ch11 TTT

Chapter 11: Transformation in Alloys
Going from one phase to another takes time. Needs Transformation Rate for solid-solid reaction. For hardening, need:
A non-fully miscible A-B binary alloy. A compound AxBy precipitate (e.g. Al-Al2Cu , Fe-Fe 3C, Al-Al 3Mg 2, )
Transformation and Age Hardening in Alloys

Issues to Address
Since transformations take time, what is fraction of transformation vs. logarithm of t?
Fe
FCC
3 Eutectoid transformation (cementite)

(ferrite)
Fe C +
(Austenite)
C
(BCC)
Can transformation be slowed to engineer microstructure?

You need to use a TTT (temperature-time-transformation) diagram.
Required Features of the Compound

Compound between two metals (Al2Cu) or a metal and non-metal (Fe3C). Narrow composition range. Strong covalent bond between the elements. Strong particles.
MSE 280: Introduction to Engineering Materials
D.D. Johnson 2004, 2006-2008
What are microstructure for steels, i.e. fine pearlite, coarse pearlite, spheroidite, bainite, martensite, and tempered martensite ?
Are the mechanical properties of these non-equilibrium microstructures better?

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Phase Transformations in Alloys

Nucleation
nuclei (seeds) act as templates on which crystals grow for nucleus to form rate of addition of atoms to nucleus must be faster than rate of loss once nucleated, growth proceeds until equilibrium is attained Driving force to nucleate increases as we increase T supercooling (eutectic, eutectoid) superheating (peritectic) Small supercooling slow nucleation rate - few nuclei - large crystals Large supercooling rapid nucleation rate - many nuclei - small crystal.
Solidification: Nucleation Types Homogeneous nucleation

nuclei form in the bulk of liquid metal requires considerable supercooling (typically 80-300C)
Heterogeneous nucleation
easier since stable nucleating surface is already present e.g., mold wall, impurities in liquid phase only very slight supercooling (0.1-10C)
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D.D. Johnson 2004, 2006-2008
Homogeneous Nucleation & Energy Effects

Surface Free Energy- destabilizes the nuclei (it takes energy to make an interface) GS = 4r 2 = surface tension
Solidification
r* = 2Tm Hf T
r* = critical radius = surface free energy Tm = melting temperature Hf = latent heat of solidification T = Tm - T = supercooling
GT = Total Free Energy = GS + GV

Volume (Bulk) Free Energy stabilizes the nuclei (releases energy) 4 GV = r 3 G
Note: Hf and are weakly dependent on T r* decreases as T increases For typical T r* ~ 10 nm
G =
volume free energy unit volume

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r* = critical nucleus: for r < r* nuclei shrink; for r >r* nuclei grow (to reduce energy)
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D.D. Johnson 2004, 2006-2008
Rate of Phase Transformations

Kinetics - study of reaction rates of transformation.
To determine reaction rate measure degree of transformation as function of time (while holding temp constant)
Fraction transformed, y
Rate of Phase Transformation

Fixed T
transformation complete maximum rate reached now amount unconverted decreases so rate slows t0.5 rate increases as surface area increases & nuclei grow
0.5
How is degree of transformation measured?

X-ray diffraction many specimens required electrical conductivity measurements on single specimen measure propagation of sound waves on single specimen
D.D. Johnson 2004, 2006-2008
log t
Adapted from Fig. 11.10, Callister & Rethwisch 3e.
Avrami equation => y = 1- exp (-kt n)

fraction transformed time
k & n are transformation specific parameters By convention

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rate = 1 / t0.5
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Temperature Dependence of Transformation

135C 119C 113C 102C 88C 43C
Transformation and undercooling: Fe - Fe3C

Eutectoid transf. (Fe-Fe3C system): For transf. to occur, must cool to below 727C (i.e., must undercool)
1600
+ Fe3C
0.76 wt% C 6.7 wt% C 0.022 wt% C
T(C)
Cast irons have 3 - 4.2wt%C
10
102
104
1400 1200
L Fe3C (cementite) +L (austenite)

FCC
Pearlite
1148C
L+Fe3C
Formed by Eutectoid Transformation (looks like mother of pearl in microscope)
Transformation rate depends on T. 1 Q / RT For the recrystallization of Cu, since r = = Ae

t0.5
BCC
ferrite
1000 800 600 0.022 400 0 (Fe)
Eutectoid:
+Fe 3C
rate increases with increasing temperature Rate often so slow that attainment of equilibrium state not possible!
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Equil. Cooling: Ttransf . = 727C 727C T +Fe 3C Undercooling by Ttransf. < 727 C
1 2 3 4 5
0.76
C, wt%C
6.7
Dark = Fe 3C Light = ferrite

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Why solubility of C more in FCC than BCC (2.1wt% vs 0.022 wt%)?

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Fe - Fe3C Eutectoid Transformation

Transformation of austenite to pearlite:
Austenite () grain boundary
Nucleation and Growth

Rate results from nucleation and growth of crystals.
Fig. 11.1
cementite (Fe3C) Ferrite () pearlite growth direction

y (% pearlite) 100
600C (T larger)
Diffusion of C during transformation
For this transformation,

rate increases with [Teutectoid T ] (i.e., T).
Carbon diffusion
Examples:
50 0
650C 675C (T smaller)
Coarse pearlite formed at higher temperatures relatively soft Fine pearlite

formed at lower temperatures relatively hard
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Isothermal TTT Diagram

Consider: the Fe-Fe3C system, for Co = 0.76 wt% C A transformation temperature of 675C.
y, % transformed 100 50 0 1
Transf. begins Transf. ends
Austenite-to-Pearlite TTT Diagram

Eutectoid composition, Co = 0.77wt%C Begin at T > 727C Rapidly cool to 625oC and hold isothermally.
T(C)
Austenite (stable)
Austenite (unstable)
T = 675C
10 2
10 4
time (s) TE (727C)
700 600 500 400
TE (727C)
- Curves show % transformation. - Note formation at GBs to reduce free energy.
T(C)
700 600 500 400
Austenite (stable)
Austenite (unstable)

50% rlite pea 0%
Pearlite
Pearlite isothermal transformation at 675C

% 100 te 50%pearli 0%
% 100
bct
10 2 10 3 10 4 10 5
10
time (s)
13
10
10 2
10 3
10 4
10 5
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time (s)
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Pearlite Morphology
Two cases:
Ttransf just below TE
--Larger T: diffusion is faster --Pearlite is coarser.
Hypereutectoid Transformations proeutectoid cementite

Consider C0 = 1.13 wt% C
900 800 700 600 A
Ttransf well below TE
--Smaller T: diffusion is slower --Pearlite is finer.
T(C)
A + C A + A P
1600
T(C)
(austenite)
TE (727C)
P
1200
+L
L+Fe3C
1000 800 0.022 600
+Fe 3C
T
0.76
Adapted from Fig. 10.6 (a) and (b), Callister 6e .
500
+Fe 3C
2 3 4 5
727C
- Smaller T: colonies are larger
- Larger T: colonies are smaller
1.13
10
10 2
time (s)
10 3
10 4
400 0 (Fe)
C, wt%C
6.7
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Fe3C (cementite)
1400
Hypo- and Hyper- Eutectoid of Fe - Fe3C
Bainite: Non-equilibrium Products in Fe-Fe3C

Bainite:
-a lathes with long rods of Fe3C in -ferrite matrix. -diffusion controlled.
Proeutectoid
(pre Eutectoid)
Fe 3C
Proeutectoid

800 Austenite (stable)
Fe3C (cementite)
(ferrite)
Fe 3C Proeutectoid eutectoid + Fe3C
Pearlite
Pearlite Proeutectoid eutectoid Fe 3C Fe 3C
T(C)
600
100% pearlite 100% bainite
TE
5 m
Fig. 11.17, Callister & Rethwisch 3e.
400
Proeutectoid wets grain boundaries as it has a lower free energy by forming at surface
200 10 -1 10
100
0%
50%
0.38 wt% C Pearlite and Proeutectoid

1.4 wt% C Pearlite and Proeutectoid Fe 3C

D.D. Johnson 2004, 2006-2008
10 3
10 5
time (s)
D.D. Johnson 2004, 2006-2008
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Spheroidite: Non-equilibrium Products in Fe-Fe3C

Spheroidite:
- spherical Fe3C in an -ferrite matrix. - diffusion dependent. (ferrite) - heat bainite or pearlite for long times just below eutectoid. - Driving Force: reduce -ferrite/Fe3C Fe3C interfacial area. (cementite)
Martensite: Non-equilibrium Products in Fe-Fe3C

Martensite:
--g(FCC) to Martensite (BCT)
(involves single atom jumps) x x x x
60 m
Fe atom sites x
potential C atom sites

Fig. 11.11
Fig. 11.22
TTT Diagram
800
T(C)
60 m
Austenite (stable)
600 400 200 10

-1
P B
5 0% 0%
TE
Martensite needles Austenite
10 0%
0% 50% 90%
to M transformation..
- is rapid (dffusionless!) - % transf. depends on T only.
M+A M+A M+A
10
10 3
105
time (s)
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Martensite Formation
(FCC) slow cooling quench M (BCT) tempering
(involves single atom jumps)
Phase Transformations of Alloys

Effect of adding other elements
Change transition temp.
x x x x
(BCC) + Fe 3C
Fe atom sites x
potential C atom sites
Cr, Ni, Mo, Si, Mn retard + Fe3C reaction (and formation of pearlite, bainite)
Martensite (M) single phase has body centered tetragonal (BCT) crystal structure Diffusionless transformation BCT if C0 > 0.15 wt% C BCT few slip planes hard, brittle
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Continuous Cooling Transformations

Conversion of isothermal transformation diagram to continuous cooling transformation diagram
Isothermal Heat Treatment Example
On the isothermal transformation diagram for a 0.45 wt% C, Fe-C alloy, sketch and label the timetemperature paths to produce the following microstructures: a) 42% proeutectoid ferrite and 58% coarse pearlite b) 50% fine pearlite and 50% bainite c) 100% martensite d) 50% martensite and 50% austenite
Cooling curve
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Solution to Part (a)

a) 42% proeutectoid ferrite and 58% coarse pearlite
Isothermally treat at ~ 680C -- all austenite transforms to proeutectoid and coarse pearlite.
Wpearlite = C0 0.022 0.76 0.022 = 0.45 0.022 = 0.58 0.76 0.022
Solution to Part (b)

b) 50% proeutectoid ferrite and 50% coarse pearlite.
Fe-Fe 3C phase diagram, for C0 = 0.45 wt% C
800

800 A A+ A+P A+B 50%
600 A 400 M (start) M (50%) M (90%)
P B
Isothermally treat at ~ 590C 50% of austenite transforms to fine pearlite.
A+ A+P A+B 50%
600 A
P B
Then isothermally treat at ~ 470C 400 M (start) all remaining austenite M (50%) transforms to bainite. M (90%)
200
200
W = 1 0.58 = 0.42
Adapted from Fig. 10.29, Callister 5e.
0 0.1
10
time (s)
10 3
10 5
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Adapted from Fig. 10.29, Callister 5e. MSE 280: Introduction to Engineering Materials
0 0.1
10
time (s)
10 3
10 5
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D.D. Johnson 2004, 2006-2008
D.D. Johnson 2004, 2006-2008
Solution to Part (c) and (d)

c) 100% Martensite - rapidly quench to room T.
800
Mechanical Behavior Influence of C

Pearlite (med) ferrite (soft)
d) 50% Martensite & 50% austenite.

-- rapidly quench to ~ 290C, hold at this T
A+ A+P A+B 50%
C0 < 0.76 wt% C Hypoeutectoid Hyper
Pearlite (med) Cementite (hard)

C0 > 0.76 wt% C Hypereutectoid Hypo
100 hardness 50 40
Impact energy (Izod, ft-lb)
600 A 400 M (start) M (50%) M (90%)
P B
TS(MPa) 1100 YS(MPa) 900 700
Hypo
%EL
Hyper
80
d)
500 300 0.76
200
0 0
Adapted from Fig. 10.29, Callister 5e. MSE 280: Introduction to Engineering Materials
0 0.1
wt% C
0.5
0.76
c)
10
0.5
wt% C
time (s)
10 3
10 5
27
Increase C content: TS and YS increase, %EL decreases

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Mechanical Props: Fine Pearlite vs. Coarse Pearlite vs. Spheroidite

Hypo
320 Brinell hardness 240 160 80 0 0.5
Mechanical Props: Fine Pearlite vs. Martensite

Hypo
Brinell hardness 600
Hyper
Ductility (%RA) fine pearlite coarse pearlite spheroidite
90
Hypo
Hyper
spheroidite
Hyper
60
martensite
400
30
wt%C
coarse pearlite fine pearlite 0 0.5
200
fine pearlite
0 0.5
wt%C
wt% C
Hardness: %RA:
fine > coarse > spheroidite fine < coarse < spheroidite
Hardness: fine pearlite << martensite.
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Tempering of Martensite
Heat treat martensite to form tempered martensite tempered martensite less brittle than martensite tempering reduces internal stresses caused by quenching
TS(MPa) YS(MPa) 1800 1600 1400 1200 1000 800 200 400 600 %RA TS
Possible Transformations
60 50 %RA 40 30
Tempering T (C)
tempering produces extremely small Fe 3C particles surrounded by . tempering decreases TS, YS but increases %RA
D.D. Johnson 2004, 2006-2008
9 m
YS
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Needs for Processing and Age Hardening

For hardening, need: A non-fully miscible A-B binary alloy. A compound A xBy precipitate (e.g. Al-Al2Cu , Fe-Fe3C, Al-Al3Mg2, ) Control the misfit dislocations. Required Features of the Compound Compound between two metals (Al2Cu) or a metal and non-metal (Fe3C). Narrow composition range. Strong covalent bond between the elements. Strong particles.
D.D. Johnson 2004, 2006-2008
Precipitation Hardening
Particles impede dislocation motion. Procedure: Ex: Al-Cu system -- Pt A: solution heat treat
T(C)
700 600 A C 20 L +L +L
CuAl2
500 400
+
30 40 50
(get solid solution) -- Pt B: quench to room temp. (retain solid solution) -- Pt C: reheat to nucleate small particles in phase.
Temp. Pt A (soln heat treat) Pt C (precipitate ) Time
(Al)
300 0 B 10
composition range available for precipitation hardening

wt% Cu
Pt B
Other alloys that precipitation harden: Cu-Be, Cu-Sn, Mg-Al

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2014 Al Alloy:
Influence of Precipitation Heat Treatment on TS, %EL

Minima on %EL curves.
Recall Why Precipitation Strengthens

Peak-aged
-avg. particle size = 64b -closer spaced particles efficiently stop dislocations.
Over-aged
-avg. particle size = 361b -more widely spaced particles not as effective.
Maxima on TS curves. Increasing T accelerates process.

no so n- eq lid u so il. lut ion ma pre ny s cip ma ita ll ag tes ed
fe p we ov recip r lar era ita ge ge tes d %EL (2 in sample)
tensile strength (MPa)
30 20 10 0 149C
400 300 200 100
149C 204C
Later: Precipitates can relieve their lattice misfit by creating misfit dislocations around precipitate, thereby reducing opposing stress field to dislocation glide. So it is not just size.
204C
- Thus, over-aged precipitates are less effective at stopping dislocations.
1min 1h 1day 1mo 1yr precipitation heat treat time
1min 1h 1day 1mo 1yr precipitation heat treat time

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Basic features required for age-hardening

T solid solution + compound T
Formation of the compound
100%
+ +
Coarse Fine
A A
alloy composition
CB
By length of annealing time
CB
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Fraction of the compound (Lever Rule)

T + T f A C C0 tie line
Al-rich Al-Mg: Al solid-solution + Al3Mg2
f =
C0 C C C
CB
=Al3Mg 2
Note that alloy is 2/5 Mg or 40at% Mg
C
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Al-rich Al-Mg: Al3Mg2 fraction

Anneal T=250 C Average C0=0.1 C=0.05 C=0.40
Hardening in Al-Cu: phases, microstructure, aging.

Heat treatment at small wt% Cu solid-solution precipitation anneal at fix T coarsening (need high enough T for diffusion) anneal time controls phase ( or in phase), size of particle and local strain. Ageing creates or phase in phase.
c0
f =
C0 C C C = 0.10 0.05 = 0.142 0.40 0.05
Plate-like precipitates (GP zones) in Al-Cu

initially 25 atoms wide and 2 layers thick coarsening creates larger zones. Coherent precipitate gives larger stress field.
C C0
14% is phase.
solid-solution
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phase in
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Hardening in Al-Cu: phases, microstructure, aging.

Heat treatment at small wt% Cu phase is disordered and coherent with phase lattice (large strain fields). phase is ordered and incoherent with lattice due to misfit dislocations that provide strain relief around particle.
Hardening in Al-Cu: mechanical properties and aging.

UTS YS
260 C
Over-aging occurs when misfit dislocations form.

149 C 204 C
Why does this affect TS?

Note that temperature affects aging. For higher T, the faster the precipitates coarsen (i.e. grows) and relaxes strain. The higher T, the faster aging occurs.
Plate-like precipitates (GP zones) in Al-Cu Coherent precipitate gives larger stress field. Incoherent precipitate reduces larger stress field.
Duration of Heat Treatment (h)

Example of misfit dislocations Boeing 767 has wing skin with Al 7150-T651 (6.2Zn, 2.3 Cu, 2.3 Mg, 0.12 Zr) forming particles MgZn2 GB decorated w/ particles.
Solid-solution
Coherent boundaries
Incoherent boundary with misfit dislocations

D.D. Johnson 2004, 2006-2008
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Hardening in Al-alloys: Boeing Airplane Skin
Synopsis on Hardening via Precipitates

Steels: increase TS, Hardness (and cost) by adding - C (low alloy steels) - Cr, V, Ni, Mo, W (high alloy steels) - ductility usually decreases w/additions. Non-ferrous: Cu, Al, Ti, Mg, Refractory, and noble metals. Fabrication techniques: forming, casting, joining. Hardenability: increases with alloy content. Microstructure dictates affect on mechanical behavior, and Phase Diagram reveals possible micorstructure.
TEM of microstructure from 7150-T651 Al-alloy (6.2Zn, 2.3Cu, 2.3Mg, 0.12Zr, Al-balance)
Light regions: Al solid-solution Dark regions: small plate-shaped (majority) -phase (non-equilibrium) remainder (minority) -phase (equilibrium)
e.g., Al-Al 2Cu (equilibrium case) and Fe-Fe3C (metastable case). planar precipitates pearlite, bainite, austenite, ferrite, spheriodite
T-T-T Diagram reveals processing to achieve microstructure. Solid-solutions, substitutional and interstitial compound different. Precipitation hardening -effective means to increase strength in Al, Cu, and Mg alloys. - do not over age, which introduces misfit dislocations.
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Melting & Glass Transition Temps.

What factors affect Tm and Tg?
Both Tm and Tg increase with increasing chain stiffness Chain stiffness increased by presence of
1. 2. 3. Bulky sidegroups Polar groups or sidegroups Chain double bonds and aromatic chain groups
Summary: TTT Diagram and Microstructure

Precipitation hardening: Two-phase regions containing metal + ordered compound needed. (Al, Mg alloys precipitation hardenable.) Two-phase microstructure (with stiffer compound) leads to increase in TS, UTS, Hardness but to decrease in ductility. Type of microstructure dictates affect on mechanical behavior. e.g., Al-Al 2Cu (equilibrium case) and Fe-Fe 3C (metastable case).
planar precipitates pearlite, bainite, austenite, ferrite, spheriodite
Regularity of repeat unit arrangements affects Tm only
Controlling composition, fractions of phases, microstructure via T-T-T diagram reveals processing route and subsequent mechanical behavior. Difference between substitutional compound or solid solution and interstitial compound (atom + small impurity).
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ch11 TTT

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Chapter 11: Transformation in Alloys

Transformation and Age Hardening in Alloys

3 Eutectoid transformation (cementite)

Can transformation be slowed to engineer microstructure?

Required Features of the Compound

Are the mechanical properties of these non-equilibrium microstructures better?

MSE 280: Introduction to Engineering Materials

D.D. Johnson 2004, 2006-2008

Phase Transformations in Alloys

Solidification: Nucleation Types Homogeneous nucleation

MSE 280: Introduction to Engineering Materials

D.D. Johnson 2004, 2006-2008

MSE 280: Introduction to Engineering Materials

D.D. Johnson 2004, 2006-2008

Homogeneous Nucleation & Energy Effects

GT = Total Free Energy = GS + GV

Note: Hf and are weakly dependent on T r* decreases as T increases For typical T r* ~ 10 nm

volume free energy unit volume

MSE 280: Introduction to Engineering Materials

D.D. Johnson 2004, 2006-2008

Rate of Phase Transformations

Rate of Phase Transformation

How is degree of transformation measured?

Adapted from Fig. 11.10, Callister & Rethwisch 3e.

Avrami equation => y = 1- exp (-kt n)

k & n are transformation specific parameters By convention

MSE 280: Introduction to Engineering Materials

Temperature Dependence of Transformation

Transformation and undercooling: Fe - Fe3C

Cast irons have 3 - 4.2wt%C

L Fe3C (cementite) +L (austenite)

Formed by Eutectoid Transformation (looks like mother of pearl in microscope)

Transformation rate depends on T. 1 Q / RT For the recrystallization of Cu, since r = = Ae

1000 800 600 0.022 400 0 (Fe)

Dark = Fe 3C Light = ferrite

Why solubility of C more in FCC than BCC (2.1wt% vs 0.022 wt%)?

Fe - Fe3C Eutectoid Transformation

Nucleation and Growth

cementite (Fe3C) Ferrite () pearlite growth direction

Diffusion of C during transformation

For this transformation,

650C 675C (T smaller)

Adapted from Fig. 11.12, Callister & Rethwisch 3e.

Coarse pearlite formed at higher temperatures relatively soft Fine pearlite

MSE 280: Introduction to Engineering Materials

MSE 280: Introduction to Engineering Materials

D.D. Johnson 2004, 2006-2008

Isothermal TTT Diagram

Austenite-to-Pearlite TTT Diagram

time (s) TE (727C)

700 600 500 400

Pearlite isothermal transformation at 675C

MSE 280: Introduction to Engineering Materials

D.D. Johnson 2004, 2006-2008

Hypereutectoid Transformations proeutectoid cementite

Ttransf well below TE

--Smaller T: diffusion is slower --Pearlite is finer.

1000 800 0.022 600

Adapted from Fig. 10.6 (a) and (b), Callister 6e .

- Smaller T: colonies are larger

- Larger T: colonies are smaller

Adapted from Fig. 11.16, Callister & Rethwisch 3e.