MS2

CH6:
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?
Solidification: the result of casting of molten material.

– 2 steps
• Nuclei form
• Nuclei grow to form crystals – grain structure
• Start with a molten material – all liquid

• Crystals grow until they meet each other
Nuclei ----> crystals ----> grain structure

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
Grains can be
- equiaxed (roughly the same size in all directions)
- columnar (elongated grains)
Grain Refiner
added to make smaller
more uniform
equiaxed grains.
Shell of equiaxed grains due to rapid cooling (greater T) near wall
Columnar in area with less undercooling
There is no such thing as a perfect crystal.
Many of the important properties of materials are due to the presence

of imperfections.
Type of Imperfections :
1)Point defects
• Vacancy atoms • Interstitial atoms • Substitutional atoms
2)Line defects
• Dislocations
3)Area defects
• Grain Boundaries
Point Defects
• Vacancies: vacant atomic sites in a structure.
• Self-Interstitials: "extra" atoms positioned between atomic sites.

Equilibrium Concentration of Vacancies :
• Equilibrium concentration varies with temperature!
Nv/N = exp(-Qv/KT) Boltzmann's constant

Where: (1.38 x 10-23 J/atom-K)
Nv: No. of defects (8.62 x 10-5 eV/atom-K)
N: No. of potential defect sites
Qv: Activation energy J/atom
K: Boltzmann's constant
T: Temperature K = C + 273
N = ρ * volume * (6.022*10^23/atomic wight)
Each lattice site is a potential vacancy site
In theory, the maximum potential number of vacancies size equal to

the number of atoms in certain volumes.
Measuring Activation Energy :

• We can get Qv from an experiment.
Impurities in Solids :
Two outcomes if impurity (B) added to host (A):
• Solid solution of B in A (i.e., random dist. of point defects)
-Substitutional solid soln.
-Interstitial solid soln.
• 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.
Impurities in Solids:
Conditions for substitutional solid solution (S.S.) – complete solubility
W. Hume – Rothery rule:(complete solubility)
1. r (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
Incomplete solubility (incomplete solution)

If some of the conditions in the complete solubility were not done.
Interstitial solid solubility(Interstitial solid solution)

The atomic radius of the host must be less than <0.075nm
The radius of an impurity atom that just fits in a BCC [r = R(0.15)]

Where: r: radius of impurity atom. R: radius of host atom.
• Specification of composition
– weight percent : C1 = [m1/(m1+m2)]*100
m1 = mass of component 1
– atom percent: C’1 = [nm1/(nm1+nm2)]*100

nm1 = number of moles of component 1
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
Dislocations are visible in electron micrographs

Interfacial Defects
Other defects
1)External Surfaces
2)Grain Boundaries
3)Phase Boundaries
4)Volume defects
5)Atomic vibrations
External Surfaces:(are defects too)

• Surface atoms are not bonded to the maximum number of atoms
• Give rise to surface energy (J/m2 )
• Liquid droplet tends to minimize surface energy, difficult in solids
Grain Boundaries:
• Boundary separating two grains with different crystallographic
orientation in polycrystalline material
• Low angle grain boundary vs. high angle grain boundary
• Give rise to interfacial energy or grain boundary energy
• The magnitude of the interfacial energy depends on the
misorientation angle (higher for high angle grain boundary)
Phase Boundaries:
• Exists in multiphase materials in which a different phase exists on
each side of the boundary
• Each phase has its own distinctive physical and/or chemical
characteristics.
• Phase boundaries play an important role in determining mechanical
properties
Volume defects: pores, cracks, foreign inclusions, and other phases

Other interfection:
Atomic vibrations
• Considered as an imperfection
• Not all atoms vibrate at the same frequency and amplitude
• There exists a distribution of vibrational energy
• The temperature of a solid is just a measure of its average
vibrational energy
• At room temperature: vibrational frequency ~ 10 13 /s and vibrational
amplitude~.001 − 0.01 nm
CH7:
Diffusion
Diffusion - Mass transport by atomic motion
Diffusion Mechanisms:
vacancy diffusion
interstitial diffusion
• Gases & Liquids – random (Brownian) motion

• Solids – vacancy diffusion or interstitial diffusion
• Interdiffusion: In an alloy, atoms tend to migrate from regions of high

conc. to regions of low con
• Self-diffusion: In an elemental solid, atoms also migrate.

“Its hard to Self-diffusion”
Vacancy Diffusion:
• atoms exchange with vacancies
• applies to substitutional impurities atoms
• rate depends on:
-- number of vacancies
-- activation energy to exchange.
• Interstitial diffusion – smaller atoms can diffuse between atoms.
Interstitial diffusion is faster and more rapid than Vacancy diffusion

Processing Using Diffusion
• Case Hardening
• Doping
Case Hardening:
-- Diffuse carbon atoms into the host iron atoms at the surface.
-- Example of interstitial diffusion is a case hardened gear.
• Result: The presence of C atoms makes iron (steel) harder.
Doping silicon with phosphorus for n-type semiconductors:

• Process:
1. Deposit P rich layers on surface.
2. Heat it.
3. Result: Doped semiconductor regions.
the amount or rate of diffusion:
J = mole(or mass)/(area)*(time)
• Measured empirically
– Make thin film (membrane) of known cross-sectional area
– Impose concentration gradient
– Measure how fast atoms or molecules diffuse through the
membrane
J = M/At
Rate of diffusion independent of time :

Flux proportional to concentration gradient =dC/dX
Fick’s first law of diffusion :
J = -D(dC/dX)
where
D diffusion coefficient
Diffusion and Temperature
• Diffusion coefficient increases with increasing T
D = Do exp(-Qd/RT)
where:
D = diffusion coefficient [m2 /s]
Do = pre-exponential [m2 /s]
Qd = activation energy [J/mol or eV/atom]
R = gas constant [8.314 J/mol-K]
T = absolute temperature [K]
D has exponential dependence on T

Non-steady State Diffusion
• The concentration of diffusing species is a function of both time and
position C = C(x,t)
• In this case Fick’s Second Law is used
Fick’s Second Law:
C0 = initial concentration
Cs = surface concentration
C(x,t) = concentration at the potion or time.
X: position
T:time
And:
Same (C0,Cs,C(x,t))
D1t1 = D2t2
Summary
• open crystal structures • close-packed structures
• materials w/secondary bonding • materials w/covalent bonding
• smaller diffusing atoms • larger diffusing atoms
• lower density materials • higher density materials
CH8:
Mechanical Properties of Metals.
1)Elastic Deformation.
1. Initial.
2. Small load
3. Unload
Elastic means reversible!
2)Plastic Deformation (Metals)
1. Initial
2. Small load
3. Unload
Plastic means permanent!
Stress:
• Tensile stress, segma:
Segma = Ft/A0 (N/(m)^2)
A0 : original area before loading
• Shear stress, t:
t = Fs/A0 (N/(m)^2)
A0 : original area before loading

Common States of Stress:
• Simple tension: cable
• Simple compression:
Strain:
• Tensile strain:
• Lateral strain:
• Shear strain:
Strain is always dimensionless.

Stress-Strain Testing(Machine):
• Typical tensile test machine
• Typical tensile specimen

Linear Elastic Properties :
• Hooke's Law:
sigma = E e
• Modulus of Elasticity, E: (also known as Young's modulus)
• Poisson's ratio, v:
V = -(eL/e)
metals: n ~ 0.33
ceramics: n ~ 0.25
polymers: n ~ 0.40
Units: E: [GPa] or [psi]

v: dimensionless
Origin of Mechanical Properties:
• Slope of stress strain plot (which is proportional to the elastic
modulus) depends on bond strength of metal:
Other Elastic Properties :

• Elastic Shear modulus:
• Special relations for isotropic materials:
Young’s Moduli: Comparison

Effect of Temperature:
If the Temperature increases the stiffness decreases
Plastic (Permanent) Deformation:

(at lower temperatures, i.e. T < Tmelt/3)
• Simple tension test:

Yield Strength, segma(y)
• Stress at which noticeable plastic deformation has occurred.
Noticeable = ep
e = delta(z)/z
Yield Strength : Comparison

Tensile Strength, TS
• Maximum stress on engineering stress-strain curve.
• Metals: occurs when noticeable necking starts.

• Polymers: occurs when polymer backbone chains are aligned and
about to break.
Tensile Strength : Comparison:

Ductility:
• Plastic tensile strain at failure:
%EL = ((Lf - L0)/L0)*100
• Another ductility measure:
%RA = ((A0 - Af)/A0)*100
Toughness
• Energy to break a unit volume of material
• Approximate by the area under the stress-strain curve.
Resilience, Ur
• Ability of a material to store energy
– Energy stored best in elastic region
If we assume a linear stress-strain curve this simplifies to
Elastic Strain Recovery:

True Stress & Strain
Note: S.A. changes when sample stretched
• True stress
• True Strain
Design or Safety Factors:
• Design uncertainties mean we do not push the limit.
• Factor of safety, N
Hardening
• Curve fit to the stress-strain response:
Hardness:
• Resistance to permanently indenting the surface.
• Large hardness means:
-- resistance to plastic deformation or cracking in compression.
-- better wear properties.
Hardness: Measurement:
• Rockwell
– No major sample damage
– Each scale runs to 130 but only useful in range 20-100.
– Minor load 10 kg
– Major load 60 (A), 100 (B) & 150 (C) kg
• A = diamond, B = 1/16 in. ball, C = diamond
• HB = Brinell Hardness
– TS (psia) = 500 x HB
– TS (MPa) = 3.45 x HB

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CH6:

Solidification: the result of casting of molten material.

• Start with a molten material – all liquid

Nuclei ----> crystals ----> grain structure

Shell of equiaxed grains due to rapid cooling (greater T) near wall

Columnar in area with less undercooling

There is no such thing as a perfect crystal.

Many of the important properties of materials are due to the presence

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

Nv/N = exp(-Qv/KT) Boltzmann's constant

N = ρ * volume * (6.022*10^23/atomic wight)

Each lattice site is a potential vacancy site

In theory, the maximum potential number of vacancies size equal to

Measuring Activation Energy :

• Solid solution of B in A plus particles of a new phase (usually for a

Incomplete solubility (incomplete solution)

Interstitial solid solubility(Interstitial solid solution)

The radius of an impurity atom that just fits in a BCC [r = R(0.15)]

– atom percent: C’1 = [nm1/(nm1+nm2)]*100

Dislocations are visible in electron micrographs

External Surfaces:(are defects too)

Volume defects: pores, cracks, foreign inclusions, and other phases

Diffusion - Mass transport by atomic motion

• Gases & Liquids – random (Brownian) motion

• Interdiffusion: In an alloy, atoms tend to migrate from regions of high

• Self-diffusion: In an elemental solid, atoms also migrate.

• Interstitial diffusion – smaller atoms can diffuse between atoms.

Interstitial diffusion is faster and more rapid than Vacancy diffusion

Doping silicon with phosphorus for n-type semiconductors:

Rate of diffusion independent of time :

D has exponential dependence on T

A0 : original area before loading

A0 : original area before loading

Strain is always dimensionless.

• Typical tensile test machine

• Typical tensile specimen

Units: E: [GPa] or [psi]

Other Elastic Properties :

• Special relations for isotropic materials:

Young’s Moduli: Comparison

Plastic (Permanent) Deformation:

• Simple tension test:

Yield Strength : Comparison

• Metals: occurs when noticeable necking starts.

Tensile Strength : Comparison:

If we assume a linear stress-strain curve this simplifies to

Elastic Strain Recovery:

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