ME201 Material Science &

Engineering
Imperfections in solids

Alfaisal University
What will you learn in this lecture?
On completion of this lecture, students should be able to:

 List the types of imperfections (i.e. point, line, and area defects)
 Describe point defects and determine the vacancy concentration

2
 Introduction
Perfect crystal The concept of a perfect crystal
is adequate for explaining some
material properties (esp. for
metals)
Defects can affect other material properties
Defects have a profound impact on the various properties of materials:
- Production of advanced semiconductor devices require not only a rather
perfect Si crystal as starting material, but also involve introduction of
specific defects in small areas of the sample.
- Forging a metal tool introduces defects … and increases strength of the
tool.
3
 Types of Imperfections
There is no such thing as a perfect crystal.
• What are these imperfections?
• Vacancy atoms: vacant atomic sites in a
structure Point
• Interstitial and substitution atoms: "extra“ defects
atoms positioned between atomic sites

• Dislocations: edge and screw dislocations Line defects

• Interfacial (grain boundaries) Area defects

• How do these defects affect the properties of materials?

4
 Point Defects
• Vacancies: vacant atomic sites in a structure

Vacancy
distortion
of planes

• Self-Interstitials: “extra” atoms positioned between atomic sites

self-
distortion interstitial
of planes

5
 Vacancy defects
Each lattice site is a potential vacancy site

Defect/vacancy concentration Energy required for the

formation of vacancy,
Number of vacancies per cm3 Activation energy

Nv æ -Q v ö
= expçç ÷
÷
Number of atoms per cm3 N è kT ø
Temperature
Boltzmann's constant
(1.38 x 10-23 J/atom-K)
(8.62 x 10-5 eV/atom-K)

6
Measuring activation energy
NV   QV 
 exp 
N  kT 
•We can get Qv from an experiment
•Measure NV/N as temperature changes
Nv Nv slope
ln
N N
-Qv /k
exponential
dependence
T 1/T
Defect/vacancy concentration

The number of vacancies goes up exponentially with temperature

What happens to the predicted density if you have a lot of vacancies?
 Test Your Understanding
Calculate the equilibrium number of vacancies per cubic meter
for copper at 10000C. The energy for vacancy formation is
Qv=0.9 eV/atom; the atomic weight ACu = 63.5 g/mol and density
(at 10000C)  = 8.4106 g/m3

Note: k = 8.62 x 10-5 eV/atom-K T = 1000+273 = 1273 K

NV   QV    0 .9  4
 exp   exp  
 (8.62  10 5 )(1273)   2. 7  10
N  kT   
NA
NA = 6.02 x 10 atoms/mol
23
For 1 m : 3 N    (1m 3 )   8  10 28 atoms
A Cu

NV = (2.7 x 10-4)(8.0 x 1028) sites = 2.2 x 1025 vacancies

8
 Example 4.1 The Effect of Temperature on
Vacancy Concentrations
Calculate the concentration of vacancies in copper at room
temperature (25°C). What temperature will be needed to heat treat
copper such that the concentration of vacancies produced will be
1000 times more than the equilibrium concentration of vacancies
at room temperature? Assume that 20,000 cal are required to
produce a mole of vacancies in copper. The lattice parameter of
FCC copper is 0.36151 nm
SOLUTION
. The basis is 1, therefore, the number of copper atoms, or lattice points,
per cm3 is:

4 atoms/cell 22 3
n  8 3
 8 .47  10 copper atoms/cm
(3.6151  10 cm)
9
Example 4.1 SOLUTION (Continued)

At room temperature, T = 25 + 273 = 298 K:

 Q 
n  n exp 
 RT 
 cal 
  20,000 
 atoms  mol
. exp 
22
  8.47  10 3 
 1.987 cal
 cm 
  298K 
 mol  K 
 1.815  108 vacancies/cm 3
We could do this by heating the copper to a temperature at which this
number of vacancies forms:
11  Q 
n  1.815  10  n exp 
 RT 
22 o
 (8.47  10 ) exp(20,000 /(1.987  T )), T  102 C
10
 Example 4.2 Vacancy
Concentrations in Iron

Determine the number of vacancies needed for a BCC iron crystal to

have a density of 7.87 g/cm3. The lattice parameter of the iron is 2.866 
10-8 cm.
Example 4.2 SOLUTION
The expected theoretical density of iron can be calculated from the
lattice parameter and the atomic mass.

11
Example 4.2 SOLUTION (Continued)

Let’s calculate the number of iron atoms and vacancies that would
be present in each unit cell for the required density of 7.87 g/cm3:

Or, there should be 2.00 – 1.9971 = 0.0029 vacancies per unit cell.
The number of vacancies per cm3 is:

12
 Vacancy defects
Island grows/shrinks to maintain
equil. vancancy conc. in the bulk.

 Vacancy can be produced

by raising the temperature
or by irradiation with fast
moving nuclear particles
 Vacancy can move in the
lattice structure and
therefore plays an
important part in diffusion
of atoms through the lattice

13
Impurities
Interstitial - atom that occupies a place outside the normal
lattice position. May be same type of atom (self interstitial)
or an impurity interstitial.

 Impurities may be added intentionally or unintentionally

Carbon in small amounts in iron makes steel. It is stronger.
Boron in silicon change its electrical properties.
 Point defects: self-interstitials, impurities

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

Arrows  local stress

5 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) 15
 Alloys
 An alloy composed of two or more elements, the principal one
of which is a metal
 An alloy properties may be different to that of the base metal
even when only small amounts of alloying additions or
impurities are present
 Most alloys are made in the molten state, i.e. base metal is
melted; alloying elements are added; and mixture is cooled
 The solid state atom arrangements have three possible
arrangements (or combinations of these three may also occur):
 Two phase structures
 Intermetallic compounds
 Solid solutions

16
 Alloys: two phase structure
A two phase structure results when the base metal and alloying
addition solidify as separate entities. E.g. when Sb is added to
Pb, each metal solidifies independently and maintains its
individual properties (i.e. two distinct crystal structures are
present in the solidified alloy)

17
Alloys – intermetallic compound
Intermetallic compounds form if the base metal and alloying
addition combine chemically in fixed proportions to produce a
new crystal structure. E.g. Mg2Si

18
 Alloys – solid solution
A solid solution forms when the base metal and alloying addition are
soluble in each other in the solid state
 Only one atomic structure is present, that of the base metal. The
solvent atoms are those of the base metal
 The atoms of the alloying addition are absorbed into that structure
forming a single phase. The solute atoms are the atoms of the
alloying addition
There are two types of solid solutions depending on the relative atomic
sizes of the solute and solvent:
1) Interstitial: solute atoms are much smaller than solvent atoms
2) Substitutional: solute and solvent atoms are about the same size
(differ by less than about 15%); Solute atom substitutes for the
solvent atom on the lattice site

19
 Effect of adding C to Fe
The. carbon content can change the hardness, tensile strength
and yield strength of steel

20
 Impurities in Solids
• Specification of composition
m1
– weight percent C1  x 100
m1  m2
m1 = mass of component 1

n m1
– atom percent C 
'
1 x 100
nm1  n m 2

nm1 = number of moles of component 1

21
 Point Defects in Alloys
Two outcomes if impurity (B) is added to host (A):
 Solid solution of B in A (i.e. random distribution of point defects)

OR

Substitution alloy Interstitial alloy

(e.g. Cu in Ni) (e.g. C in Fe)
 Solid solution of B in A plus particles of a new phase
Second phase particle
--different composition
--often different structure.

22
 Substitutional Solid Solution
Will mixing 2 (or more) different types of atoms always lead
to a substitutional solid-solution phase?

+1 +2

Empirical observations have identified 4 major contributors:

Atomic Size Factor, Crystal Structure, Electronegativity, Valences

23
 Hume-Rothery conditions for Substitutional Solid
Solution
1) Atomic Size Factor The 15% Rule
Difference in atomic radii between the two atom types needs to be less than 15%.
Otherwise the solute atoms will create substantial lattice distortions and a new
phase will form.

2) Crystal Structure Like elemental crystal structures are better

For appreciable solubility, the crystal structure for metals must be the same.

3) Electronegativity Differences in E ~ 0% favors solid-solution.

The more electropositive one element and the more electronegative the other, then
"intermetallic compounds" (order alloys) are more likely.

4) Valences Similar or Higher valence

All else being equal, a metal will have a greater tendency to dissolve a
metal of higher valence than one of lower valence

24
 Test Your Understanding
Is Cu-Ni substitutional solid-solution favorable, or not?
· Cu-Ni Alloys
Rule 1: rCu = 0.128 nm and rNi= 0.125 nm. DR%= 2.3%
favorable √
Rule 2: Both Ni and Cu have the FCC crystal structure
favorable √
Rule 3: ECu = 1.90 and ENi= 1.80. Thus, E%= -5.2%
favorable √
Rule 4: Valencies of Ni and Cu are both +2
favorable √
Expect Ni and Cu to form substitutional solid solution
over wide composition range
25
Interstitial Solid Solution
Impurity atoms fill the voids or
interstices in host lattice.

So, atomic diameter of interstitial

impurity must be substantially
smaller than that of host atoms

Normally, maximum allowable

concentration of interstitial impurity
atoms is < 10%, as even very small
atoms introduce huge lattice
distortions

W. Hume – Rothery rules do not apply!

26
Interstitial solid solution
An important solid solution is Carbon in Iron
Carbon BCC below 910 °C

Element C Fe
*Radii 0.071nm 0.124nm

Unit cell Hex BCC

Electronegativity 2.5 1.6

Valence +4 +2 (+3)

Not subsitutional! Why

C - 2s 2p
2 2

Fe – 3d6 4s2 Check Rothery rulesNot satisfy

 Interstitial solid solution.
 Composition of Alloy
Amount of impurity (B) and host (A) in the system.
Two descriptions:
• Weight (wt) % • Atom (at) %
mass of B # atomsof B
CB = x 100 C'B = x 100
total mass total # atoms
 Conversion between wt % and at% in an A-B alloy:
C' BAB C B/AB
CB = x 100 C' B =
C' AAA +C' BAB C A/AA +C B/AB

 Basis for conversion: atomic weight of B

mass of B =moles of B x AB atomic weight of A
mass of A =moles of A x AA

28
 Test Your Understanding
Determine the composition, in atom percent, of an alloy that
consists of 97 wt% aluminum and 3 wt% copper.

Denote the respective weight percent compositions as CAl = 97%

and CCu = 3%,
C Al A Cu (97)(63.55)
C 'Al  100  100  98.7(atom %)
C Al A Cu  C Cu A Al (97)(63.55)  (3)( 26.98)

C Cu A Al (3)( 26.98)
C 'Cu  100  100  1.3(atom %)
C Al A Cu  C Cu A Al (97)(63.55)  (3)( 26.98)

29
 Review quiz of previous lecture
Describe the microscopic structure of polycrystalline materials

Polycrystalline materials
comprised of many small crystals
or grains. The grains have
different crystallographic
orientation. There exist atomic
mismatch within the regions
where grains meet. These regions
are called grain boundaries.

30