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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.
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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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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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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
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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
Adapted from Fig. 10.15, Callister & Rethwisch 3e.

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)

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

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)

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

Adapted from Fig. 10.28, Callister & Rethwisch 3e.

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

Isothermal TTT Diagram


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


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1.4 wt% C Pearlite and Proeutectoid Fe 3C


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10 3

10 5

Adapted from Fig. 11.18, Callister & Rethwisch 3e.

time (s)
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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

Isothermal TTT Diagram

TTT Diagram
800

T(C)
60 m
Fig. 11.19, Callister & Rethwisch 3e.

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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Adapted from Fig. 11.24, Callister & Rethwisch 3e.

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Continuous Cooling Transformations


Conversion of isothermal transformation diagram to continuous cooling transformation diagram

Isothermal Heat Treatment Example

Adapted from Fig. 11.26, Callister & Rethwisch 3e.

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

Fe-Fe 3C phase diagram, for C0 = 0.45 wt% C


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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Solution to Part (c) and (d)


c) 100% Martensite - rapidly quench to room T.
Fe-Fe 3C phase diagram, for C0 = 0.45 wt% C
800

Mechanical Behavior Influence of C


Pearlite (med) ferrite (soft)
Adapted from Fig. 10.34, Callister & Rethwisch 3e.

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
Adapted from Fig. 10.37, Callister & Rethwisch 3e.

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
Adapted from Fig. 11.30, Callister & Rethwisch 3e.

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
Fig. 11.33, Callister & Rethwisch 3e.

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

Adapted from Fig. 11.31, Callister & Rethwisch 3e.

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
Fig. 11.34, Callister & Rethwisch 3e.

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
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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.
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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


Fig. 11.43, Callister & Rethwisch 3e.

wt% Cu

Pt B

Fig. 11.41, Callister & Rethwisch 3e.

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
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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
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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


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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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