Chapter 3: Imperfection in Crystals.

Learning objectives

 Describe both vacancy and self-intersticial defects.

 Calculate the equilibrium number of vacancies in a material at
some specified temperature.
 Describe all the puntual defects.
 Describe the dislocations and surface defects.
 Calculate the number of grains using a microphotography.

Engineering Physics Program – MsC. Ivan Arellano – Ch_3 Imperfections in Crystals

 3.1. Point Defects
a) Vacancies: The simplest point defect is a vacancy. This refers to an empty
(unoccupied) site of a crystal lattice, i.e. a missing atom or vacant atomic site.
They arise due to thermal vibrations of
the atoms at higher temperatures.
n T
n: the number of vacancies
𝐸𝑣 per cm3.
𝑛 = 𝑁𝑒𝑥𝑝 − N: the number of atoms per
𝑘𝐵 𝑇 cm3.
𝑬𝒗 : Energy to form one
vacancy
𝒌𝑩 : Boltzmann constant

Engineering Physics Program – MsC. Ivan Arellano – Ch_3 Imperfections in Crystals

Problem 1: Compute the number of vacancies per atom if Ev = 1 eV and T =
1000K.
Ans: 1 vacancy in 105 atoms

Problem 2: Calculate the concentration of vacancies in copper at 25 oC. 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? Ans: ̴ 100 oC
Hint: FCC structure and a lattice parameter of 3.615 Å.

Problem 3: Determine the number of vacancies needed for a BCC iron crystal
to have a density of 7.87 g/cm3. The lattice parameter of BCC iron is 2.866 Å.
Ans: 1.078 × 1020 𝑣𝑎𝑐/𝑐𝑚3 Find T assuming an Ev = 0.89 eV

Engineering Physics Program – MsC. Ivan Arellano – Ch_3 Imperfections in Crystals

b) Intersticial defect: An interstitial defect is formed when an extra atom or
ion is inserted into the crystal structure at a normally unoccupied position.
Problem 4: Interstitial Sites for Carbon in Iron

In FCC iron, carbon atoms are located at octahedral sites at

the center of each edge of the unit cell (1/2, 0, 0) and at the
center of the unit cell (1/2, 1/2, 1/2). In BCC iron, carbon
atoms enter tetrahedral sites, such as 1/4, 1/2, 0. The lattice
parameter is 0.3571 nm for FCC iron and 0.2866 nm for BCC
iron.
Assume that carbon atoms have a radius of 0.071 nm. (1)
Would we expect a greater distortion of the crystal by an
interstitial carbon atom in FCC or BCC iron? (2) What would
be the atomic percentage of carbon in each type of iron if all
the interstitial sites were filled?

Engineering Physics Program – MsC. Ivan Arellano – Ch_3 Imperfections in Crystals

Instersticial sites for FCC metal.
Instersticial sites for BCC metal.

Engineering Physics Program – MsC. Ivan Arellano – Ch_3 Imperfections in Crystals

c) Substitutional defect: A substitutional defect is introduced when one atom
or ion is replaced by a different type of atom or ion.

small substitutional atom large substitutional atom

Engineering Physics Program – MsC. Ivan Arellano – Ch_3 Imperfections in Crystals

Hume – Rothery Rules: Determine the conditions of an atom to form a
substitutional defect.
1. Atomic size: the difference in atomic radii between the guest and host
atoms should be about 15%.
2. Crystal structure: the crystal structure for both atoms must be the same.
3. Electronegativity: electronegativity must be similar.
4. Valence: Similar valences of both atoms.

Cu and Ni are perfect! RCu = 1.28 Å RNi = 1.25 Å Cu: 1 val. Ni: 2 val

FCC structure for both elements

Engineering Physics Program – MsC. Ivan Arellano – Ch_3 Imperfections in Crystals

d) Schottky defect: this defect is caused, whenever a pair of positive and
negative ions is missing from a crystal.

Missing a positive ion

Missing a negative ion

Electroneutrality

Cation-anion vacancy pair

Engineering Physics Program – MsC. Ivan Arellano – Ch_3 Imperfections in Crystals

 e) Frenkel defect: formed by a cation leaving its normal position and moving
into an interstitial site.
Frenkel pair (vacancy-interstitial)
−𝑄𝑓𝑟
𝑁𝑓𝑟 = 𝑁𝑒𝑥𝑝
2𝑘𝑇

−𝑄𝑠
𝑁𝑠 = 𝑁𝑒𝑥𝑝
2𝑘𝑇
N = Number of lattice sites.
Nfr,s = Number of Frenkel or Schottky defects.
Qfr,s = Energy required for the formation of a Frenkel or Schottky defect.

Engineering Physics Program – MsC. Ivan Arellano – Ch_3 Imperfections in Crystals

 Computation of the Number
of Schottky Defects in KCl

Calculate the number of Schottky

defects per cubic centimeter in
potassium chloride at 500◦C. The
energy required to form each
Schottky defect is 2.6 eV, while
the density for KCl (at 500◦C) is
1.955 g/cm3. PA(K) = 39.10 g/mol
and PA(Cl) = 35.45 g/mol

Ans: 5.31 × 1013 defects/cm3

Engineering Physics Program – MsC. Ivan Arellano – Ch_3 Imperfections in Crystals

 3.2. Kröger – Vink Notation
The Kröger-Vink notation is used to write the defect chemistry equations.

X: Main letter element or vacancy

𝑐
𝑋𝑠 C: Charge of the defect
S: Site of the defect (element)

𝑥 𝑥 ∙
𝐴𝑙𝐴𝑙 𝑁𝑖𝐶𝑢 𝑉𝑁𝑎

Engineering Physics Program – MsC. Ivan Arellano – Ch_3 Imperfections in Crystals

When point defects are introduced the following rules have to be observed:

(a) a charge balance must be maintained so that the crystalline material as a

whole is electrically neutral.
(b) a mass balance must be maintained.
(c) the number of crystallographic sites must be conserved.

Exercise 1: Use the Kroger – Vink notation for the incorporation of MgO in NiO.

Exercise 2: Use the Kroger – Vink notation for the formation of one Schottky
defect in Al2O3.
Exercise 3: Use the Kroger – Vink notation for the incorporation of CaO in ZrO2.

Engineering Physics Program – MsC. Ivan Arellano – Ch_3 Imperfections in Crystals

 3.3. Linear defects or dislocations
A dislocation is a linear or one-dimensional defect around which some of
the atoms are misaligned. They are introduced typically into the crystal
during solidification of the material or when the material is deformed
permanently. Screw and Edge dislocations

Screw dislocation: The screw dislocation can be illustrated by cutting

partway through a perfect crystal, then skewing the crystal one atom
spacing. If we follow a crystallographic plane one revolution around the
axis on which the crystal was skewed, starting at point x and traveling
equal atom spacing in each direction, we finish one atom spacing below
our starting point (point y).

Engineering Physics Program – MsC. Ivan Arellano – Ch_3 Imperfections in Crystals

The magnitude and direction of the lattice distortion associated with a
dislocation is expressed in terms of a Burgers vector, denoted by a b.

Engineering Physics Program – MsC. Ivan Arellano – Ch_3 Imperfections in Crystals

Edge dislocation: An edge dislocation can be illustrated by slicing partway
through a perfect crystal, spreading the crystal apart, and partly filling the
cut with an extra plane of atoms.

Engineering Physics Program – MsC. Ivan Arellano – Ch_3 Imperfections in Crystals

Occurs plastic deformation Ductility

Engineering Physics Program – MsC. Ivan Arellano – Ch_3 Imperfections in Crystals

Exercise 1: Find the length of the Burgers vector in Copper (a = 3.615Å).

Identification of Preferred Slip Planes

The planar density of the (112) plane in BCC iron is 9.94x1014 atoms/cm2.
Calculate a) the planar density of the (110) plane and b) the interplanar
spacings for both the (112) and (110) planes. On which plane would slip
more probably occur?

Engineering Physics Program – MsC. Ivan Arellano – Ch_3 Imperfections in Crystals

 3.4. Surface defects
Surface defects are the boundaries, or planes, that separate a material into regions, each
region having the same crystal structure but different orientations. Surface imperfections
are of two types: external and internal.

The external surface of a material is an imperfection itself

because the atomic bonds do not extend beyond it.

The surface atoms have neighbours on one side only while

atoms inside the crystal have neighbours on either side of
them.

Engineering Physics Program – MsC. Ivan Arellano – Ch_3 Imperfections in Crystals

Grain Boundaries: The microstructure of many engineered ceramic and
metallic materials consists of many grains. A grain is a crystalline portion of
the material within which the arrangement of the atoms is nearly identical.
However, the orientation of the atom arrangement, or crystal structure, is
different for each adjoining grain.

Engineering Physics Program – MsC. Ivan Arellano – Ch_3 Imperfections in Crystals

 One method of controlling the
properties of a material is by
controlling the grain size. By
reducing the grain size, we
increase the number of grains
and, hence, increase the
amount of grain boundary
area.

Hall-Petch equation relates the grain size to the

𝜎𝑦 = 𝜎𝑜 + 𝐾𝑑 −1/2
yield strength.

d: average diameter of the grains, and σ0 1 𝑚𝑚 < 𝑑 < 100 𝑛𝑚

and K are constants for the metal.

Engineering Physics Program – MsC. Ivan Arellano – Ch_3 Imperfections in Crystals

Problem 1: The yield strength of steel with an average grain size of 0.05 mm
is 20000 psi. The yield stress of the same steel with a grain size of 0.007 mm
is 40000 psi. What will be the average grain size of the same steel with a
yield stress of 30000 psi? Assume the Hall-Petch equation is valid and that
changes in the observed yield stress are due to changes in grain size.
Ans: 14.8 µm

Engineering Physics Program – MsC. Ivan Arellano – Ch_3 Imperfections in Crystals

 3.5. Microscopic techniques
Optical microscopy is one technique that is used to reveal microstructural
features such as grain boundaries that require less than about 2000
magnification. The process of preparing a metallic sample and observing
or recording its microstructure is called metallography.

Engineering Physics Program – MsC. Ivan Arellano – Ch_3 Imperfections in Crystals

Measuring grain size
a) ASTM grain size number (ASTM is the American Society for Testing and
Materials).
𝑁 = 2𝑛−1

𝑁: Number of grains per square inch 100X

n: ASTM grain size number

A large ASTM number indicates many grains, or a finer grain size, and
correlates with high strengths for metals and alloys.

Engineering Physics Program – MsC. Ivan Arellano – Ch_3 Imperfections in Crystals

Calculation of ASTM Grain Size Number
Problem 1:
Suppose we count 60 grains per square inch in a photomicrograph taken
at magnification of 100X. What is the ASTM grain size number?

Problem 2:
Suppose we count 82 grains per square inch in a photomicrograph taken
at magnification of 200X. What is the ASTM grain size number?

Problem 3:
Suppose we count 13 grains per square inch in a photomicrograph taken
at magnification of 250X. What is the ASTM grain size number?

Engineering Physics Program – MsC. Ivan Arellano – Ch_3 Imperfections in Crystals

Measuring grain size
𝑙
b) Diameter of grain 𝑑=
𝑛𝑀
16
14 15
13
11
𝑙: 𝑙𝑒𝑛𝑔𝑡ℎ 𝑜𝑓 𝑡ℎ𝑒 𝑙𝑖𝑛𝑒
12
8 9 10
𝑛: 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑐𝑢𝑡𝑡𝑒𝑑 𝑔𝑟𝑎𝑖𝑛𝑠
6 7
5 l
4
3
𝑀: 𝑀𝑎𝑔𝑛𝑖𝑓𝑖𝑐𝑎𝑡𝑖𝑜𝑛
1 2

Engineering Physics Program – MsC. Ivan Arellano – Ch_3 Imperfections in Crystals