A substitutional solid solution of
incomplete solubility
c. An interstitial solid solution
Addis Ababa institute of technology, School. of Mechanical and Industrial Engineering
4
 Introduction To Materials Science, Chapter 4, Imperfections in solids

• For both FCC and BCC crystal structures, there

are two different types of interstitial sites.
• octahedral interstitial site: For FCC, is
located at the center of each edge of the unit
cell;
• tetrahedral interstitial site: for BCC this site
is found at 0 ½ ¼ positions—that is, lying on
{100} faces.
• For both FCC and BCC crystal structures,
compute the radius r of an impurity atom that
will just fit into one of these sites in terms of
the atomic radius R of the host atom.

Addis Ababa institute of technology, School. of Mechanical and Industrial Engineering

4
 Introduction To Materials Science, Chapter 4, Imperfections in solids

Summary
Understand language and concepts:
 Alloy
 Atom percent
 Atomic vibration
 Boltzmann’s constant
 Burgers vector
 Composition
 Dislocation line
 Edge dislocation
 Grain size
 Imperfection
 Interstitial solid solution
 Microstructure
 Point defect
 Screw dislocation
 Self-Interstitial
 Solid solution
 Solubility limit
 Solute
 Solvent
 Substitutional solid solution
 Vacancy
 Weight percent
Addis Ababa institute of technology, School. of Mechanical and Industrial Engineering
4