METE 230
Fundamentals of Materials Science
and Engineering
Chapter 4
Assist. Prof. Irmak Sargın
Fall 2022
Chapter 4 - 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?
Chapter 4 - 2
vacancies dislocations
[Link] [Link]
[Link]/wiki/V ki/Dislocation#/media/File:
acancy_defect TEM_micrograph_dislocat
ions_precipitate_stainless
_steel_2.jpg
Grain boundaries
Heuer, Arthur H., et al. "The band structure
Crystals are like people. It's the of polycrystalline Al2O3 and its influence on
transport phenomena." Journal of the
defects that make them American Ceramic Society 99.3 (2016):
733-747.
interesting. Colin Humpreys. Chapter 4 - 3
All your perfect imperfections*
• Point Defects (0-D)
✓ Vacancies
✓ Interstitial and substitutional atoms
• Linear Defects (1-D)
✓ Edge dislocation
✓ Screw Dislocation
• Planar Defects (2-D)
✓ Free surfaces
✓ Grain boundaries
✓ Tilt boundaries
✓ Twist boundaries
✓ Interphase boundaries
✓ Twin boundaries
• Bulk or volume defects (3-D)
*:a lattice irregularity having one or more its
dimensions on the order of atomic diameter Chapter 4 - 4
Dimensional Ranges of Defects
[Link] Chapter 4 - 5
But why?
Because just like perfectly ideal human beings, perfectly ideal
materials are very very very rare-almost non-existent.
So what we try to do is understanding these defects and try to
engineer them according to our property requirements dictated
by performance Defects are
components
of structure
Many of the important
properties of materials are due
to the presence of imperfections Chapter 4 - 6
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
Chapter 4 - 7
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
Chapter 4 - 8
Equilibrium Concentration:
Point Defects
• Equilibrium concentration varies with temperature!
No. of defects Activation energy
Nv −Q v
No. of potential = exp
defect sites N kT
Temperature (K)
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
Chapter 4 - 9
Measuring Activation Energy
• We can get Qv from Nv - Qv
an experiment. = exp
N kT
• Measure this... • Replot it...
Nv Nv slope
ln
N N
-Qv /k
exponential
dependence!
T 1/T
defect concentration
Chapter 4 - 10
Estimating Vacancy Concentration
• Find the equil. # of vacancies in 1 m3 of Cu at 1000C.
• Given:
ρ = 8.4 g/cm 3 A Cu = 63.5 g/mol
Qv = 0.9 eV/atom NA = 6.02 x 1023 atoms/mol
Chapter 4 - 11
Observing Equilibrium Vacancy Conc.
• Low energy electron
microscope view of
a (110) surface of NiAl.
• Increasing temperature
causes surface island of
atoms to grow.
• Why? The equil. vacancy
conc. increases via atom
motion from the crystal
to the surface, where Reprinted with permission from Nature (K.F. McCarty,
they join the island. J.A. Nobel, and N.C. Bartelt, "Vacancies in
Solids and the Stability of Surface Morphology",
Nature, Vol. 412, pp. 622-625 (2001). Image is
Island grows/shrinks to maintain 5.75 mm by 5.75 mm.) Copyright (2001) Macmillan
equil. vancancy conc. in the bulk. Publishers, Ltd.
Chapter 4 - 12
Imperfections in Metals (i)
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.
Chapter 4 - 13
Imperfections in Metals -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.
Chapter 4 - 14
Imperfections in Metals -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.
Chapter 4 - 15
Imperfections in Metals -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.
Chapter 4 - 16
Imperfections in Metals -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.
Chapter 4 - 17
Imperfections in Metals -Alloys
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
Chapter 4 - 18
Imperfections in Metals -Alloys
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
Chapter 4 - 19
Imperfections in Metals -Alloys
Application of Hume–Rothery rules – Solid
Solutions Element Atomic Crystal Electro- Valence
Radius Structure nega-
(nm) tivity
1. Would you predict Cu 0.1278 FCC 1.9 +2
C 0.071
more Al or Ag H 0.046
O 0.060
to dissolve in Zn? Ag 0.1445 FCC 1.9 +1
Al 0.1431 FCC 1.5 +3
Co 0.1253 HCP 1.8 +2
Cr 0.1249 BCC 1.6 +3
2. More Zn or Al Fe 0.1241 BCC 1.8 +2
Ni 0.1246 FCC 1.8 +2
in Cu? Pd 0.1376 FCC 2.2 +2
Zn 0.1332 HCP 1.6 +2
Table on p. 135, Callister & Rethwisch 9e.
Chapter 4 - 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 =
'
x 100
n m1 + n m 2
1
nm1 = number of moles of component 1
Chapter 4 - 21
• What is the composition, in atom
percent, of an alloy that consists of 30
wt% Zn and 70 wt% Cu?
Chapter 4 - 22
• Determine the approximate density of a
high-leaded brass that has a
composition of 64.5 wt% Cu, 33.5 wt%
Zn, and 2.0 wt%Pb.
Chapter 4 - 23
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 loading
slip steps
Chapter 4 - 24
Chapter 4 - 25
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 perpendicular (⊥) to dislocation line
• Screw dislocation:
– spiral planar ramp resulting from shear deformation
– b parallel () to dislocation line
Burger’s vector, b: measure of lattice distortion
Chapter 4 - 26
Video Time!!!
[Link]
9-jlmdw
Chapter 4 - 27
Line Defects
Dislocations:
• are line defects,
• slip between crystal planes result when dislocations move,
• produce permanent (plastic) deformation.
From: Guy, "Introduction to Materials Science, "McGraw Hill (1972)
[Link] Chapter 4 - 28
Line Defects
[Link]
Chapter 4 - 29
Dislocation in 3D
Chapter 4 - 30
Dislocation in 3D
Chapter 4 - 31
Imperfections in Solids
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.)
Chapter 4 - 32
[Link]
Imperfections in Solids
Screw Dislocation
Screw Dislocation
b
Dislocation
line (b)
Burgers vector b
(a)
Open circles are upper half atoms
Closed circles are lower half atom
Adapted from Fig. 4.5, Callister & Rethwisch 9e.
[Figure (b) from W. T. Read, Jr.,Dislocations in Crystals,
McGraw-Hill Book Company, New York, NY, 1953.]
Chapter 4 - 33
Screw Dislocations
Analogous to a Parking Garage
Adapted from Assist. Prof. Dr. Mert Efe Lecture Notes, Metu, Ankara
Chapter 4 - 34
Imperfections in Solids
Dislocations are visible in electron micrographs
Fig. 4.7, Callister & Rethwisch 9e.
(Courtesy of M. R. Plichta, Michigan
Technological University.)
Chapter 4 - 35
Burgers Vector
b is perpendicular to dislocation line
b is parallel to dislocation line
Chapter 4 - 36
Edge, Screw, and Mixed Dislocations
Mixed
Edge
Adapted from Fig. 4.6, Callister & Rethwisch 9e.
Screw [Figure (b) from W. T. Read, Jr., Dislocations in Crystals,
McGraw-Hill Book Company, New York, NY, 1953.]
Chapter 4 - 37
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;
BCC: none
• Specimens that Mg (HCP)
were tensile
tested. tensile direction
Al (FCC)
Chapter 4 - 38
Planar Defects—Free Surfaces
Chapter 4 - 39
Planar Defects—Free Surfaces
𝑁𝑜. 𝑜𝑓 𝑐ℎ𝑒𝑚𝑖𝑐𝑎𝑙 𝑏𝑜𝑛𝑑𝑠 𝑏𝑟𝑜𝑘𝑒𝑛 energy
𝛾= ( )
𝑈𝑛𝑖𝑡 𝑎𝑟𝑒𝑎 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑢𝑟𝑓𝑎𝑐𝑒 𝑓𝑜𝑟𝑚𝑒𝑑 bond
1) Surface energy is anisotropic
2) Highest density plane has lower energy
A. Bulk(generally)
truncation structures
fcc(100) fcc(110) fcc(111)
bcc(100) bcc(110)
bcc(111)
hcp(100) hcp(111)
hcp(110)
4
Chapter 4 - 40
Free Surfaces FCC(100)
Chapter 4 - 41
Free Surfaces FCC(111)
Chapter 4 - 42
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. 4.8,
Callister & Rethwisch 9e.
Chapter 4 - 43
Polycrystalline Materials
These are large grains on handrail.
They are likely zinc or some other
sacrificial coating for rust prevention.
Chapter 4 - 44
Planar Defects in Solids
Twin boundary (plane)
– Essentially a reflection of atom positions across the twin
plane.
– Occur between two separate crystals that share
lattice points in a symmetrical manner.
Adapted from Fig. 4.10,
Callister & Rethwisch 9e.
Chapter 4 - 45
Twin Boundaries
Adapted from Fig. 4.10,
Callister & Rethwisch 9e.
Growth Twins Deformation Twins Annealing Twins
FCC
[Link]
[Link] superelasticity/[Link]?print
able=1 Chapter 4 - 46
[Link] HCP, BCC.
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 light post or garbage can - see the
individual grains
• Crystallites (grains) can be quite small (mm
or less) – necessary to observe with a
microscope.
Chapter 4 - 47
Optical Microscopy
• Useful up to 2000X magnification.
• Sample preparation includes sectioning and sampling,
grinding, polishing, and etching.
Chapter 4 - 48
Sampling and sectioning
To remove a conveniently sized, representative specimen from a larger sample
Chapter 4 - 49
Grinding
•to obtain a flat surface
•to remove the distorted metal layer which does not reveal th
e true microstructure
Material Used
•emery papers are used in succession from the coarsest to
the finest. Number of the emery paper indicates the number
of abrasive particles ina uni area of paper, and thus the
coarseness or finess of the abrasives in it.
220→320→400→500→600→800→1200
Chapter 4 - 50
Polishing
To obtain a mirror like scratch-free surface
What if polishing is
not carried out properly?
Chapter 4 - 51
Etching
As-polished specimens do
not exhibit their microstructure,
simply because light is reflected unif
ormly. Etching is carried out to
create image contrast by creating
level differences on the specimen
surface.
Method
Level differences are created by a co
ntrolled acid attack on the specimen
surface. This is achieved by dipping
the specimen ina suitable dilute acid
solution, called etchant. 0.75 mm
crystallographic planes
Chapter 4 - 52
Optical Microscopy
Grain boundaries...
• are imperfections,
• are more susceptible
to etching,
• may be revealed as polished surface
dark lines,
• change in crystal surface groove
orientation across grain boundary
(a)
boundary. Fig. 4.15(a) & (b), Callister &
Rethwisch 9e.
[Fig. 4.15(b) is courtesy of L.C.
Smith and C. Brady, the National
Bureau of Standards, Washington,
DC (now the National Institute of
Standards and Technology,
Gaithersburg, MD).]
Fe-Cr alloy
(b)
Chapter 4 - 53
Grain Size Determination
Linear Intercept method
• Straight lines are drawn through several
photomicrographs that show the grain
structure.
• The grains intersected by each line
segment are counted
• The line length is then divided by an
average number of grains intersected. ASTM grain
size number
•The average grain diameter is found by
dividing this result by the linear N = 2 n -1
magnification of the photomicrographs.
number of grains/in2
at 100x
magnification
Chapter 4 -
Chapter 4 - 55
Optical Microscopy
• Polarized light
– metallographic scopes often use polarized
light to increase contrast
– Also used for transparent samples such as
polymers
Chapter 4 - 56
Microscopy
Optical resolution ca. 10-7 m = 0.1 μm = 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.
Chapter 4 - 57
