MicrostructureandPropertiesII

MSE 27-302
Fall, 2002 (2nd mini-course)
Prof. A. D. Rollett
http://neon.mems.cmu.edu/rollett/27302/ 27302.html

CourseContent

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

Wheredoesmicrostructurecomefrom?Phasetransformations,kineticsof
transformations,theKolmogorovJohnsonMehlAvramiequation.
PropertiesofCompositematerials:backgroundmaterialonglassceramicsforLab1.
Phasetransformations:drivingforces,thermodynamicsofnucleation(precipitation
reactions).
Transformations:kineticsofgrowth:asimpleTTTdiagram.Howtocalculateandpredict
TTTandCCTdiagrams.
Theroleofinterfacesinheterogeneousnucleation;exampleoftheAlCusystem;
sequencesofmetastableprecipitates.
Theagehardeningcurve;methodsofmeasuringtransformations.Thesimilaritiesbetween
mechanicalhardnessandmagnetichardness.
Impactofprecipitationoncomplexproperties:exampleoffatigueasamicrostructure
sensitiveproperty.
Morecomplexdiffusivetransformations:exampleofFeCsystemforeutectoidreactions.
Continuoustransformations:spinodaldecomposition.
Coarseningoftwophasestructures;effectoftwophasestructuresoncreepproperties(Ni
alloysasanexample).
Competitionbetweentransformationmechanisms;discussionofnondiffusive
transformations;massivetransformations,martensitictransformations;exploitationof
martensiticreactionsforshapememoryalloys.

Theultimateincomplicatedmicrostructures:introductiontoweldingandjoining.

Technicaltopics
Technical Issues:

Solid 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.

MaterialProperties,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.

MaterialsSystems
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

StudentInputfor302
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.

MaterialsDesign

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 statusquo 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)

302Jeopardy:1
1.Rankissumoftherankof
thequantitiesoneachside

4.RTln{X0/Xe}.

Q1.Howistherankofaproperty
Q4.Whatistheformulaforthedriving
tensordeterminedfromtherankofeach
forceforprecipitationinasimple2
relatedquantity?
phasesystem?

2.Freeenergy

Q2.Whatthermodynamicquantity
shouldweusetopredictwhetherornot
areactionwilloccur?

3.2foldsymmetryaxes(diads)
Q3.Whichsymmetryelementis
foundon<110>directionsinfcc

materials?

5.Nonucleationbarrier
Q5.Nameakeydifferencebetween
discontinuousandcontinuousphase
transformation.
6.Approximately3timesthe
yieldstress.
Q6.Howmuchgreateristhehardness
thantheyieldstress(sameunits)?

302Jeopardy:2
1.Proportionalto
undercooling
Q1.Howisdrivingforcerelatedto
undercooling?

4.Hf(T/Tmelt).
Q4.Whatistheformulaforthedriving
forceforsolidification?

2.Differencebetweenthetemp.atwhich
thecompositionintersectsthesolvus
5.Twophasesinacompositegenerally
(liquidus)andthecurrenttemp.
expand/contractatdifferentrateswith
T.
Q2.Howistheundercoolingdefined?
Q5.Whatisonecauseofresidualstress
inacompositematerial?

3.Einsteinnotation
Q3.Whatisthenamefortheconvention
thatstatesthatrepeatedindicesare
summedover?

6.Differentiatethetotalenergy.
Q6.Howdowedeterminethepointat
whichanenergyreleaserateiszero?

302Jeopardy:3
1.Balancebetweenratesofadding
surfaceenergyandgainingfreeenergy
fromtransformation
Q1.Howdoesonedeterminethe
barriertonucleation?

4.Becauselargeinterfacialenergies
meanhighbarrierstonucleation(and
heterogeneoussites,ifavailable,operate
first).
Q4.Whyishomogeneousnucleation
2.Inprecipitationofproeutectoidferrite, onlyobservedinafewcases?
thethermodynamicterminvolvesthelog
5.163/GV2.
ofaratiooftermsin(1X).
Q2.Whyisthedrivingforcefora
Q5.Whatistheformulaforthecritical
eutectoiddecompositionsmall
freeenergyofnucleation?
comparedtodecompositionofasimple
solidsolution(e.g.proeutectoid
decompositionofaustenite)?
6.Itisavolumetricenergyandis
subtractedoffthechemicalfreeenergy
3.2/GV
fortransformation.
Q3.Whatistheformulaforthecritical
Q6.Whatistheroleofelasticenergyin
radius?

nucleation?

302Jeopardy:4
1.163/{GVGS}2
Q1.Whatisthefreeenergybarrierin
thepresenceofanelasticenergy?
2.Al2Cuplateletsalignedwith{100}
planes.
Q2.Whateffectdoeselasticanisotropy
haveonprecipitationintheAlCu
system?

4.Therateincreasesbecauseof
increasingdrivingforcebutthen
decreasesbecauseofdecreasing
diffusionrate.
Q4.Whydoesthegrowthratefirst
increasewithundercoolingandthen
decrease?
5.D 2C = C/t.
Q5.Whatisthediffusionequation(w/o
sourceterms)?

3.Matchingofclosepacked
planes,e.g.{110}bcc//{111}fcc

6.Linearizedgradients.

Q3.Whatimpactdoesatomicmatching
haveontheorientationrelationship
betweenparentandproductphases?

Q6.Whatapproximationcanwemaketo
solvethediffusionequationforpptgrowthin
1D?

302Jeopardy:5
1.Thechangeinconcentrationaround
oneprecipitateaffectstheconcentration
aroundadjacentprecipitates.
Q1.Whatisthecauseof
impingementofconcentrationfields?
2.Grainboundariesactasshortcircuit
diffusionpathsfortransportofsoluteto
precipitates.
Q2.Whydoprecipitatesgrowmore
rapidlyongrainboundariesthaninthe
bulk(atlowtemperatures)?

3.Decreasingradiusofa
precipitateraisesitssolubility.
Q3.WhatdoestheGibbsThomson
effectdotoprecipitates?

4.Solutediffusesfromsmall
precipitatestolargeones.

Q4.Whatcausescoarseningof
precipitates?
5.<R3(t)><R3(t=0)>=kt.
Q5.Whatistherelationshipbetween
radiusandtimeforcoarsening?
6.x = C0/ (C - Ce) (Dt).
Q6.Whatistherelationshipbetweenpptsize
andtimefordiffusioncontrolledgrowthin
1D?

Officehours,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.

ExamRules
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.)

27302,Labs
Lab 1 = Investigation of precipitation in glassceramics. 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.

TopicList:302

Wheredoesmicrostructurecomefrom?Phasetransformations,kineticsoftransformations,theKolmogorovJohnson
MehlAvramiequation.
PropertiesofCompositematerials:ruleofmixtures.BackgroundmaterialonglassceramicsforLab1.
Phasetransformations:drivingforces,thermodynamicsofnucleation(precipitationreactions).
Transformations:kineticsofgrowth:asimpleTTTdiagram.
Theroleofinterfacesinheterogeneousnucleation;exampleoftheAlCusystem;sequencesofmetastableprecipitates.
Theagehardeningcurve;methodsofmeasuringtransformations.
Impactofprecipitationoncomplexproperties:exampleoffatigueasamicrostructuresensitiveproperty.
Morecomplexdiffusivetransformations:exampleofeutectoidreactions.
Continuoustransformations:spinodaldecomposition.
Coarseningoftwophasestructures;effectoftwophasestructuresoncreepproperties(Nialloysasanexample).
Competitionbetweentransformationmechanisms;discussionofnondiffusivetransformations;massive
transformations,martensitictransformations;exploitationofmartensiticreactionsforshapememoryalloys.
Parallelsbetweenmagneticandmechanicalhardness.
Theultimateincomplicatedmicrostructures:introductiontoweldingandjoining:notaddressedin2001.
Cellularstructures:foams,wood,bread(!),bone,composites.
GuestLecture(Prof.E.Towe):quantumdotstructuresinsemiconductors.

Sampleproblem: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)/ tn
Assume k=k0exp-Q/RT; => -Q/RT=ln(k/k 0)
So, -Q=RT1ln(k1/k0) =RT2ln(k2/k0)
-Q/R*(1/T1-1/T2) = ln(k1/k2)
Q=R ln(t12/t22) /(1/T1-1/T2)
Q= 8.31 ln(302/3002) (1/673 - 1/773)
n
n
f = 1 exp{kt } f = 1exp{kt }
Q = 199,086 J/mole
n
n

0.1 =1 exp{kt }

0.9 =1 exp{kt }

ln0.9 =ktn

ln0.1=ktn

ln0.91/ n

t =
k

ln0.11/ n

t =
k

SampleProblem: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 = VA(1/EA) + VB(1/EB)
= 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.

SampleProblems: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
106 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. GV=(HT/Te)/Vm
= 50,000.50/(850+273)/10-6
= 2.23.109 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=163/3 /(2.23.109)2
so, = 3(0.276) = 0.65 J.m-2.

SampleProblem:4
Precipitate growth rates: for a precipitate that is pure element B, and a
solvus line described by log10(XB) = 2.853 - 2.875.10+3/T, where XB is the
composition in atomic %, what is the growth rate at T=600C for a
matrix composition X0B=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 m2.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):
XB = 0.36
Then the growth rate is given by v=X/2(Xb-Xe) * (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!

SampleProblem:5
Coherency Loss: show how the following expression can be derived
for the critical size of a precipitate at which coherency is lost.

rcrit = 3/42.

Answer: recall that

Gcoherent
= 42 * 4r3/3 + 4r2coherent
Gnon-coherent =
4r2non-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
424rcrit3/3 + 4rcrit2coherent=
4rcrit2non-coherent
Write =(non-coherent - coherent)
Thus rcrit = 3/42.

SampleProblem: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:
rcrit = 3/42 <=> =rcrit* 42 /3.
The misfit = a/a = 0.1/3.8 = 0.0263.
Thus =5.10-9* 4 * 45.109 * 0.02632 /3 = 0.21 J.m-2.
This is a reasonable value.

SampleProblem: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(X0.5)4(X0.5)2}J.mole1
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:
d2G/dX2 = 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

SampleProblem7:graph
A plot of G(X) ={4(X0.5)4(X0.5)2}
0.01
0
-0.01

ChemicalSpinodal

-0.02

-0.03
-0.04
-0.05

MiscibilityGap

-0.06
-0.07

-0.2

0.2

0.4

0.6

0.8

1.2

SampleProblem: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 = 2AB cos
= cos-1 (AA/ 2AB) = 53.1
Then calculate the shape factor, S():
S() = 0.5 (2 + cos)(1 - cos)2 = 0.208
The ratio in nucleation rates is given by P&E Eq. 5.25:
Nhet/Nhomo = C1/C0 exp-{(G*homo-G*hetero)/kT}

SampleProblem:8,contd.

Nhet/Nhomo = C1/C0 exp{(G*homo-G*hetero)/kT}

= /D exp{(G*homo- S() G*homo)/kT}
= /D exp{((1- S()* 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.).

Grain
boundary
inalpha

SampleProblem,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.
<M>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, ,
which is 54 w/o Cu, and the in equilibrium with it, 0.5 w/o Cu.
Wt. % Al = (54-4)/(54-0.5) = 93.5; wt. % = 4-0.5/(54-0.5)=6.5
Volume of = 93.5gm/2.7 gm/cm 3 =34.6 cm3
Volume of = 6.5/ 4.443 gm/cm3 = 1.5 cm3
Volume fraction of = 0.96; volume fraction of = 0.04.
Use =4r(1-f)/3f (slide 22): r =3*0.04*35.7/4/(1-0.04) = 1.12 nm.

CheatingPolicy

StudentsarereferredtotheUniversityPolicyAboutCheatingandPlagiarism
(OrganizationAnnouncementNo.297,6116/80).Itshallbethepolicyinthis
coursetodiscouragecheatingtotheextentpossible,ratherthantotrytotrapand
topunish.Ontheotherhand,infairnesstoallconcerned,cheatingandplagiarism
willbetreatedseverely.
Cheatingincludesbutisnotnecessarilylimitedto:
1.Plagiarism,explainedbelow.
2.Submissionofworkthatisnotthestudent'sownforreportsorquizzes.
3.Submissionoruseoffalsifieddata.
Plagiarismincludes(butisnotlimitedto)failuretoindicatethesourcewith
quotationmarksorfootnotes,whereappropriate,ifanyofthefollowingare
reproducedintheworksubmittedbyastudent:
1.Agraphortableofdata.
2.Specificlanguage.
3.Exactwordingtakenfromthework,publishedorunpublished,ofanother
person."

Test,Exams,GradingPolicy

Homeworks:1perweek 100points
Quizzes:1perweek
20points
Exams:two:seeweightingbelow
GradingPolicy A>90%
B>80%
C>70%
D>55%
TheinstructorwillrequestanOralexaminborderlinecases.
Weighting(%):
Homeworks
15
Quizzes
5
Lab 30
Exams
50
Notes:thedistributionbetweenthetwoexamsistobedetermined.Thequizzesare
mainlytheretoencouragestudentstostayontopofthematerial.The30%weighting
fortheLab(orProject)reflectsthenumberofunitsassignedtotheLabpartoftheclass.