Microstructure and Properties II

MSE 27-302
Fall, 2002 (2nd mini-course)
Prof. A. D. Rollett
http://neon.mems.cmu.edu/rollett/27302/ 27302.html
Course Content
27-302 is the second of a pair of
(mini-)courses that describe the relationship between materials
microstructure and properties.
This course deals mainly with multi-phase microstructures.
There is a strong emphasis on phase transformations as the
basis for understanding the origin of (useful) microstructures.
27-301 dealt mainly with single phase microstructures and their
properties.
Multi-phase materials made through natural processes will be
contrasted with (man-made) composite materials and
biomaterials.
Students are expected to learn a set of technical skills in addition
to improving various attributes of scientist/engineers
(communications, ethics, how to design experiments, )
Topics
Where does microstructure come from? Phase transformations, kinetics of
transformations, the Kolmogorov-Johnson-Mehl-Avrami equation.
Properties of Composite materials: background material on glass-ceramics for Lab 1.
Phase transformations: driving forces, thermodynamics of nucleation (precipitation
reactions).
Transformations: kinetics of growth: a simple TTT diagram. How to calculate and predict
TTT and CCT diagrams.
The role of interfaces in heterogeneous nucleation; example of the Al-Cu system;
sequences of metastable precipitates.
The age-hardening curve; methods of measuring transformations. The similarities
between mechanical hardness and magnetic hardness.
Impact of precipitation on complex properties: example of fatigue as a microstructure-
sensitive property.
More complex diffusive transformations: example of Fe-C system for eutectoid reactions.
Continuous transformations: spinodal decomposition.
Coarsening of two-phase structures; effect of two-phase structures on creep properties (Ni-
alloys as an example).
Competition between transformation mechanisms; discussion of non-diffusive
transformations; massive transformations, martensitic transformations; exploitation of
martensitic reactions for shape-memory alloys.
The ultimate in complicated microstructures: introduction to welding and joining.
Technical topics
Technical Issues:
S olid state transformations
Differences between transformations from the liquid state
and transformations starting from the solid state: the
influence of crystalline structure
Driving forces - should the reaction take place?
Nucleation and growth (thermodynamics, kinetics): the rate
at which reaction takes place
Influence of defects on transformations
Prediction of temperature-time-transformation (TTT) curves
(and/or continuous-cooling-transformation, CCT, curves)
Military transformations
Precipitate coarsening
These topics are some of the underpinnings for
understanding various phenomena that are
important for microstructure-property relationships.
Material Properties, Phenomena
Examples of phenomena for which microstructure-
property relationships are significant:
Age Hardening
Shape memory effect, alloys
Alloy optimization
Multiphase materials and creep
Energy absorption in structures
Fatigue resistance
Exploitation of nanostructured, amorphous materials
Optimization of Materials Design
All the technical topics are relevant to understanding
and engineering the phenomena.
Certain material systems are important examples.
Materials Systems
Clearly there are too many material systems
to study in one course. Certain systems are
very useful as examples, however.
Al-Cu: precipitation, metastable phases, age
hardening, effects of crystal structure,
coarsening
Fe-C-X (steel): allotropic transformations,
eutectoids, military transformations,
tempering, hardenability
Student Input for 302
In 27-301, each student was required to make a
short presentation in class.
In 27-302, student input will be sought through
discussion sessions. The objective is to learn how to
apply the understanding of microstructure-property
relationships to a specific system(s).
The culmination of the student input exercise will be
a discussion of the pros and cons and changing a
given material (for a specific application).
Discussions will be held in the second half of the
Weds class.
Next we discuss the sequence of steps required.
Materials Design
The sequence of steps leading towards the
discussion of materials design:
1. Each student chooses an application for which a material is
critical in at least one component (Oct. 23rd, Weds).
2. The application is analyzed to determine which component
is materials-critical (Oct. 30th, Weds).
3. The material is analyzed to determine its microstructure
and likely processing history (Oct. 30th, Weds).
4. The microstructure-property relationships are analyzed
(Nov. 13th, Weds).
5. Possible changes to the microstructure are analyzed for
their effect on properties (Nov. 20th, Weds).
6. Discussion between a pro-change group and a status-
quo group on the merits of optimization of the material
(Nov. 25th, Monday).
7. Each student writes up a report on materials optimization.
Applications
Stents
Sutures
Bone substitute
Stealth aircraft (Low Observable materials)
Nuclear reactors (fuels)
Solar cells
Light weight armor (ceramic armor)
302 Jeopardy: 1
1. Rank is sum of the rank of
the quantities on each side
Q1. How is the rank of a property
tensor determined from the rank of each
related quantity?
2. Free energy
Q2. What thermodynamic quantity
should we use to predict whether or not
a reaction will occur?
3. 2-fold symmetry axes (diads)
Q3. Which symmetry element is
found on <110> directions in fcc
materials?
4. -RT ln{X
0
/X
e
}.
Q4. What is the formula for the driving
force for precipitation in a simple 2-
phase system?
5. No nucleation barrier
Q5. Name a key difference between
discontinuous and continuous phase
transformation.
6. Approximately 3 times the
yield stress.
Q6. How much greater is the hardness
than the yield stress (same units)?
302 Jeopardy: 2
1. Proportional to
undercooling
Q1. How is driving force related to
undercooling?
2. Difference between the temp. at which
the composition intersects the solvus
(liquidus) and the current temp.
Q2. How is the undercooling defined?
3. Einstein notation
Q3. What is the name for the convention
that states that repeated indices are
summed over?
4. -H
f
(T/T
melt
).
Q4. What is the formula for the driving
force for solidification?
5. Two phases in a composite generally
expand/contract at different rates with T.
Q5. What is one cause of residual stress
in a composite material?
6. Differentiate the total energy.
Q6. How do we determine the point at
which an energy release rate is zero?
302 Jeopardy: 3
1. Balance between rates of adding
surface energy and gaining free energy
from transformation
Q1. How does one determine the barrier
to nucleation?
2. In precipitation of pro-eutectoid ferrite,
the thermodynamic term involves the log
of a ratio of terms in (1-X).
Q2. Why is the driving force for a
eutectoid decomposition small compared
to decomposition of a simple solid
solution (e.g. pro-eutectoid
decomposition of austenite)?
3. 2/G
V

Q3. What is the formula for the critical
radius?
4. Because large interfacial energies
mean high barriers to nucleation (and
heterogeneous sites, if available, operate
first).
Q4. Why is homogeneous nucleation
only observed in a few cases?
5. 16
3
/G
V
2
.
Q5. What is the formula for the critical
free energy of nucleation?
6. It is a volumetric energy and is
subtracted off the chemical free energy
for transformation.
Q6. What is the role of elastic energy in
nucleation?
302 Jeopardy: 4
1. 16
3
/{G
V
-G
S
}
2
Q1. What is the free energy barrier in
the presence of an elastic energy?
2. Al
2
Cu platelets aligned with {100}
planes.
Q2. What effect does elastic anisotropy
have on precipitation in the Al-Cu
system?
3. Matching of close-packed
planes, e.g. {110}
bcc
// {111}
fcc
Q3. What impact does atomic matching
have on the orientation relationship
between parent and product phases?
4. The rate increases because of
increasing driving force but then
decreases because of decreasing
diffusion rate.
Q4. Why does the growth rate first
increase with undercooling and then
decrease?
5. D V
2
C = cC/ct.
Q5. What is the diffusion equation (w/o
source terms)?
6. Linearized gradients.
Q6. What approximation can we make to
solve the diffusion equation for ppt growth in
1D?
302 Jeopardy: 5
1. The change in concentration around
one precipitate affects the concentration
around adjacent precipitates.
Q1. What is the cause of
impingement of concentration fields?
2. Grain boundaries act as short circuit
diffusion paths for transport of solute to
precipitates.
Q2. Why do precipitates grow more
rapidly on grain boundaries than in the
bulk (at low temperatures)?
3. Decreasing radius of a
precipitate raises its solubility.

Q3. What does the Gibbs-Thomson
effect do to precipitates?
4. Solute diffuses from small
precipitates to large ones.
Q4. What causes coarsening of
precipitates?
5. <R
3
(t)> - <R
3
(t=0)> = k t.
Q5. What is the relationship between
radius and time for coarsening?
6. x = C
0
/ (C
|
- C
e
) (Dt).
Q6. What is the relationship between ppt size
and time for diffusion controlled growth in
1D?
Office hours, CAs
Office hours will be as in 301: 3:30-5
Monday, 11:30-12:30 Weds/Fri.
The CA for the Lab is Ms. Mitra Taheri.
Exam Rules
No books; no lecture notes; no computers
One cheat sheet with notes (both sides if you like);
hand in the the cheat sheet with the exam
paper/book. You must write the notes yourself:
copying and pasting is OK, but not literal cut and
paste. The idea of the cheat sheet is for you to go
through the course material and extract the most
important ideas, equations, etc.
Calculator OK (but not a device, such as a Palm
Pilot, in which you can store lecture notes etc.)
27-302, Labs
Lab 1 = Investigation of precipitation in glass-
ceramics. Purpose: to demonstrate the
effect of phase transformation on mechanical
and optical properties.
Lab 2 = Short experiments on crystallization
of amorphous metals, magnetic domain
imaging and age hardening curves.
Calendar: 302
Please consult the separate file posted on the website.
Topic List: 302
Where does microstructure come from? Phase transformations, kinetics of transformations, the Kolmogorov-Johnson-
Mehl-Avrami equation.
Properties of Composite materials: rule of mixtures. Background material on glass-ceramics for Lab 1.
Phase transformations: driving forces, thermodynamics of nucleation (precipitation reactions).
Transformations: kinetics of growth: a simple TTT diagram.
The role of interfaces in heterogeneous nucleation; example of the Al-Cu system; sequences of metastable precipitates.
The age-hardening curve; methods of measuring transformations.
Impact of precipitation on complex properties: example of fatigue as a microstructure-sensitive property.
More complex diffusive transformations: example of eutectoid reactions.
Continuous transformations: spinodal decomposition.
Coarsening of two-phase structures; effect of two-phase structures on creep properties (Ni-alloys as an example).
Competition between transformation mechanisms; discussion of non-diffusive transformations; massive transformations,
martensitic transformations; exploitation of martensitic reactions for shape-memory alloys.
Parallels between magnetic and mechanical hardness.
The ultimate in complicated microstructures: introduction to welding and joining: not addressed in 2001.
Cellular structures: foams, wood, bread(!), bone, composites.
Guest Lecture (Prof. E. Towe): quantum dot structures in semiconductors.
Sample problem: 1
KJMA equation (transformation kinetics): an alloy is
recrystallized at 2 different temperatures, 400 and 500C. The
KJMA exponent is found to be 2. By interpolating the f vs time
data, the time required for 50% recrystallization is found to be
30s and 5m, respectively. Estimate the activation energy for
the process.
Answer: use the form of the equation from the homework:
t={-ln(.5)/k}
1/n
=> k = -ln(.5)/ t
n

Assume k=k
0
exp-Q/RT; => -Q/RT=ln(k/k
0
)
So, -Q=RT
1
ln(k
1
/k
0
) =RT
2
ln(k
2
/k
0
)
-Q/R*(1/T
1
-1/T
2
) = ln(k
1
/k
2
)
Q=R ln(t
1
2
/t
2
2
) /(1/T
1
-1/T
2
)
Q= 8.31 ln(30
2
/300
2
) (1/673 - 1/773)
Q = 199,086 J/mole

f = 1 exp kt
n
{ }
0.1 = 1 exp kt
n
{ }
ln 0.9 = kt
n
t =
ln 0.9
k




`
)
1/ n
f = 1 exp kt
n
{ }
0.9 = 1 exp kt
n
{ }
ln 0.1 = kt
n
t =
ln 0.1
k




`
)
1 / n
Sample Problem: 2
Composites: a certain type of (cheap) plywood is made up of
two thin outer sheets of a high density wood with a lower
density filler material inside. If the modulus of the cladding is
10 Gpa, and each sheet is 2mm thick, and the modulus of the
filler layer is 100 Mpa with a thickness of 10mm, what is the
stiffness of the plywood, measured through the thickness?
Apply elementary isostress theory.
Modulus = V
A
(1/E
A
) + V
B
(1/E
B
)
= 1/14 (4/10 + 10/0.1) GPa
= 0.14 GPa.
The composite is dominated by the softer filler layer because of
the loading method. It would be much stiffer if it were loaded
on its edge.
Sample Problems: 3
Nucleation: in a problem on solidification, the latent heat is
50,000 J/mole and the melting point (liquidus) is 850C. The
molar volume is 10
6

m
-3
. No appreciable nucleation is observed
in a carefully controlled experiment in which only homogeneous
nucleation can occur. What is the volumetric driving force for
an undercooling of 50C?
Answer - use the expression for driving force where the latent
heat (enthalpy) is known. G
V
=(HT/T
e
)/V
m

= 50,000.50/(850+273)/10
-6

= 2.23.10
9
J.m
-3
Based on this information, what is the apparent interfacial
energy?
Answer: assume that G* ~ 60kT at the point where nucleation
occurs; 60*1.38.10
-23
*1123=16
3
/3 /(2.23.10
9
)
2

so, =
3
(0.276) = 0.65 J.m
-2
.
Sample Problem: 4
Precipitate growth rates: for a precipitate that is pure element B,
and a solvus line described by log
10
(X
B
) = 2.853 - 2.875.10
+3
/T,
where X
B
is the composition in atomic %, what is the growth
rate at T=600C for a matrix composition X
0B
=1.5% 1 minute
after nucleation has taken place? Assume 1D growth (e.g. of a
slab of precipitate nucleated on a grain boundary). The pre-
factor and activation energy for diffusion of B in A are 7.4.10
-5
m
2
.s
-1
and Q=217.2 kJ.mole
-1
, respectively.
Answer - first calculate the equilibrium concentration of matrix
(alpha) in equilibrium with the precipitate (beta):
X
B
= 0.36
Then the growth rate is given by v=X/2(X
b
-X
e
) * (D/t)
= (1.5-0.36)/2/(100-0.36)*(7.4.10
-5
*exp-{217,200/8.31/873}/60)
= 2.0 10
-12
m.s
-1
, or 7nm per hour!
Pretty slow!
Sample Problem: 5
Coherency Loss: show how the following expression can be
derived for the critical size of a precipitate at which coherency is
lost.
r
crit
= 3/4o
2
.
Answer: recall that
G
coherent
= 4o
2
* 4r
3
/3 + 4r
2

coherent
G
non-coherent
= 4r
2

non-coherent

At the transition size, the two free energies will be the same,
and above this size, the precipitate with incoherent interface will
have the lower energy. Therefore we can write that


4o
2
4r
crit
3
/3 + 4r
crit
2

coherent
= 4r
crit
2

non-coherent

Write =(
non-coherent
-
coherent
)

Thus r
crit
= 3/4o
2
.
Sample Problem: 6
Coherency Loss, contd.: for the problem outlined in number 5,
given a (cubic) precipitate with lattice parameter 3.9 , and a
matrix with a=3.8 , shear modulus =45GPa, and an observed
loss of coherency at r=5nm, what difference in interfacial
energy would you estimate for incoherent versus coherent
interfaces?
Answer: turn the equation around and estimate the difference:
r
crit
= 3/4o
2
<=> = r
crit
* 4o
2
/3.
The misfit = a/a = 0.1/3.8 = 0.0263.
Thus = 5.10
-9
* 4 * 45.10
9 *
0.0263
2
/3 = 0.21 J.m
-2
.
This is a reasonable value.
Sample Problem: 7
Spinodal Decomposition: how can we represent the
phenomenology of spinodal decomposition? One key is to
postulate a function for the dependence of free energy on
composition. The simplest form that will yield a G(X) curve with
a central hump is this:
G(X) = 25,000 * {4(X-0.5)
4
- (X-0.5)
2
} J. mole
-1
Based on this constitutive description, we can now ask, for
example, what the limits of the chemical spinodal are?
Answer: differentiate the formula to find the curvature and set it
equal to zero to locate the inflection points:
d
2
G/dX
2
= 25,000 * {4*4*3(X-0.5)
2
- 2} = 0
48(X-0.5)
2
= 2
X = 0.5 (2/48) = 0.704 or 0.296
We can also easily obtain the miscibility gap because of the
symmetry of the function about X=0.5: dG/dX=0 =>
dG/dX = 25,000 * {4*4(X-0.5)
3
- 2(X-0.5)} = 0 =>
(X-0.5)
2
= 1/8 => X = 0.146 or 0.854
Sample Problem 7: graph
A plot of G(X) = {4(X-0.5)
4
- (X-0.5)
2
}
-0.07
-0.06
-0.05
-0.04
-0.03
-0.02
-0.01
0
0.01
-0.2 0 0.2 0.4 0.6 0.8 1 1.2
G
X
Chemical Spinodal
Miscibility Gap
Sample Problem: 8
Heterogeneous Nucleation versus Homogeneous:
Consider problem 5.5 from P&E and estimate the ratio between
the homogeneous and heterogeneous nucleation rates. The
critical free energy for homogeneous nucleation is 10
-19
J and
the temperature is 500C. Assume that the effective grain
boundary thickness is ~0.4nm and the grain size ~25m;
AA
=
500,
AB
= 600 mJ.m
-2
.
Answer: First calculate the contact angle:

AA
= 2
AB
cosu
u = cos
-1
(
AA
/ 2
AB
) = 53.1
Then calculate the shape factor, S(u):
S(u) = 0.5 (2 + cosu)(1 - cosu)
2
= 0.208
The ratio in nucleation rates is given by P&E Eq. 5.25:
N
het
/N
homo
= C
1
/C
0
exp-{(G*
homo
-G*
hetero
)/kT}

Sample Problem: 8, contd.
N
het
/N
homo
= C
1
/C
0
exp{(G*
homo
-G*
hetero
)/kT}
= /D exp{(G*
homo
- S(u) G*
homo
)/kT}
= /D exp{((1- S(u)* G*
homo
)/kT}
= 0.4/25,000 exp{(1-0.208)*10
-19
/(1.38. 10
-23
*773)
= 0.027
Note the sign of the exponential which gives a large number.
The ratio of the (effective) grain boundary thickness to grain
size decreases the ratio quite significantly. In practical terms,
heterogeneous nucleation is most significant at (or adjacent) to
the nucleation sites (boundaries, dislocations etc.).

o|

|
o

oo

u
Grain
boundary
in alpha
Sample Problem, no. 9
From Dieter, p219 (adapted):
Question: Al-4%Cu (by wt.) has a yield stress of 600MPa. Estimate
the particle size and spacing.
Solution: recognize that this stress relates to age hardening beyond
the peak hardness. Therefore use the Orowan bowing stress to
estimate the stress.
o = <M> t
crss
= <M> Gb/
G=27.6GPa; b=0.25nm; <M>=3.1:
spacing = 3.1*27,600*0.25.10
-9
/ 600= 35.7 nm
Now we must estimate the volume fraction of particles for which we
use the phase diagram, assuming that we are dealing with the
equilibrium phase, u, which is 54 w/o Cu, and the o in equilibrium
with it, 0.5 w/o Cu.
Wt. % Al = (54-4)/(54-0.5) = 93.5; wt. % u = 4-0.5/(54-0.5)=6.5
Volume of o = 93.5gm/2.7 gm/cm
3
=34.6 cm
3

Volume of u = 6.5/ 4.443 gm/cm
3
= 1.5 cm
3
Volume fraction of o = 0.96; volume fraction of u = 0.04.
Use =4r(1-f)/3f (slide 22): r =3*0.04*35.7/4/(1-0.04) = 1.12 nm.


Cheating Policy
Students are referred to the University Policy About Cheating and Plagiarism
(Organization Announcement No. 297, 6116/80). It shall be the policy in this
course to discourage cheating to the extent possible, rather than to try to trap and
to punish. On the other hand, in fairness to all concerned, cheating and plagiarism
will be treated severely.
Cheating includes but is not necessarily limited to:
1.Plagiarism, explained below.
2.Submission of work that is not the student's own for reports or quizzes.
3.Submission or use of falsified data.
Plagiarism includes (but is not limited to) failure to indicate the source with
quotation marks or footnotes, where appropriate, if any of the following are
reproduced in the work submitted by a student:
1.A graph or table of data.
2. Specific language.
3.Exact wording taken from the work, published or unpublished, of another
person."

Test, Exams, Grading Policy
Homeworks: 1 per week 100 points
Quizzes: 1 per week 20 points
Exams: two: see weighting below
Grading Policy A > 90%
B > 80%
C > 70%
D > 55%
The instructor will request an Oral exam in borderline cases.
Weighting (%):
Homeworks 15
Quizzes 5
Lab 30
Exams 50
Notes: the distribution between the two exams is to be determined. The
quizzes are mainly there to encourage students to stay on top of the material.
The 30% weighting for the Lab (or Project) reflects the number of units
assigned to the Lab part of the class.