MATERIAL SCIENCE AND ENGINEERING

Course No. : CHE F243

Instructor-in-charge : Nandini Bhandaru
Instructors : Karthik Chethan V. , Nandini Bhandaru,

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Q1) Calculate the atomic packing density along [011]
direction of aluminum (Al). Express your answer in units
of atoms cm–1. (𝜌=2.70 g/cm3)

Q2) Dalium (Da) is BCC. Its molar volume is 6.66 cm3

/mol. Calculate the density of atoms in (001) of Da.
Express your answer in atoms/cm2.

Q3) For which set of crystallographic planes will a first

order diffraction peak occur at a diffraction angle of
44.53° for FCC nickel (Ni) when monochromatic
radiation having a wavelength of 0.1542 nm is used?
(rNi= 0.1246 nm) 2
Q4) The following diffractometer data (expressed as 2θ )
were generated from a specimen irradiated with silver
(Ag) K𝛼 radiation: 14.10°; 19.98°; 24.57°; 28.41°; 31.85°;
34.98°; 37.89°; 40.61°.
(a) Determine the crystal structure.
(b) Calculate the lattice constant, a.
(c) Assume that the crystal is a pure metal and on the
basis of the hard-sphere approximation calculate the
atomic radius.

incident x-ray → λ=0.574 Å

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 IMPERFECTIONS IN SOLIDS
ISSUES TO ADDRESS...

• What types of defects arise in solids?

• Can the number and type of defects be varied

and controlled?

• How do defects affect material properties?

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 Defects
So far, perfect, but it is unreal and not very insightful.

Perfection:
– Chemical composition
– Atomic arrangement

Bonding
+
Structure = Properties
+
Defects
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 Type of Defects
• Point defects: atoms missing or in irregular places
in the lattice (lattice vacancies, self-interstitials,
substitutional and interstitial impurities).
• 1D, Linear defects: groups of atoms in misaligned
positions (e.g. screw and edge dislocations).
• 2D, Planar defects: the interfaces (interphases)
between homogeneous regions of the material
(e.g. grain boundaries)
• 3D, Volume defects: extended defects (pores,
cracks)
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 Defects (pros and cons)

• Pros: ----------------, additional advantages

• Cons:----------------

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 Defects and Dimensions
• Sub-atomic defects (dynamic) (10-14 to 10-12 m).
• Atomic defects (dynamic and structural) (10-11 to
10-10 m).
• Edge defects (dynamic and structural) (10-9 to 10-7
m).
• Phase defects (dynamic and structural) (10-8 to
10-4 m).
• Grains (structural) (10-8 to 10-2 m).
• Macro defects (voids, cracks) (10-4 to 10-1 m).

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 History
• Fracture mechanics came out of necessity
• Theoretical calculations with factor of safety
not consistent with catastrophic failures.
• Bridges
• Dams
• Walkways
• Ships
• Space shuttle

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• Defects can be introduced/removed during processing.
• Processing allows one to achieve the required properties without changes in
composition of the material, but just by manipulating the crystal defects.
• Control (and intentional introduction) of defects is in the core of many types
of material processing.

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

• Dislocations Line defects

• Grain Boundaries Area defects

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 Point Defects (Vacancies)
• Vacancies are always present in crystals and they
are particularly numerous at high temperatures,
when atoms are frequently and randomly change
their positions leaving behind empty lattice sites
(vacancies).

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 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

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 Entropy
“Any method involving the notion of entropy, the very existence of
which depends on the second law of thermodynamics, will
doubtless seem to many far-fetched, and may repel beginners as
obscure and difficult of comprehension.”
WILLARD GIBBS

“ Same old, same old, death, decay and increase in entropy

BIG BANG THEORY

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15
 Equilibrium Concentration:
Point Defects
• Equilibrium concentration varies with temperature!

No. of defects Energy of defect formation

-Q 
= exp 
Nv ÷
 v ÷
No. of potential
N  kT 
defect sites.
Temperature
Boltzmann's constant
(1.38 x 10 -23 J/atom-K)
(8.62 x 10 -5 eV/atom-K)
Each lattice site
is a potential
vacancy site
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Measuring energy of defect formation
• We can get Qv from -Q 
Nv
= exp  v 
an experiment. N  kT 
• Measure this... • Replot it...

Nv Nv slope
ln
N N
-Qv /k
exponential
dependence!

T 1/T
defect concentration
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Effect of Energy of Defect Formation

Ln Nv/N
B

1/T

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 Estimating Vacancy Concentration
• Find the equil. # of vacancies in 1 m 3 of Cu at 1000C.
• Given:
r = 8.4 g /cm 3 A Cu = 63.5 g/mol
Qv = 0.9 eV/atom NA = 6.02 x 1023 atoms/mol
0.9 eV/atom
-Q 
exp 
Nv = ÷
 v ÷= 2.7 x 10-4
N  kT 
1273K
8.62 x 10-5 eV/atom-K
NA
For 1 m3 , N= r x x 1 m3 = 8.0 x 1028 sites
A Cu
• Answer:
Nv = (2.7 x 10-4)(8.0 x 1028) sites = 2.2 x 1025 vacancies
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 Vacancy Concentration

• We can estimate for copper: at room temperature -

one vacancy per 10^15 lattice sites.
• at high temperature, just below the melting point –
one vacancy for every 10,000 atoms.
• Note, that the above equation gives the lower end
estimation of the number of vacancies in real
materials, a large numbers of additional (non-
equilibrium) vacancies can be introduced in a growth
process or as a result of further treatment (plastic
deformation, quenching from high temperature to the
ambient one, etc.)

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 Self-Interstitials
• Self-interstitials in metals introduce large
distortions in the surrounding lattice.
• The energy of self-interstitial formation is ~ 3
times larger as compared to vacancies
(Qi ~ 3×Qv)
• Equilibrium concentration of self-interstitials is
very low (less than one self-interstitial per
cm^3 at room T).

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• Schematic representation of different point defects:
• vacancy;
• self-interstitial;
• interstitial impurity;
• substitutional impurities

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 Impurities
• Impurities - atoms which are different from the host.
• All real solids are impure. Very pure metals 99.9999%
one impurity per 10^6 atoms.
• May be intentional or unintentional
• Examples: carbon added in small amounts to iron
makes steel, which is stronger than pure iron. Boron
added to silicon change its electrical properties.
• Alloys - deliberate mixtures of metals
• Example: sterling silver is 92.5% silver – 7.5% copper
alloy. Stronger than pure silver.

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 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.

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 Imperfections in Solids
Conditions for substitutional solid solution (S.S.)
• W. Hume – Rothery rule
– 1. r (atomic radius) < 15%
– 2. Proximity in periodic table
• i.e., similar electronegativities
– 3. Same crystal structure for pure metals
– 4. Valency (oxidation states)
• All else being equal, a metal will have a greater tendency
to dissolve a metal of higher valency than one of lower
valency

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What determines solution formation
or precipitation

• Atomic size factor - atoms need to “fit” ⇒ solute and solvent atomic
radii should be comparable.
• Crystal structures of solute and solvent should be the same.
• Electronegativities of solute and solvent should be comparable
(otherwise new inter-metallic phases are encouraged).
• Generally, in metals, more solute goes into solution when it has
higher valency than solvent. 26
 Carbon interstitial
atom in BCC iron

• Interstitial solid solution of C in α-Fe. The C atom is small

enough to fit, after introducing some strain into the BCC
lattice.
• For fcc, bcc, hcp structures the voids (or interstices)
between the host atoms are relatively small ⇒ atomic
radius of solute should be significantly less than solvent.
• Normally, maximum solute concentration ≤ 10%, e.g. 0.25
wt.% for C in α-Fe (BCC), 2.06 wt.% for C in γ-Fe (FCC).
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 Imperfections in Solids
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

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

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

nm1 = number of moles of component 1

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 Defects in Ceramic Structures
• Frenkel Defect
--a cation is out of place.
• Shottky Defect
--a paired set of cation and anion vacancies.
Shottky
Defect:

Frenkel
Defect

-QD / kT
• Equilibrium concentration of defects ~e
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 Impurities
• Impurities must also satisfy charge balance = Electroneutrality
• Ex: NaCl Na + Cl -
cation
• Substitutional cation impurity vacancy
Ca 2+
Na +
Na +
Ca 2+
initial geometry Ca 2+ impurity resulting geometry

• Substitutional anion impurity anion vacancy

O2-

Cl - Cl -
initial geometry O2- impurity resulting geometry
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Questions/Doubts
1. What is the unit of KB?
2. What is KBT?
3. At what temperature does the first vacancy become stable in a Cu crystal?
Data:
No. of atoms in the crystal = NAvagadro
 Hf (Cu) = 1.24 eV/vacancy
Element Atomic Crystal Electro-
 kB = 8.62  10–5 eV/K Valence
 nv = 1 Radius Structure nega-
(nm) tivity
4. Do Cu and Ni satisfy Hume- Cu 0.1278 FCC 1.9 +2
Rothery’s rules for complete solid C 0.071
solubility? H 0.046
O 0.060
Ag 0.1445 FCC 1.9 +1
5. What is the effect of temperature on Al 0.1431 FCC 1.5 +3
the concentration of vacancy? What is Co 0.1253 HCP 1.8 +2
the effect of temperature on the Cr 0.1249 BCC 1.6 +3
concentration of Schottky defect? Fe 0.1241 BCC 1.8 +2
Ni 0.1246 FCC 1.8 +2
Pd 0.1376 FCC 2.2 +2
6. Can we create vacancy in an ionic Zn 0.1332 HCP 1.6 +2
crystal?
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7. If the metal is suddenly quenched (for example in liquid nitrogen at 77 K) from high
temperature to a lower temperature, what will happen to fraction of vacancies?

8. Does the Frenkel disorder in AgBr create vacancies of Ag+, vacancies of Br−, or both?

9. Write the reaction that represents the formation of a Schottky defect in ZrO2.

10. To increase the population of oxide vacancies ZrO2 can be doped with calcia (CaO).
Write the reaction showing that for each CaO that is incorporated into the ZrO2 crystal an
oxide vacancy is formed.

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 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

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 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

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 Imperfections in Solids
Edge Dislocation

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 Imperfections in Solids
Screw Dislocation
Screw Dislocation

b
Dislocation
line
Burgers vector b (b)
(a)

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Edge, Screw, and Mixed Dislocations
Mixed

Edge

Screw

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 Dislocations Density
• The number of dislocations in a material is
expressed as the dislocation density - the total
dislocation length per unit volume or the
number of dislocations present on a surface of
unit area.
• Dislocation densities can vary from 10^5 cm^-
2 in carefully solidified metal crystals to 10^12
cm^-2 in heavily deformed metals.

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Why do dislocations form and how can
they be prevented
• Most crystalline materials, especially metals, have
dislocations in their as-formed state, mainly as a
result of the following:
• Stresses (mechanical, thermal...) associated with
the forming process.
• Prevention (less number of grain boundaries,
maintain molecular rearrangement or mobility)
• -----------
• -----------

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 Planar Defects
• Interfaces
• Interphases/intergrains
• External Surfaces: Surface atoms have unsatisfied
atomic bonds, and higher energies than the bulk
atoms ⇒ Surface energy, γ (J/m2).
• Minimization of number of surfaces, surface
tension or surface energy reduces the energy of
the system (e.g. liquid drop).
• Solid surfaces can reconstruct to satisfy atomic
bonds at surfaces.

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 Minimization of surface energy
• Surfaces and interfaces have structure that is
different from the bulk and can be reactive →
impurities tend to segregate there.
• Since energy is associated with interfaces,
grains tend to grow in size at the expense of
smaller grains to minimize energy. This occurs
by diffusion, which is accelerated at high
temperatures (ostwald ripening, secondary
crystallization).

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• Grain Boundaries: Polycrystalline material 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.

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 High and Low Angle Grain Boundaries
• Depending on degree of misalignments of atomic
planes between adjacent grains we can distinguish
between the low and high angle grain boundaries.

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Interactions between dislocations and
grain boundaries
• Consequences

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 Bulk or Volume Defects
• Pores
• Cracks (micro-cracks, crazing)
• Foreign inclusions (other phases)
• Macro defects
• Reasons (------------------)

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 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.)

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