Chapter 10: Phase Transformationsdocs.neu.edu.tr/staff/filiz.shanableh/ME211-Leture notes... ·...

29
Chapter 10 - 1 ISSUES TO ADDRESS... Transforming one phase into another takes time. How does the rate of transformation depend on time and temperature? Is it possible to slow down transformations so that non-equilibrium structures are formed? Are the mechanical properties of non-equilibrium structures more desirable than equilibrium ones? Fe (Austenite) Eutectoid transformation C FCC Fe 3 C (cementite) (ferrite) + (BCC) Chapter 10: Phase Transformations

Transcript of Chapter 10: Phase Transformationsdocs.neu.edu.tr/staff/filiz.shanableh/ME211-Leture notes... ·...

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Chapter 10 - 1

ISSUES TO ADDRESS... • Transforming one phase into another takes time.

• How does the rate of transformation depend on

time and temperature? • Is it possible to slow down transformations so that

non-equilibrium structures are formed?

• Are the mechanical properties of non-equilibrium

structures more desirable than equilibrium ones?

Fe

(Austenite)

Eutectoid transformation

C FCC

Fe3C

(cementite)

(ferrite)

+

(BCC)

Chapter 10:

Phase Transformations

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Chapter 10 - 2

Phase Transformations

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 crystals

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Chapter 10 - 3

Solidification: Nucleation Types

• Homogeneous nucleation

– nuclei form in the bulk of liquid metal

– requires considerable supercooling (typically 80-300ºC)

• Heterogeneous nucleation – much easier since stable “nucleating surface” is

already present — e.g., mold wall, impurities in liquid phase

– only very slight supercooling (0.1-10ºC)

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Chapter 10 - 4

r* = critical nucleus: for r < r* nuclei shrink; for r >r* nuclei grow (to reduce energy)

Adapted from Fig.10.2(b), Callister & Rethwisch 8e.

Homogeneous Nucleation & Energy Effects

GT = Total Free Energy

= GS + GV

Surface Free Energy - destabilizes

the nuclei (it takes energy to make

an interface)

24 rGS

= surface tension

Volume (Bulk) Free Energy –

stabilizes the nuclei (releases energy)

GrGV3

3

4

volume unit

energy free volumeG

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Chapter 10 - 5

Solidification

TH

Tr

f

m2*

Note: Hf and are weakly dependent on T

r* decreases as T increases

For typical T r* ~ 10 nm

Hf = latent heat of solidification

Tm = melting temperature

= surface free energy

T = Tm - T = supercooling

r* = critical radius

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Chapter 10 - 6

Rate of Phase Transformations

Kinetics - study of reaction rates of phase

transformations

• To determine reaction rate – measure degree

of transformation as function of time (while

holding temp constant)

measure propagation of sound waves –

on single specimen

electrical conductivity measurements –

on single specimen

X-ray diffraction – many specimens required

How is degree of transformation measured?

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Chapter 10 - 7

Rate of Phase Transformation

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

– k & n are transformation specific parameters

transformation complete

log t

Fra

ction tra

nsfo

rmed, y

Fixed T

fraction

transformed

time

0.5

By convention rate = 1 / t0.5

Adapted from

Fig. 10.10,

Callister &

Rethwisch 8e.

maximum rate reached – now amount unconverted decreases so rate slows

t0.5 rate increases as surface area increases

& nuclei grow

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Chapter 10 - 8

Temperature Dependence of

Transformation Rate

• For the recrystallization of Cu, since

rate = 1/t0.5

rate increases with increasing temperature

• Rate often so slow that attainment of equilibrium

state not possible!

Adapted from Fig.

10.11, Callister &

Rethwisch 8e.

(Fig. 10.11 adapted

from B.F. Decker and

D. Harker,

"Recrystallization in

Rolled Copper", Trans

AIME, 188, 1950, p.

888.)

135 C 119 C 113 C 102 C 88 C 43 C

1 10 102 104

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Chapter 10 - 9

Transformations & Undercooling

• For transf. to occur, must

cool to below 727ºC

(i.e., must “undercool”)

• Eutectoid transf. (Fe-Fe3C system): + Fe3C

0.76 wt% C 0.022 wt% C

6.7 wt% C

Fe

3C

(ce

me

ntite

)

1600

1400

1200

1000

800

600

400 0 1 2 3 4 5 6 6.7

L

(austenite)

+L

+Fe3C

+Fe3C

L+Fe3C

(Fe) C, wt%C

1148ºC

T(ºC)

ferrite 727ºC

Eutectoid: Equil. Cooling: Ttransf. = 727ºC

T

Undercooling by Ttransf. < 727 C

0.7

6

0.0

22

Adapted from Fig.

9.24,Callister & Rethwisch

8e. (Fig. 9.24 adapted from

Binary Alloy Phase

Diagrams, 2nd ed., Vol. 1,

T.B. Massalski (Ed.-in-

Chief), ASM International,

Materials Park, OH, 1990.)

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Chapter 10 - 10

The Fe-Fe3C Eutectoid Transformation

Coarse pearlite formed at higher temperatures – relatively soft

Fine pearlite formed at lower temperatures – relatively hard

• Transformation of austenite to pearlite:

Adapted from

Fig. 9.15,

Callister &

Rethwisch 8e.

pearlite growth direction

Austenite ( )

grain boundary

cementite (Fe3C)

Ferrite ( )

• For this transformation,

rate increases with

[Teutectoid – T ] (i.e., T). Adapted from

Fig. 10.12,

Callister &

Rethwisch 8e.

675ºC

( T smaller)

0

50

y (

% p

earlite)

600ºC

( T larger) 650ºC

100

Diffusion of C during transformation

Carbon

diffusion

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Chapter 10 - 11

Adapted from Fig. 10.13,Callister &

Rethwisch 8e. (Fig. 10.13 adapted from H.

Boyer (Ed.) Atlas of Isothermal

Transformation and Cooling

Transformation Diagrams, American

Society for Metals, 1977, p. 369.)

Generation of Isothermal Transformation

Diagrams

• The Fe-Fe3C system, for C0 = 0.76 wt% C

• A transformation temperature of 675ºC.

100

50

0 1 10 2 10 4

T = 675ºC

y,

% tra

nsfo

rme

d

time (s)

400

500

600

700

1 10 10 2 10 3 10 4 10 5

Austenite (stable) TE (727ºC)

Austenite (unstable)

Pearlite

T(ºC)

time (s)

isothermal transformation at 675ºC

Consider:

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Chapter 10 - 12

• Eutectoid composition, C0 = 0.76 wt% C

• Begin at T > 727ºC

• Rapidly cool to 625ºC

• Hold T (625ºC) constant (isothermal treatment)

Adapted from Fig.

10.14,Callister &

Rethwisch 8e. (Fig. 10.14

adapted from H. Boyer

(Ed.) Atlas of Isothermal

Transformation and

Cooling Transformation

Diagrams, American

Society for Metals, 1997,

p. 28.)

Austenite-to-Pearlite Isothermal Transformation

400

500

600

700

Austenite (stable) TE (727ºC)

Austenite

(unstable)

Pearlite

T(ºC)

1 10 10 2 10 3 10 4 10 5

time (s)

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Chapter 10 - 13

Transformations Involving

Noneutectoid Compositions

Hypereutectoid composition – proeutectoid cementite

Consider C0 = 1.13 wt% C

TE (727ºC)

T(ºC)

time (s)

A

A

A +

C

P

1 10 102 103 104

500

700

900

600

800

A +

P

Adapted from Fig. 10.16,

Callister & Rethwisch 8e. Adapted from Fig. 9.24,

Callister & Rethwisch 8e.

Fe

3C

(ce

me

ntite

)

1600

1400

1200

1000

800

600

400 0 1 2 3 4 5 6 6.7

L

(austenite)

+L

+Fe3C

+Fe3C

L+Fe3C

(Fe) C, wt%C

T(ºC)

727ºC T

0.7

6

0.0

22

1.1

3

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Chapter 10 - 14

10 10 3

10 5

time (s) 10

-1

400

600

800

T(ºC) Austenite (stable)

200

P

B

TE A

A

Bainite: Another Fe-Fe3C

Transformation Product • Bainite:

-- elongated Fe3C particles in

-ferrite matrix

-- diffusion controlled • Isothermal Transf. Diagram,

C0 = 0.76 wt% C

Adapted from Fig. 10.18,

Callister & Rethwisch 8e.

Adapted from Fig. 10.17, Callister &

Rethwisch 8e. (Fig. 10.17 from Metals

Handbook, 8th ed., Vol. 8, Metallography,

Structures, and Phase Diagrams, American

Society for Metals, Materials Park, OH,

1973.)

Fe3C

(cementite)

5 m

(ferrite)

100% bainite

100% pearlite

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Chapter 10 - 15

• Spheroidite: -- Fe3C particles within an -ferrite matrix

-- formation requires diffusion

-- heat bainite or pearlite at temperature

just below eutectoid for long times

-- driving force – reduction

of -ferrite/Fe3C interfacial area

Spheroidite: Another Microstructure

for the Fe-Fe3C System

Adapted from Fig. 10.19, Callister &

Rethwisch 8e. (Fig. 10.19 copyright

United States Steel Corporation,

1971.)

60 m

(ferrite)

(cementite)

Fe3C

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Chapter 10 - 16

• Martensite: -- (FCC) to Martensite (BCT)

Adapted from Fig. 10.21, Callister &

Rethwisch 8e. (Fig. 10.21 courtesy

United States Steel Corporation.)

Adapted from Fig. 10.20,

Callister & Rethwisch 8e.

Martensite: A Nonequilibrium

Transformation Product

Martensite needles Austenite

60

m

x

x x

x

x

x potential

C atom sites

Fe atom

sites

Adapted from

Fig. 10.22,

Callister &

Rethwisch 8e.

• Isothermal Transf. Diagram

• to martensite (M) transformation..

-- is rapid! (diffusionless)

-- % transf. depends only on T to

which rapidly cooled

10 10 3

10 5 time (s) 10

-1

400

600

800

T(ºC) Austenite (stable)

200

P

B

TE A

A

M + A M + A

M + A

0% 50% 90%

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Chapter 10 - 17

(FCC) (BCC) + Fe3C

Martensite Formation

slow cooling

tempering

quench

M (BCT)

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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Chapter 10 - 18

Phase Transformations of Alloys

Effect of adding other elements

Change transition temp.

Cr, Ni, Mo, Si, Mn

retard + Fe3C

reaction (and formation of

pearlite, bainite)

Adapted from Fig. 10.23,

Callister & Rethwisch 8e.

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Chapter 10 - 19

Adapted from Fig. 10.25,

Callister & Rethwisch 8e.

Continuous Cooling

Transformation Diagrams

Conversion of isothermal transformation diagram to continuous cooling transformation diagram

Cooling curve

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Chapter 10 - 20

Isothermal Heat Treatment Example

Problems On the isothermal transformation diagram for

a 0.45 wt% C, Fe-C alloy, sketch and label

the time-temperature 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

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Chapter 10 - 21

Solution to Part (a) of Example

Problem a) 42% proeutectoid ferrite and 58% coarse pearlite

Isothermally treat at ~ 680ºC

-- all austenite transforms

to proeutectoid and

coarse pearlite.

A + B

A + P

A + A

B P

A 50%

0

200

400

600

800

0.1 10 103 105 time (s)

M (start)

M (50%)

M (90%)

Adapted from

Fig. 10.29,

Callister 5e.

Fe-Fe3C phase diagram,

for C0 = 0.45 wt% C

Wpearlite C0 0.022

0.76 0.022

= 0.45 0.022

0.76 0.022 = 0.58

W = 1 0.58 = 0.42

T (ºC)

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Chapter 10 - 22

b) 50% fine pearlite and 50% bainite

Solution to Part (b) of Example

Problem

T (ºC)

A + B

A + P

A + A

B P

A 50%

0

200

400

600

800

0.1 10 103 105 time (s)

M (start)

M (50%)

M (90%)

Adapted from

Fig. 10.29,

Callister 5e.

Fe-Fe3C phase diagram,

for C0 = 0.45 wt% C

Then isothermally treat

at ~ 470ºC

– all remaining austenite

transforms to bainite.

Isothermally treat at ~ 590ºC

– 50% of austenite transforms

to fine pearlite.

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Chapter 10 - 23

Solutions to Parts (c) & (d) of Example

Problem c) 100% martensite – rapidly quench to room

temperature

d) 50% martensite

& 50% austenite -- rapidly quench to

~ 290ºC, hold at this

temperature

T (ºC)

A + B

A + P

A + A

B P

A 50%

0

200

400

600

800

0.1 10 103 105 time (s)

M (start)

M (50%)

M (90%)

Adapted from

Fig. 10.29,

Callister 5e.

Fe-Fe3C phase diagram,

for C0 = 0.45 wt% C

d)

c)

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Chapter 10 - 24

Mechanical Props: Influence of C Content

Adapted from Fig. 9.30,

Callister & Rethwisch 8e.

• Increase C content: TS and YS increase, %EL decreases

C0 < 0.76 wt% C

Hypoeutectoid

Pearlite (med) ferrite (soft)

Adapted from Fig. 9.33,

Callister & Rethwisch 8e.

C0 > 0.76 wt% C

Hypereutectoid

Pearlite (med)

C ementite (hard)

Adapted from Fig.

10.29, Callister &

Rethwisch 8e. (Fig.

10.29 based on data

from Metals

Handbook: Heat

Treating, Vol. 4, 9th

ed., V. Masseria

(Managing Ed.),

American Society for

Metals, 1981, p. 9.) 300

500

700

900

1100 YS(MPa)

TS(MPa)

wt% C 0 0.5 1

hardness

0.7

6

Hypo Hyper

wt% C 0 0.5 1

0

50

100

%EL

Imp

act e

ne

rgy (

Izo

d, ft

-lb

)

0

40

80

0.7

6

Hypo Hyper

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Chapter 10 - 25

Mechanical Props: Fine Pearlite vs.

Coarse Pearlite vs. Spheroidite

Adapted from Fig. 10.30, Callister &

Rethwisch 8e. (Fig. 10.30 based on

data from Metals Handbook: Heat

Treating, Vol. 4, 9th ed., V. Masseria

(Managing Ed.), American Society for

Metals, 1981, pp. 9 and 17.)

• Hardness:

• %RA: fine > coarse > spheroidite

fine < coarse < spheroidite

80

160

240

320

wt%C 0 0.5 1

Bri

ne

ll h

ard

ne

ss

fine pearlite

coarse pearlite

spheroidite

Hypo Hyper

0

30

60

90

wt%C D

uctilit

y (

%R

A)

fine pearlite

coarse pearlite

spheroidite

Hypo Hyper

0 0.5 1

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Chapter 10 - 26

Mechanical Props: Fine Pearlite vs.

Martensite

• Hardness: fine pearlite << martensite.

Adapted from Fig. 10.32,

Callister & Rethwisch 8e. (Fig.

10.32 adapted from Edgar C.

Bain, Functions of the Alloying

Elements in Steel, American

Society for Metals, 1939, p. 36;

and R.A. Grange, C.R. Hribal,

and L.F. Porter, Metall. Trans. A,

Vol. 8A, p. 1776.)

0

200

wt% C 0 0.5 1

400

600

Bri

ne

ll h

ard

ne

ss

martensite

fine pearlite

Hypo Hyper

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Chapter 10 - 27

Tempered Martensite

• tempered martensite less brittle than martensite

• tempering reduces internal stresses caused by quenching

Adapted from Fig.

10.33, Callister &

Rethwisch 8e. (Fig.

10.33 copyright by

United States Steel

Corporation, 1971.)

• tempering decreases TS, YS but increases %RA

• tempering produces extremely small Fe3C particles surrounded by

Adapted from

Fig. 10.34,

Callister &

Rethwisch 8e.

(Fig. 10.34

adapted from

Fig. furnished

courtesy of

Republic Steel

Corporation.)

9

m

YS(MPa)

TS(MPa)

800

1000

1200

1400

1600

1800

30

40

50

60

200 400 600 Tempering T (ºC)

%RA

TS

YS

%RA

Heat treat martensite to form tempered martensite

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Chapter 10 - 28

Summary of Possible Transformations Adapted from

Fig. 10.36,

Callister &

Rethwisch 8e.

Austenite ( )

Pearlite ( + Fe3C layers + a

proeutectoid phase)

slow cool

Bainite ( + elong. Fe3C particles)

moderate cool

Martensite (BCT phase

diffusionless transformation)

rapid quench

Tempered Martensite ( + very fine

Fe3C particles)

reheat

Str

en

gth

Du

ctilit

y

Martensite T Martensite

bainite fine pearlite

coarse pearlite spheroidite

General Trends

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Chapter 10 - 29

Core Problems:

Self-help Problems:

ANNOUNCEMENTS

Reading: