Imperfections in Solids

(Chapter 4 of Callister)

Coordinator: An Mai, PhD, PEng

 Learning Objectives

• By the end of this chapter, you will be able to:

• Identify the 4 types of point defects in crystals

• Visualize the placement of atoms in alloys
• Describe the difference between an edge and screw dislocation
• Explain why surfaces are considered a defect
• Calculate the weight percent and atom percent for each element in a metal
alloy

2
 Introduction

There is no such thing as a perfect crystal!

→Crystalline imperfections (or defects) are always present.
• Many of the properties of materials are sensitive to the presence of
imperfections.
• Crystalline defect refers to a lattice irregularity with dimensions on
the order of an atomic diameter.
• What kinds of crystalline imperfections exist in solids?

3
 Solidification
• Solidification- result of casting of molten material
• Nuclei of the solid phase form
• Crystals grow until their boundaries meet each other – the crystals
become grains
• Start with a molten material – all liquid

(now the National Institute of Standards

Bureau of Standards, Washington, DC

and Technology, Gaithersburg, MD.)]

[Photomicrograph courtesy of L. C.
Smith and C. Brady, the National
nuclei crystals growing grain structure
liquid Adapted from Fig. 4.15 (b), Callister & Rethwisch 10e.

4
 Solidification Cont.
Grains can be - equiaxed (roughly the same dimension in all directions)
- columnar (grains elongated in one direction)
~ 8 cm Adapted from Fig. 5.17,
Callister & Rethwisch 3e.
(Reproduced with permission
from Metals Handbook, Vol. 9,
9th edition, Metallography and
Microstructures, ASM
International, Materials Park,
OH, 1985.)

heat
flow

Shell of
Columnar in equiaxed grains
region with due to rapid
slower cooling cooling (greater
ΔT) near wall

Grain Refiner - added to make smaller, more uniform, equiaxed grains.

5
 Grains and Grain Boundaries

Grain Boundaries
• Regions between grains
(crystals)
• Crystallographic
misalignment across a grain
boundary
• Slight atomic disorder
• high atomic mobility
• high chemical reactivity

Fig. 4.8, Callister & Rethwisch 10e.

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 Types of Imperfections in Solids

• Vacancy atoms
• Interstitial atoms Point defects
• Substitutional atoms
• Self-interstitial atoms

• Dislocations Line defects

1D Defects

• Grain Boundaries Area defects

• Surfaces 2D defects
 Point Defects in Metals
• Vacancies -vacant atomic sites in a structure.

Vacancy
distortion
of planes

• Self-Interstitials -"extra" atoms positioned between atomic sites.

self-
interstitial
distortion
of planes
 Calculating the Number of Vacancies

• Equilibrium concentration varies with temperature!

No. of defects Activation energy

Nv −Q v
No. of potential = exp
defect sites N kT
Temperature
Boltzmann's constant
-23
(1.38 x 10 J/atom-K)
-5
(8.62 x 10 eV/atom-K)
Each lattice site
is a potential
vacancy site
 Example

• Find the equilibrium number of vacancies in 1 m3 of Cu at 1000°C.

• Given:
ρ = 8.4 g /cm 3 A Cu = 63.5 g/mol
Qv = 0.9 eV/atom NA = 6.022 x 1023 atoms/mol

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 Impurities in Solids

• Pure metal consisting of only ONE type of atom is IMPOSSIBLE!

• Most metals are not highly pure; they are ALLOYS.
• Impurity atoms were added to improve specific property of the materials.
• Examples:
• Sterling silver: 92.5% silver + 7.5% copper
→ increase mechanical strength while maintaining corrosion resistance
• 24 kt gold: pure gold (VERY SOFT)
• 18 kt gold: 18 parts gold + 6 parts of another metal(s) → 75% gold
• 14 kt gold: 14 parts gold + 10 parts of another metal(s) → 58.3% gold

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 Impurities in Solids Cont.

• The addition of impurity atoms to a metal results in the formation of

a solid solution and/or a new second phase.
• Depending on kinds of impurity, concentrations, and temperature.
• Some terminologies:
• Solvent: element that is present in the greatest amount (host atoms)
• Solute: element that is present in minor concentration.

• Solid solution: when solute atoms are added to the host material, the
crystal structure is maintained, and no new structures are formed.

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 Alloying in Metals
Two outcomes if impurity (B) added to host (A):
• Solid solution of B in A (i.e., random dist. of point defects)

OR

Substitutional solid soln. Interstitial solid soln.

(e.g., Cu in Ni) (e.g., C in Fe)
• 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.
 Alloying in Metals Cont.

• Pure metals are soft and susceptible to rusting

→alloys can be created to be corrosive resistant, harder, and stronger
than pure metal!
• Some common substitutional alloys (metal + metal):
• Bronze (78 - 95% copper + 5 - 22% tin)
• Sterling silver (93% silver + 7% copper)
• Brass (60 - 90% copper + 10 - 35% zinc)
• Some common interstitial alloys (metal + non-metal):
• Steel (99% copper + 1% carbon)
• Cast iron (96 - 98% iron + 2 - 4% carbon)

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 Conditions for Solid Solutions – Substitutional Impurity

Conditions for substitutional solid solution (S.S.)

• W. Hume – Rothery rule
– 1. Δr (atomic radius) < 15%
– 2. Proximity in periodic table
• i.e., similar electronegativities
– 3. Same crystal structure for pure metals
– 4. Valency
• All else being equal, a metal will have a greater tendency
to dissolve a metal of higher valency than one of lower
valency
 Example of Substitutional Solid Solution

• Copper and nickel → completely soluble!

• Atomic radii for Cu and Ni: 0.128 and 0.125 nm, respectively
• Both have FCC crystal structure
• Electronegativities for Cu and Ni: 1.9 and 1.8, respectively
• Valences: +1 (or +2) for Cu and +2 for Ni

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 Application of Hume–Rothery rules – Substitutional

Ex: Would you predict

Element Atomic Crystal Electro- Valence
more Al or Ag to Radius Structure nega-
dissolve in Zn? (nm) tivity
Cu 0.1278 FCC 1.9 +2
C 0.071
H 0.046
O 0.060
Ag 0.1445 FCC 1.9 +1
1. Δr – slightly favors Al Al 0.1431 FCC 1.5 +3
Co 0.1253 HCP 1.8 +2
2. Electronegativity – favors Al Cr 0.1249 BCC 1.6 +3
3. Crystal structure – tie Fe 0.1241 BCC 1.8 +2
4. Valences –higher valance more Ni 0.1246 FCC 1.8 +2
soluble so favors Al Pd 0.1376 FCC 2.2 +2
Zn 0.1332 HCP 1.6 +2

This suggests Al is more soluble Table on p. 135, Callister & Rethwisch 9e.

17 in Zn. This agrees with experimental observations.

 Try This!

• 4.6 Below, atomic radius, crystal structure,

electronegativity, and the most common
valence are tabulated, for several elements;
for those that are nonmetals, only atomic
radii are indicated.

• Which of these elements would you expect

to form the following with copper:
(a) A substitutional solid solution having
complete solubility
(b) A substitutional solid solution of
incomplete solubility
(c) An interstitial solid solution

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 Imperfections – Interstitial Impurities
• Interstitial impurities exist in gaps between
the atoms in the lattice.
• These gaps have defined sizes, depending
on BCC or FCC crystals

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 Imperfections – Interstitial Impurities Cont.
• Two types of interstitial sites:
• Tetrahedral (coordination # = 4)
• Octahedral (coordination # = 6)

• BCC:
• # of tetrahedral sites: ?
• # of octahedral sites: ?
• FCC:
• # of tetrahedral sites: ?
• # of octahedral sites: ?

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 Imperfections – Interstitial Impurities Cont.

• Metallic materials:
• High APF → interstitials sites are very small → r << R!
• Concentration of interstitial impurity atoms is low ( <
10%).
• Steel: maximum concentration of C is about 2%.
• Ceramic materials:
• Atomic point defects are possible for ceramics!
• Ceramic materials contains at least two kinds of ions
→ Defects for each ion type may occur!
• Atomic point defects: both vacancies and interstitials
are possible.
• Solid solutions of both substitutional and interstitial
types are also possible.
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 Size of Octrahedral Site in BCC

• Compute the radius, r, of an impurity

atom that just fits into a BCC octahedral
site in term of R, radius of host atom,
without introducing lattice strains).

22
 Size of Tetrahedral Site in BCC

23
 Interstitial Sites in FCC

• Size of tetrahedral sites in FCC = ?

• Size of octahedral sites in FCC = ?

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 Calculating Composition of Alloy

• Specification of composition
m1
– weight percent C1 = x 100
m1 + m2
m1 = mass of component 1

nm1
– atom percent C =
'
x 100
nm1 + nm 2
1

nm1 = number of moles of component 1

 Calculating Composition of Alloy Cont.

• Density and atomic weight:

100
𝜌𝑎𝑣𝑒 =
𝐶1 𝐶2
+
𝜌1 𝜌2

100
𝐴𝑎𝑣𝑒 =
𝐶1 𝐶2
+
𝐴1 𝐴2

With 𝜌 being density and A is the atomic weight.

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 Example

• 4.14 What is the composition, in weight percent, of an alloy that consists of 6

at% Pb and 94 at% Sn?

• Given that:
• APb = 207.2 g/mol
• ASn = 118.71 g/mol

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 Another Example

• 4.35 Silver and palladium both have the FCC crystal structure, and Pd forms a
substitutional solid solution for all concentrations at room temperature. Compute
the unit cell edge length for a 75 wt% Ag & 25 wt% Pd alloy. The room-
temperature density of Pd is 12.02 g/cm3, and its atomic weight and atomic radius
are 106.4 g/mol and 0.138 nm, respectively.

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 Summary on Point Defects

• There are 4 types of point defects

• Vacancy
• Self-interstitial
• Interstitial
• Substitutional
• Alloy concentration can be expressed as mass % or atomic %
• Must be able to switch back and forth between the two
• Point defects change the perfect periodicity of the crystal
• This often changes dislocation/electron transport in the crystal

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 Observation of Dislocations
Dislocations appear as dark lines in this electron micrograph

Fig. 4.7, Callister & Rethwisch 10e.

(Courtesy of M. R. Plichta, Michigan
Technological University.)

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 Dislocations – Linear Defects
Dislocations:
• move when stresses are applied,
• permanent (plastic) deformation results from dislocation motion.

Schematic of a single crystal metal

• unstressed • after tensile elongation
(undeformed) (after plastic deformation)

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 Dislocations – 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 perpendicular ( ) to dislocation line
• Screw dislocation:
• spiral planar ramp resulting from shear deformation
• b parallel ( ) to dislocation line

https://www.doitpoms.ac.uk/tlplib/dislocations
/dislocations_in_3D.php

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 Edge Dislocation

Edge Dislocation

Fig. 4.4, Callister & Rethwisch 9e. (Adapted from

A. G. Guy, Essentials of Materials Science, McGraw-Hill
Book Company, New York, NY, 1976, p. 153.)
 Screw Dislocation
(a) Schematic of screw (b) Top view of screw
dislocation in (a)
dislocation in a crystal

[010]

Burgers vector b (b)

(a)

• Lattice plane shifts by one layer (or more).

• Burgers vector is parallel to the dislocation lines
 Mixed Dislocations

• Mixed dislocations:
• Consisting of both screw and edge characteristics!
• Where the line direction and Burgers vector are neither perpendicular
nor parallel!
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 Planar Defects

• Grain boundaries
• Phase boundaries Twin plane (boundary)

• Twin boundaries (or planes)

• Mirror reflections of atom positions of one side of twin
plane to the other side.
• Stacking faults
• Occur when there is an error in the planar stacking
sequence
• Ex: for FCC metals
 normal sequence is ABCABC
Fig. 4.10, Callister &
 becomes ABCABABC when there is a packing fault Rethwisch 9e.

36
 Summary

• Defects in materials are responsible for many material properties we

observe daily.
• Alloying through substitutional/interstitial defects make materials stronger.
• Vacancies can make materials weaker/softer (eg. melting processes).
• Plastic/permanent deformation occurs through dislocation motion.
• At the surface/grain boundaries, there is atomic mismatch, which create areas
of high energy → more chemically reactive!
 Summary Cont.
• Point, Linear, and Interfacial defects exist in solids.
• Point defects • Linear defects
- Vacancies - Dislocations
- Interstitial atoms • Interfacial defects
- Substitutional impurity - Grain boundaries
atoms - Twin boundaries
- Stacking Faults

• The equilibrium number vacancy defects depends on temperature

æ Q ö
NV = N exp ç - v ÷
è kT ø
• Dislocation types include edge, screw, and mixed

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 Suggested Problems

• 4.2, 4.3, 4.5

• 4.6, 4.7
• 4.8, 4.9, 4.10
• 4.12, 4.13, 4.16, 4.22, 4.23, 4.28
• 4.36, 4.37, 4.38

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