NENG 506 Mechanics of

Nanomaterials
Class 11
J. Lloyd

Point Defects and Dislocations
Point defects are those we just looked at
Substitutional Impurities
Interstitials
Vacancies
The point defects have a hydrostatic compressive or
tensile stress field associated with them depending
on relative size to the host

Point Defects
The volume change realized by the
interjection of a point defect is

The hydrostatic stress component of an edge
dislocation is

The elastic interaction energy with the
dislocation is
a
a a
where a V

'
= = A c c t
3
4
( )
( )r
Gb
h
v t
u v
o

+
=
1 3
sin 1
( )
( ) r
A
r
Gba
V U
h e
u
v
u c v
o
sin
1 3
sin 1 4
3
~

+
= A =
Solution Hardening
Two kinds
Substitutional solution hardening
Interstitial solution hardening
Not all metal and alloys are suitable for this to
occur

15% rule
Solution Hardening
Chemical Affinity
If they like each other too much you get intermetallic
compounds
In other cases you can get complete solid solubility






Valence
Higher valence has higher solubility in lower valence
Linear relationship with Cu

Cu-Ni
Solution Hardening
For each specific solute, the more you can get
into solution the better things are
Vacancies
A vacancy is a point defect with a non-zero thermal
equilibrium concentration
Can be derived from entropy of mixing



where AH
f
is the enthalpy of formation of a vacancy and C
0
is
the concentration number of lattice sites
Recall that the enthalpy has the PV term so that the
vacancy concentration in the presence of an applied stress
is




kT
H
C C
f
v
A
= exp
0
kT
C C
h
vo vs
O
=
o
exp
Vacancies
Also consider that since vacancy consists of a
vacant lattice site there is some collapse of the
lattice surrounding the vacancy
The vacancy thus is a point source of tensile stress
As such, it will be attracted to compressive side of an
edge dislocation
This will produce a Cottrell atmosphere of a higher
than normal concentration of vacancies in this region
In addition the vacancies will be attracted to the core
region
So, what happens if a vacancy collapses into the
core
Dislocation Climb
Dislocations can move out of the glide plane,
but with difficulty
The process must occur via diffusion of vacancies
to or from the dislocation core
There is no significant thermal equilibrium
concentration of self-interstitials
Dislocation Climb
If climb occurs the glide plane changes





Keep in mind that the dislocation has extension into and
out of the page
Thus when a single vacancy is absorbed or emitted causing climb,
a jog is created
It takes the diffusion of many vacancies to enable a dislocation to
climb out of a crystal
The presence of a climb induced jog in an edge or mixed
dislocation does not impede glide
But for a screw dislocation it does
Dislocation Climb
Depends on the diffusion of vacancies to or
from the core
Therefore climb is thermally activated
Arrhenius Relation






kT
H
D D
D
A
= exp
0
Homework #5
Consider a dislocation situated near the edge
of a crystal and another one situated in the
center with no applied stress
Comment on the relative behavior with respect to
climb of those two dislocations
Justify your answers with BOE (back of the
envelope) calculations
Dislocation climb
Let us put an applied stress, o
xx
, on the crystal
We now have a stress at the dislocation core as well as an
increased stress in the dislocation stress field
There will now be a chemical potential given by the stress
Recall that the equilibrium concentration of vacancies is thermally
activated with an activation enthalpy
Thus the vacancy concentration in equilibrium with the stressed
core is now


so that depending on the sign of the stress the core will either emit
or swallow vacancies to maintain equilibrium causing climb
kT
C C
xx
3
exp
0
O
=
o
Dislocation climb
The equilibrium vacancy concentration on the
x side of the crystal is increased similarly
However at the y face where there is no applied
stress it is not increased
We are infinite in z
Therefore there is a chemical potential for the
vacancies to be emitted or swallowed by the core
o
xx
o
xx

Hydrostatic Pressure
Let us place our crystal in under hydrostatic pressure
The vacancy concentration in contact with the core is now


But this increase is also experienced on all the other faces of
the crystal and there is no net force
Just like for yield, hydrostatic pressure does nothing for
climb
kT
P
C C
O
= exp
0
o
xx
= o
yy

o
xx
= o
yy

o
xx
= o
yy

o
xx
= o
yy

Dislocation Climb Force
Consider the applied stress in the x direction and
if we remove or add a line of atoms to the
dislocation at the core, the total energy change
per unit length is

where h is the distance advanced (lattice constant)
The force is then then simply (per unit length)

The force depends on the sign of the applied stress

bh W
xx
o = c
b F
xx
o =
The social life of a dislocation
Let us have two dislocations of opposite sign on
parallel slip planes opposite one another




Recall


and that the equilibrium vacancy concentration is increased,
thus they will annihilate reducing the total strain energy of
the crystal
Thermally activated glide
Takes place at jogs and kinks
Jogs and kinks are generally not on a glide plane
They can be eliminated by climb processes
(thermally activated) freeing a dislocation to glide




Thermally activated glide
Due to kink motion
The kink itself (in a screw dislocation) can be
considered to diffuse conservatively (without a
vacancy involved)
The jump frequency is given as

The diffusion coefficient is then

And similar to the climb force

Invoking the Relation Einstein

The kink diffusivity in FCC materials has a very low
activation energy
Not so for diamond cubic (Si) where thermally activated
glide is relatively slow even close to the melting point.




|
.
|

\
|
=
kT
E
k
exp v e
|
.
|

\
|
=
kT
E
a D
k
k
exp
2
v
ba F o =
kT
ba
D
kT
F D
v
k
k
dk
o
= =
Thermally activated glide processes
Dislocation climb
Self interstitials can be formed by extreme stress
Let us imagine a dislocation pinned at an impurity or at a
precipitate
Increased shear stresses and perhaps dislocation pileups
can increase the stress at the pinned location to where
interstitials may be emitted by the climb process
This takes a lot of energy
Precipitation Hardening
Similar to solution hardening but in this case the
dislocation barriers are second phase particles
Proper Heat Treating is crucial to the performance
At higher temperatures, more solute is soluble, the
metal is heated in a solution anneal
The metal is then quenched to a much lower
temperature, trapping the solute in a supersaturated
solution.
The temperature is then raised slightly to allow the
solute to form precipitates
The second phase will act as pins for dislocations
making the metal much stronger
Precipitation Hardening
Precipitation Hardening
The precipitate can pin dislocations making it
More difficult to yield. The more precipitates there
are, the more resistant the material to dislocation
motion
In addition, the tighter the spacing, the more
energy required to free the dislocation
Precipitation Hardening
The interparticle spacing, , can be expressed as


where f is the volume fraction of particles of radius, r
The shear stress needed for the dislocation to move
through the sea of particles is (Orowan)


So it is easily seen that a large number of fine particles
is the best thing for strength
( )
f
r f
3
1 4
=

t
Gb
=
Precipitation Hardening
If we also account for the increase in strain
hardening as well due to the stress fields of all
these dislocation loops we get The Orowan-
Ashby equation
b
r Gb
ln
13 . 0

o = A
Al/Cu
Duralumin
(Al/Cu often with a little Mn and Mg for stabilizing)
Aluminum alloy used primarily in
aviation
First used extensively in rigid airships
Aluminum by itself is light weight, but relatively weak
FCC atomic weight = 27
Alloying the Al with Cu produced an alloy that was
nearly as strong as steel when properly heat treated
It was found to get stronger just by letting it sit around at
room temperature
Discovered in 1903
Became the standard metal to make airplanes and is
still in use
Precipitation Hardening
(Coherency)
Al/Cu system
Heat treating will strengthen
the alloy initially, but if the
heating is continued the alloy
becomes weaker
This is called over-aging
There is an optimum
time/temperature
relationship that must be
maintained to get the best
properties

Al/Cu
Guinier Preston Zones (GP Zones)
Al/Cu
The GP I zone is relatively soft (although harder than pure Al) as the solute begins
to cluster with other solute atoms in the supersaturated solution
For Al/Cu room temperature is a mild annealing temperature. This is how it was
discovered in 1903, but dislocations were not yet known and the reason for the
hardening was not understood

The GP II zone occurs when the precipitates begin to occupy {100} planes in the
matrix in a manner coherent with the lattice.






This coherency very effectively pins the dislocations making it very difficult to deform
the crystal
This effectiveness is in part due to the strain in the local lattice near the dislocation.
There is a slight reduction in yield point, but strain hardening is greatly enhanced leading
to strength overall rivaling steels
Al/Cu
The GP III zone occurs when the precipitates grow to the point
where coherency is lost and dislocations can more easily
move through the lattice



Al/Cu is kept in a refrigerator until it is used so that it can be
formed in the soft state, then strengthened later by annealing
at mild temperatures
The use of Al/Cu alloys is not good for very high speed aircraft where
compression at high Mach increases the temperature to over-aging
conditions
Dispersion Hardening
A similar case can be made for what is known as
dispersion hardening
Here the second phase is not created by the precipitation
from a supersaturated solution, but is created by the
presence of a different material that has been mixed into
the lattice
Internal oxidation
Mechanical mixing
Good for high temperature alloys
NENG 303 Mechanics of
Nanomaterials
Class 12
J. Lloyd

Roscoe Turner
Homework #5
Consider a dislocation situated near the edge
of a crystal and another one situated in the
center with no applied stress
Comment on the relative behavior with respect to
climb of those two dislocations
Justify your answers with BOE (back of the
envelope) calculations
Katana
The most famous and sophisticated ancient
use of the metallurgical art
Precipitation hardening at its finest
Also known as a Samurai Sword
In the Russo-Japanese war of 1905, a Japanese Samurai
attacked a Russian machine gun and cut the barrel in
half with his sword
Katana
First you start with a very high grade ore (Tamahagane jewel
steel) (traditionally from an iron bearing river sand) and smelt
with charcoal for about three days
Do not let it melt
This is to ensure that the carbon goes into solution at
exactly the proper composition
It varies in the location of the Tamahagane from ~0.5% to 1.5%

Katana
The steel is separated according to carbon content by
its appearance and ease with which it can be
separated
It is then heated, folded and pounded many times to
extract all the impurities in the form of slag and to
disburse the carbon (spheroidization)
Typically 16 times

This produces 2
16
65,000 layers
Katana
Then the lower carbon steel is placed in an envelope
of higher carbon steel and forge welded
Producing a hard sharp more brittle case surrounding a
tougher more resilient core
This produces the desired properties of a fine sharp edge
and resistance to breaking
Katana
The blade is then heat treated and properly quenched (cooled),
using a sophisticated process of painting with clay, to produce the
proper microstructure and as an added benefit, the difference in
the properties of the two steels makes the blade curve elegantly









It is then polished to show the texture

A proper Katana can cost upwards of $50,000
The transverse stress is significantly higher in the
pipe than the pressure it is containing






This can be used to approximate encapsulated thin
film conductors
Hoop Stress
Creep Rupture
Creep
If a material is loaded above the yield point, before
catastrophic failure and kept there for a period of time, slow
deformation will take place until eventually failure will occur.
Initially creep is rather rapid (Primary Creep), then it proceeds at a
constant rate (Steady State Creep)
If held at constant load, the creep rate increases when the cross
sectional area is reduced (Tertiary Creep)
At constant stress the creep rate remains constant
Creep Rate
Empirical
Andrade (1932)
Cumbersome
where c
0
is the elastic strain limit and | and k are
adjustable constants
Obviously this represents a lack of understanding
whats going on physically

Garofalo (1960)
where c
0
is the instantaneous strain, c
t
is the limit of
stage 1 creep and c dot is the steady state creep rate


t
e t
k
| c c
|
|
.
|

\
|
+ =
3
1
0
1
( ) t e
s
t r
t
c c c c

+ + =

1
0
Creep
Creep rate is temperature and stress dependent








Engineering expressions have 4 material dependent
adjustable parameters!
kT
H
G T
A
ely alternativ or
kT
H
AB
c
m
n
s
c
s
A
=
A
=
exp
exp
t
c
o c
o

Deformation Map
Harold Frost (Dartmouth) and Mike Ashby (Harvard)
Deformation Maps
Stress Temperature Map Strain Rate Stress Map
at a given temperature
Deformation Maps
The general form is true
for most materials
Creep
Creep takes place by a number of deformation processes
Slip
Sub-grain formation
Grain boundary sliding
Diffusive Creep
Many of the deformation processes only occur at high
temperatures
High temperature is operationally defined as above the melting
temperature T
mp
This temperature is, of course, different for different metals
For Al, this would be 140C
For Cu, this would be 400C
For Fe, this would be 635C
For Pb, this would be 27C . Room temperature
Power Law Creep
Complicated
constant temperature



where n varies between 3 and 10
Complex variety of mechanisms operating
Recent modeling (2012) shows that
power law creep can be accounted for
by dislocation climb
n
s
G
|
.
|

\
|

High Temperature Creep

Slip
New slip systems can become activated at high
temperature that do not operate at low temperature
Al
At low temperature slip plane is {111}
Above 260C, we add {100} and {211} planes
The CRSS is reduced with temperature
Zr
CRSS = 1kg/mm
2
at 77K
CRSS = 0.2kg/mm
2
at 575K (300C)
CRSS = 0.02 kg/mm
2
at 1,075K (800C)
Dislocation sources can be more active due to
increased climb at jogs/kinks etc.
Creep
Sub-boundary formation
At higher temperatures dislocations can climb and
arrange into energetically favorable positions
This provides bending of the crystal
Which makes the grain boundaries very uncomfortable
Creep
Grain Boundary Sliding
At high temperatures another mechanism can
dominate called grain boundary sliding
Shear occurs along the grain boundary
Mostly at relatively slow creep rates
The precise mechanism is controversial
Thought Experiment









Imagine a mobile solute component in a liquid which has no
solubility in the solid (hashed line). The solute, however, has
solubility in the solid. It can be shown that under the same
pressure on the different faces the chemical potential is the
same
Perpetual motion machine
The Thermodynamics of Stressed Solids
J.C.M. Li, R.A. Oriani and L.S. Darken
Zeit. Physik. Chem. Neue Folge, 49, 271 (1966)
Li, Oriani and Darken
For a not necessarily uniformly stressed solid
We will consider a closed isothermal system in
equilibrium
Only elastic stresses will be applied
Satisfies the conditions reversibility and constant
temperature



The first two terms can be rearranged to produce the
expression for the free energy
Thus the last term can be considered the free energy but
according to Moutiers Theorem the work to obtain this is
independent of path
Note also that the condition for equilibrium for a chemical
process is that the change in free energy is at a minimum
} } }
+ = dW dS T dU
Li, Oriani and Darken
Determine the work to add or remove a component by
two methods and equate them since the theorem
states that the work is path independent
The first path with be the direct transfer of a quantity of
the solute to the fluid
The work done on the body to add or remove the n
k
of
solute is defined as W
k

This is all the work/energy needed to remove or add the quantity of
solute
The work done on the fluid is the work of expansion (or
contraction) with the addition of the solute to the fluid
at the pressure of the fluid, this is W
k
F

Thus the total work for this procedure is


( )
k k
F
k
n W W o
Li, Oriani and Darken
The second pathway will be to completely relax the stresses in the
solid, but not in the fluid (by magic) and transfer some solute from
the solid to the fluid, then reapply the stress to its original value
The amount of work done by the relaxation is w.
Now the chemical potentials ( = dE/dn
k
)of the solute on the surface
of the unstressed solid
k
0

and the pressurized liquid
k
can be
expressed.
The work of transferring the solute from the solid to the liquid is then
(
k
-
k
0
)n
k

Now we reapply the stress and also add the work of expansion for a
total by this procedure




Equating the work from the two procedures and realizing at
equilibrium they must vanish overall




















k
F
k
k
k k
n W
n
w
o
|
|
.
|

\
|
+
c
c

0
k
k
k k
W
n
w
+
c
c
=
0

Li, Oriani and Darken
Examining this we realize that the one term is the
partial molal strain energy and the other is the
normal stress times the molal volume


where is the chemical potential in the stressed
solid,
0
the chemical potential in the unstressed
solid, w is the strain energy with the addition (or
subtraction) of the solute and is the partial
molal (or atomic) volume (depending on units)
O + = o w
0
Li, Oriani and Darken
What does this tell us
For one, this tells us for a given stress that the chemical
potential and therefore the solubility will change with the
normal stress component (or pressure)
If the solute increases the volume of the solid (ie the
solute atoms are bigger than solvent atoms) tensile stress
will increase solubility and compressive stress reduce
solubility
Vice versa
The story of a vacancy is interesting
The creation of a vacancy increases the volume, therefore it is
promoted by tensile stress
But a vacancy is a point source of tensile stress so it is attracted to
a compressive stress field.
Diffusive Creep
Diffusion proceeds down a chemical potential
gradient
In the absence of all other gradients that is the
concentration gradient
Entropy gradient
However, any contributor to the chemical
potential can drive diffusion
Stress gradients are most important

o V O V = V w
Strain Energy
The strain energy is given as



The stress is that of a vacancy, but the strain energy is mitigated by
the ratio of the stress to the modulus
Stresses are generally in the range of tens or hundreds of MPa
Moduli are in the range of tens or hundreds of Gpa
Thus the strain energy term is usually negligible

Thus the chemical potential gradient due to stress is usually
described as



Where the stress is the normal component to the boundary



















O =
E
w
2
2
o
o V O = V
Stress Gradients
Mass diffusion is due to the motion of vacancies
If the vacancies are going to the left, the atoms are going
to the right
Vacancies annihilate when they meet a surface or a sink
like a grain boundary
Consider a polycrystalline metal undergoing a uniaxial tensile
stress in the y direction
The equilibrium vacancy concentration
on grain boundaries parallel to the applied
stress in the y direction is

|
|
.
|

\
|
A
=
|
.
|

\
|
O
=
kT
H
C C
kT
C C
f
L
v
exp
exp
0
0
o
Diffusive Creep
Since the diffusive flux of vacancies (or atoms)
will be


the crystals will grow in the
direction of the applied
tensile stress
This is strictly true at all
temperatures and all stress
levels
But at low temperatures it may
be exceedingly slow
v v v v
C D J V =
Final Exam
Question 1
Wafer
Normal






Sidewall
Normal







Along
Trench
Question 1
(10 Points)
On the previous page we have EBSD (Electron Back
Scattered Diffraction) images of a polycrystalline Cu
material. The images are taken such that the orientation of
the grains are analyzed with respect to three orthogonal
directions (up, right, and out of the page). The color code is
explained in the pie slice, where the crystal orientation
with respect to the direction is denoted. Ie. If its blue, the
crystal is oriented with (111) plane perpendicular to that
direction

Why do the red grains not change color when the others
do?



Question 2
(20 points)
We have a single crystal of Al in a tensile
tester. We are applying a tensile stress, o

perpendicular to the 212 plane and we have
found that slip has occurred.
What is the shear stress that produced the
slip?

Given a crack in an Aluminum wing spar that is 2
cm long.
What is the stress concentration for this crack?
Let us assume atomic dimensions at the crack tip
(unrealistic perhaps) but

What size drill would you use to reduce the stress
to ten times the applied load with a pilot hole?
(10 points)

For three times the applied stress? (5points)



Question 4
15 points)
Question 3
(5 points)
Discuss why quasicrystals are brittle
Also discuss the modulus of elasticity for a
quasicrystal as compared to a real crystal