MSE-101

Fundamentals of
Engineering Materials

Chapter 4
IMPERFECTIONS IN SOLIDS
Dr. Zubair Khan

1
CHAPTER 4:
IMPERFECTIONS IN SOLIDS
ISSUES TO ADDRESS...
• What are the solidification mechanisms?

• What types of defects arise in solids?

• Can the number and type of defects be varied and controlled?

• How do defects affect material properties?

• Are defects undesirable?

2
Imperfections in Solids

There is no such thing as a perfect crystal.

• What are these imperfections?
• Why are they important?

Many of the important properties of materials are due to

the presence of imperfections.

Examples
• Alloys
• Catalytic Converter
• Electronics ( Semiconductors )

3
Imperfections in Solids
Atomic defects are responsible for
reductions of gas pollutant emissions
from today’s automobile engines.

(a) High-resolution transmission

electron micrograph that shows
surface defects on single crystals
of one material that is used in
catalytic converters.

(b) Ceramic monolith on which the

metallic catalyst substrate is
deposited 4
Imperfections in Solids
• Solidification- result of casting of molten material
• 2 steps
• Nuclei form
• Nuclei grow to form crystals – grain structure
• Start with a molten material – all liquid

nuclei crystals growing grain structure

liquid Adapted from Fig.4.14 (b), Callister 7e.

• Crystals grow until they meet each other

5
 Polycrystalline Materials

Grain Boundaries
• regions between crystals
• transition from lattice of one region
to that of the other
• slightly disordered
• low density in grain boundaries
• high mobility
• high diffusivity
• high chemical reactivity

Adapted from Fig. 4.7, Callister 7e.

6
Solidification
Grains can be - equiaxed (roughly same size in all directions)
- columnar (elongated grains)
~ 8 cm

heat
flow

Shell of
Columnar in equiaxed grains
area with less due to rapid
undercooling cooling (greater
T) near wall
Adapted from Fig. 4.12, Callister 7e.

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

7
Types of Imperfections
• Vacancy atoms
• Interstitial atoms Point defects
• Substitutional atoms

• Dislocations Line defects

• Grain Boundaries Area defects

8
Point Defects
• Vacancies:
-vacant atomic sites in a structure.

Vacancy
distortion
of planes

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

self-
interstitial
distortion
of planes

Interstitial site: a small void space that under ordinary

9
circumstances is not occupied
Point Defects

10
C in alpha Fe - Interstitial solid solution
Equilibrium Concentration: Point Defects

• Equilibrium concentration varies with temperature!

No. of defects Activation energy

 -Q 
= exp  
Nv v
No. of potential
N  kT 
Atomic sites.
Temperature
Boltzmann's constant
(1.38 x 10 -23 J/atom-K)
(8.62 x 10 -5 eV/atom-K)

For most metals, the fraction of vacancies /N just below the melting
temperature is on the order of 10-4; that is, one lattice site out of
10,000 will be empty.
12
13
IMPURITIES IN SOLIDS
• Even with relatively sophisticated techniques, it is difficult to
refine metals to a purity in excess of 99.9999%.
• At this level, on the order of 1022 to 1023 impurity atoms will be present
in one cubic meter of material.

• Most familiar metals are not highly pure; rather, they are alloys,
• In which impurity atoms have been added intentionally to impart
specific characteristics to the material.

• Ordinarily, alloying is used in metals to improve mechanical

strength and corrosion resistance.

14
Solid solution / Solute, Solvent
• The addition of impurity atoms to a metal will result in the
formation of a solid solution and/o a new second phase:
• depending on the kinds of impurity, their concentrations, and the
temperature of the alloy.

• Solvent represents the element or compound that is present in

the greatest amount; on occasion, solvent atoms are also called
host atoms.

• Solute is used to denote an element or compound present in a

minor concentration.
15
Impurity point defects in solid solutions
• Two types: substitutional and interstitial.
• For the substitutional type, solute or
impurity atoms replace or substitute for the
host atoms
• Atomic size factor: atomic radii between
the two atom types is less than about ±15%;
substantial lattice distortions and a new
phase will form
• Crystal structure: crystal structures for
metals of both atom types must be the
same
• Electronegativity: with high difference,
intermetallic compound
• Valences: tendency to dissolve another
metal of higher valency than one of a lower
valency 16
Point Defects in Alloys
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.

17
Imperfections in Solids
To express the composition (or concentration) of an alloy in terms of its
constituent elements:

• 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

18
Line Defects
Dislocations

• Dislocations are linear defects / one-dimensional defect around

which some of the atoms are misaligned.
• Dislocations could be EDGE, SCREW or MIXED character
• Edge dislocation is an extra half plane whose edge terminates
within the crystal. The edge is called the dislocation line.
• Localized lattice distortion around the dislocation line. It
decreases as distance from the line increases.
Highest distortion is around the core of the dislocation

TS - ME106 19
Line Defects
Dislocations:
• are line defects,
• slip between crystal planes result when dislocations move,
• produce permanent (plastic) deformation.

Schematic of Zinc (HCP):

• before deformation • after tensile elongation

slip steps

Adapted from Fig. 7.8, Callister 7e.

20
Imperfections in Solids
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 ⊥ to dislocation line
• Screw dislocation:
• spiral planar ramp resulting from shear deformation
• b  to dislocation line

Burger’s vector, b: measure of lattice distortion in term of magnitude and direction.

21
Imperfections in Solids

Edge Dislocation

Fig. 4.3, Callister 7e.

22
Imperfections in Solids

Screw Dislocation Screw Dislocation

b
Dislocation
line
Burgers vector b (b)
(a)
Adapted from Fig. 4.4, Callister 7e.

23
Edge, Screw, and Mixed Dislocations
Most dislocations found in crystalline materials are probably neither pure edge
nor pure screw, but exhibit components of both types; these are termed mixed
dislocations.
Mixed

Edge

Adapted from Fig. 4.5, Callister 7e.

Screw 24
Dislocations are visible in electron micrographs

A transmission electron micrograph

of a titanium alloy in which the dark
lines are dislocations. 51,450X
(Courtesy of M. R. Plichta, Michigan
Technological University.)

25
Burgers vector of an edge dislocation
The magnitude and direction of the lattice distortion associated with a
dislocation is expressed in terms of a Burgers vector, denoted by a b.
Dislocation Characteristics
• Compressive stresses above the dislocation line and tensile
stresses below the dislocation line
• Atomic distortion associated with a screw dislocation is
shear. There is no extra half plane. A spiral path could be
traced around the dislocation line
• Most dislocations found in crystals are neither pure edge
nor pure screw but mixed

TS - ME106 27
• The magnitude and direction associated with a
dislocation is represented by a “Burgers vector” b
• The orientation of the Burgers vector relative to the
dislocation line depends on the type of dislocation
Edge - b is perpendicular to line
Screw - b is parallel to line
Mixed - b is at an angle to line

TS - ME106 28
• A dislocation may change its character from edge to screw
to mixed within a crystal but its Burgers vector is an
invariant.
• Dislocations must begin and end on a surface, grain
boundary or another dislocation
• For metals, the Burgers vector of a dislocation will be in
the close packed direction and its magnitude will be equal
to one inter-atomic spacing
• Dislocations play an important role in the plastic
deformation of crystalline materials.

TS - ME106 29
 Dislocations & Crystal Structures
• Structure: close-packed view onto two
planes & directions close-packed
planes.
are preferred.
close-packed directions
close-packed plane (bottom) close-packed plane (top)

• Comparison among crystal structures:

FCC: many close-packed planes/directions;
HCP: only one plane, 3 directions [100], [010] and [110] ;
BCC: none

• Specimens that were tensile Mg (HCP)

tested.
tensile direction
Al (FCC)
30
Motion of Edge Dislocation
• Dislocation motion requires the successive bumping
of a half plane of atoms (from left to right here).
• Bonds across the slipping planes are broken and
remade in succession.

Atomic view of edge

dislocation motion from
left to right as a crystal
is sheared.

(Courtesy P.M. Anderson)

31
INCREMENTAL SLIP
• Dislocations slip planes incrementally...
• The dislocation line (the moving red dot)...
...separates slipped material on the left
from unslipped material on the right.

Simulation of dislocation
motion from left to right
as a crystal is sheared.

(Courtesy P.M. Anderson)

12
Interfacial Defects
• Two dimensions and separate regions of the materials that
have different crystal structures and/or crystallographic
orientations.
• Planar defects such as
• external surfaces
• grain boundaries
• twin boundaries
• phase boundaries/interfaces
• Ferromagnetic domain walls
• stacking faults

TS - ME106 33
 External surfaces
• Most obvious boundaries along which the crystal structure
terminates
• Surface atoms are not bounded to the maximum number of nearest
atoms.
• Higher energy state than the atoms at interior positions…..give rise
to surface energy.
• To reduce this energy, material tend to minimize the total surface
area.

34
External surfaces

35
Grain Boundaries
• Many crystalline materials are composed of many
small crystals called grains. Such materials are
polycrystalline
• Grain boundary is the region separating two
grains
• There is a change in the orientation of the crystals
across a grain boundary
Planar Defects in Solids
• One case is a twin boundary (plane)
• Essentially a reflection of atom positions across the twin
plane.

Adapted from Fig. 4.9, Callister 7e.

• Stacking faults
• For FCC metals an error in ABCABC packing sequence
• Ex: ABCABABC
38
Stacking Faults
• Perfect Stacking (FCC)
ABCABCABCABC
Twin

ABCABCBACBA

Stacking Fault

ABCABCBCABC
Microscopic Examination
• Crystallites (grains) and grain boundaries. Vary considerably in
size. Can be quite large
• ex: Large single crystal of quartz or diamond or Si
• ex: Aluminum streetlight posts (highway guard rails) or garbage can -
see the individual grains

• Crystallites (grains) can be quite small (mm or less) – necessary

to observe with a microscope.
• Grain size and shape

40
Optical Microscopy
• Useful up to 2000X magnification.
• Polishing removes surface features (e.g., crystallographic planes
scratches)
• Etching changes reflectance, depending on
crystal
orientation. Micrograph of
brass (a Cu-Zn alloy)

0.75mm

Adapted from Fig. 4.13(b) and (c), Callister

7e. (Fig. 4.13(c) is courtesy
of J.E. Burke, General Electric Co.

41
Optical Microscopy
Grain boundaries...
• are imperfections, polished surface
• are more susceptible to etching,
surface groove
• may be revealed as dark lines,
grain boundary
• change in crystal orientation across (a)
boundary.
Adapted from Fig. 4.14(a)
ASTM grain and (b), Callister 7e.
size number (Fig. 4.14(b) is courtesy
of L.C. Smith and C. Brady,
the National Bureau of
N = 2n-1 Standards, Washington, DC
[now the National Institute of
Fe-Cr alloy Standards and Technology,
Gaithersburg, MD].)
number of grains/in2
(b)
at 100x
magnification

42
 Optical Microscopy
• Polarized light
• metallographic scopes often use polarized (made to
move in one direction only) light to increase contrast

• Also used for transparent samples such as

polymers

Polarized light optical

microscope images for the
cross-sections of original foils
and fibre embedded samples

43
 Microscopy
Optical resolution ca. 10-7 m = 0.1 m = 100 nm
For higher resolution need higher frequency
• X-Rays? Difficult to focus.
• Electrons
• wavelengths ca. 3 pm (0.003 nm)
• (Magnification - 1,000,000X)
• Atomic resolution possible
• Electron beam focused by magnetic lenses.

44
Scanning Tunneling Microscopy
(STM)
• Atoms can be arranged and imaged!
Photos produced from
the work of C.P. Lutz,
Zeppenfeld, and D.M.
Eigler. Reprinted with
permission from
International Business
Machines Corporation,
copyright 1995.

Carbon monoxide Iron atoms arranged

molecules arranged on a copper (111)
on a platinum (111) surface. These Kanji
surface. characters represent
the word “atom”.

45
Summary
• Point, Line, and Area defects exist in solids.

• The number and type of defects can be varied

and controlled (e.g., T controls vacancy conc.)

• 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.)

46
SUMMARY
• Atoms may assemble into crystalline or amorphous structures.
• Common metallic crystal structures are FCC, BCC, and HCP. Coordination
number and atomic packing factor are the same for both FCC and HCP crystal
structures.
• We can predict the density of a material, provided we know the atomic
weight, atomic radius, and crystal geometry (e.g., FCC, BCC, HCP).

• Crystallographic points, directions and planes are specified in terms

of indexing schemes.
Crystallographic directions and planes are related to atomic linear
densities and planar densities.

47
SUMMARY
• Materials can be single crystals or polycrystalline.
Material properties generally vary with single crystal
orientation (i.e., they are anisotropic), but are generally
non-directional (i.e., they are isotropic) in polycrystals
with randomly oriented grains.
• Some materials can have more than one crystal
structure. This is referred to as polymorphism (or
allotropy).

• X-ray diffraction is used for crystal structure and

interplanar spacing determinations.

48