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Phase Transformation

‰ Nucleation
‰ Growth
‰ APPLICATIONS
™ Transformations in Steel
™ Precipitation
™ Solidification & crystallization
™ Gl
Glass transition
ii
™ Recovery, Recrystallization & Grain growth

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PHASE TRANSFORMATIONS
Based on
Mass
t
transport
t
Diffusional Martensitic

PHASE TRANSFORMATIONS

Based on
order
1nd order 2nd order
nucleation & growth Entire volume transforms

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Bulk Gibbs free energy ↓

Energies involved Interfacial energy ↑

Strain energy ↑ Solid-solid transformation

New interface created

Volume off transforming


f g material

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1nd order
nucleation & growth

Growth
Nucleation
Transformation till
= of + α is
α→β β phase
exhausted

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Liquid → Solid phase transformation

ƒ On cooling just below Tm solid becomes stable


ƒ But solidification does not start
ƒ e.g. liquid Ni can be undercooled 250 K below Tm
↑T
Solid stable Liquid stable

ΔG
G →

Solid (GS)

ΔT Liquid (GL)
ΔG → +ve
ve
“For sufficient
ΔT - Undercooling Tm T → Undercooling”
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Solidification = Nucleation + Growth

Nucleation
Homogenous

Nucleation
ƒ Liquid → solid
walls of container, inclusions
Heterogenous
g
ƒ Solid → solid
inclusions, grain boundaries,
dislocations,, stacking
g ffaults
‰ In Homogenous solidification the probability of nucleation occurring at
points in the parent phase is same throughout the parent phase
‰ In heterogeneous solidification nucleation there are some preferred sites in
the parent phase where nucleation can occur
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Negligible in L → S
Homogenous nucleation transformations
Free energy change on nucleation =

ΔG = (Volume).( (Surface) (γ )
(Volume) (ΔGv ) + (Surface).
X
Reduction in bulk free energy + increase in surface energy + increase in strain energy

⎛4 3⎞
ΔG = ⎜ πr ⎟.((ΔGv ) + 4πr .((γ )
2
( )
⎝3 ⎠

ΔGv = f (ΔT )
r3
r2

ro
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4.5

3.5

2.5
Energy

1.5

0.5
Volume energy
Surface energy
0
0 0.2 0.4 0.6 0.8 1 1.2

Radius

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0.4

0.2

0
0 02
0.2 04
0.4 06
0.6 08
0.8 1 12
1.2
ystem Energy
y

-0.2
Critical Radius=RC
Total Sy

-0.4

-0.6

-0.8

-1
Radius

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⎛4 3⎞
ΔG = ⎜ πr ⎟.(ΔGv ) + 4πr .(γ )
2
( )
⎝3 ⎠
ƒ By setting dΔG/dr = 0 the critical values (corresponding to the maximum)
are obtained (denoted by superscript *)
ƒ Reduction in free energy is obtained only after r0 is obtained
2γ As ΔGv is _ , r*is +
dΔG
r1 = 0 r2 = −
* *
=0 ΔGv
dr
Trivial dΔG
2γ =0
r =−
* dr
ΔGv ΔG = 0

16 γ 3
ΔG * = π
ΔG →

r* r0
3 ΔGv2
Embryos Supercritical nuclei

ΔG = 0 r0 = − r →
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ΔGv
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Solid stable Liquid stable

ΔG
G →

S lid (GS)
Solid

ΔT Liquid (GL)
ΔG → +ve
ΔT - Undercooling Tm

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ΔGv = f (ΔT ) The bulk free energy reduction is a function of undercooling

G*
Decreaasing ΔG Tm

Decreasing r*
G →
ΔG

r →

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T 2<T1

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No. of critical sized x Frequency with which they
Rate of nucleation = particles become supercritical

⎛ ΔG * ⎞ ⎛ ΔH d ⎞
dN ⎜− ⎟ ⎜− ⎟
I= ⎜ kT ⎟
dt N * = Nt e ⎝ ⎠
ν '= s ν e
* ⎝ kT ⎠

No. of particles/volume in L

s* atoms of the liquid facing the nucleus

Critical nucleus

Jump taking particle to supercriticality


→ nucleated (enthalpy of activation = ΔHd)

Critical sized nucleus


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⎛ ΔG * + ΔH d ⎞ ΔG* ↑ ⇒ I ↓
−⎜⎜ ⎟

I = Nt s ν e
* ⎝ kT ⎠ T↑ ⇒I ↑

Tm T = Tm → ΔG* = ∞ → I = 0

γ
Increeasing ΔT
T

3
16
ΔG * = π
3 ΔGv2
T (K) →

0 T=0→I=0
I →
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Heterogenous nucleation
Consider the nucleation of β from α on a pplanar surface of inclusion δ
Interfacial Energies
α γαβ
C t d
Created Alens γαβ
β
θ
γαδδ γβδ Created i l γβδ
Acircle

δ γ αδ − γ βδ Lost Acircle γαδ


Cosθ =
γ αβ

Surface tension force balance γ αββ Cosθ + γ βδ = γ αδδ


ΔG = (Vlens )ΔGv + (A lens )γ αβ + ( Acircle ) γ βδ − ( Acircle ) γ αδ
Vlens = πh2(3r-h)/3 Alens = 2πrh h = (1-Cosθ)r rcircle = r Sinθ
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dΔ G 2γ αβ γ αβ
3

dr
=0 r *
hetero =−
ΔGv
ΔG *
hetero
4
= π
3 ΔGv
2
2 − 3Cos θ + Cos 3
(
θ )

ΔG * =
16 γ
π
3
ΔG *
hetero
1
= ΔGhomo
4
*
(
2 − 3Cosθ + Cos 3θ )
3 ΔGv2

1
ΔG*hetero / ΔG*homoo →

ΔG*hetero
h t (0o) = 0
ΔG*hetero (180o) = ΔG*homo
no barrier to nucleation
0.75
ΔG*hetero ((90o) = ΔG*homo/2
0.5
Δ

0.25
Complete wetting Partial wetting No wetting
0
0 30 60 90 120 150 180
θ (degrees)
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Choice of heterogeneous nucleating agent

ƒ Small value of θ
ƒ Choosing a nucleating agent with a low value of γβδ (low energy βδ interface)
ƒ (Actually the value of (γαδ − γβδ) will determine the effectiveness of the
heterogeneous nucleating agent → high γαδ or low γββδ)
ƒ low value of γβδ →
Crystal structure of β and δ are similar and lattice parameters are as close as
possible
ƒNi (FCC, a = 3.52 Å) is used a heterogeneous nucleating agent in the
pproduction of artificial diamonds ((FCC,, a = 3.57 Å)) from ggraphite
p

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Growth
Trasformation Nucleation
till
= of +
α→β α is
β phase
exhausted
Growth
ƒ At transformation temperature the probability of jump of atom from α → β
(across the interface) is same as the reverse jump
ƒ Growth
G h proceeds
d bbelow
l theh transformation
f i temperature, wherein
h i theh activation
i i
barrier for the reverse jump is higher

ΔHd
ΔHd – vatom
t ΔGv

α phase

β phase
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PHASE TRANSFORMATIONS

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

Fe 3 Fe C
γ Eutectoid
transformation (cementite)
(Austenite) +
α
C FCC (BCC)
(ferrite)

• How does the rate of transformation depend on


time and T?
• How can we slow down the transformation so that
we can engineering non-equilibrium structures?
• Are the mechanical properties of non-equilibrium
structures better?
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COOLING AUSTENITE
Austenite

Pearlite

• Mainly interested in eutectoid cooling: γ Ù α + Fe3C (pearlite), 0.78 wt% C


• Cooling rate can result in a wide variety of phases and microstructures
– Equilibrium phases: pearlite,
pearlite bainite
– Non-equilibrium phases: martensite
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FRACTION OF TRANSFORMATION
• Fraction transformed depends on time,
at constant temperature (e.g., γ Î pearlite)

− kt n
y = 1− e
Avrami equation
(k, n are constants)
• Transformation rate , r = 1/t0.5
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1.2

0.8
Y=Ratte

0.6

0.4

0.2

0
0 10 20 30 40 50 60 70 80

Time (S)

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EUTECTOID TRANSFORMATION RATE ~ ΔT
• Growth of pearlite from austenite:

• Reaction rate increases with ΔT.

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EUTECTOID TRANSFORMATION RATE ~
ΔT
Diffusive flow
• Growth of pearlite from austenite: of C needed
Austenite (γ) cementite (Fe3C)
grain
g α ferrite (α) α
boundary α
γ
γ α γ
γ
α pearlite α
α
α growth
direction α

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TIME-TEMPERATURE TRANSFORMATION
(TTT) DIAGRAMS
• Fe-C system, Eutectoid
composition
p ((Co = 0.77wt%C))
• Transformation at T = 675C.

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PEARLITE MORPHOLOGY
Two cases:
• Ttransf just below TE • Ttransf well below TE
--Larger T: diffusion is faster --Smaller T: diffusion is slower
--Pearlite is coarser. --Pearlite is finer.

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2E-08

1.5E-08
cient (M2//s)

1E-08
on Coeffic

D (A in B)
D (A in C)
5E-09
Diffusio

2.5E-22
0 1000 2000 3000 4000

-5E-09
T (K)

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Eutectoid & Peritectic
Peritectic transition γ + L δ
Cu-Zn Phase diagram

Adapted from
Fig 9.21,
Fig. 9 21 Callister 7e
7e.
Eutectoid transition δ γ+ε
Peritectic Trans. L +δ ε
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Figure 2. Microstructure of the Hyper Eutectoid.

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FRACTION OF TRANSFORMATION
• Fraction transformed depends on time,
at constant temperature (e.g., γ Î pearlite)

− kt n
y = 1− e
Avrami equation
(k, n are constants)
• Transformation rate , r = 1/t0.5
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EX: COOLING HISTORY Fe-C SYSTEM
• Eutectoid composition, Co = 0.77wt%C
• Begin at T > 727C
• Rapidly cool to 625C and hold isothermally.
• Cooling
C li to t lower
l temperatures
t t results
lt in
i fi
finer microstructures
i t t

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OTHER TRANSFORMATION PRODUCTS
• Bainite:
--α strips with long, fine
rods of Fe3C
Fe3C
• Isothermal Transf. Diagram (cementite)
α (ferrite)


μm
(Adapted from Fig. 10.8, Callister, 6e. (Fig.
10.8 from Metals Handbook, 8th ed.,
Vol. 8, Metallography, Structures, and
Phase Diagrams, American Society for
Metals, Materials Park, OH, 1973.)

Note: reaction rate


increases with decreasing
temperature first
first, and then
decreases
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Bainite is a phase that exists in steel microstructures after certain heat treatments.
First described by Davenport E. S. and Edgar Bain, it is one of the decomposition
products that may form when austenite (the face centered cubic crystal structure of
iron)) is cooled past a critical temperature off 723 °C (about
( 1333 °F).
° ) Davenport and
Bain originally described the microstructure as being similar in appearance to
tempered martensite.

A fine
fi non-lamellar
l ll structure, bainite
b i i commonly l consists
i off ferrite,
f i carbide,
bid and d
retained austenite. In these cases it is similar in constitution to pearlite, but with the
ferrite forming by a displacive mechanism similar to martensite formation, usually
followed by precipitation of carbides from the
supersaturated
t t d ferrite
f it or austenite.
t it

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NUCLEATION AND GROWTH
• Reaction rate is a result of nucleation and growth
of crystals.
Nucleation rate increases with ΔT
Growth rate increases with T

• Examples:
pearlite
γ colony γ γ

T just below TE T moderately below TE T way below TE


Nucleation rate low Nucleation rate med . Nucleation rate high
Growth rate high Growth rate med. Growth rate low

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TRANSFORMATIONS & UNDERCOOLING
• Eutectoid transf. (Fe-C System): γ ⇒ α + Fe3 C
• Can make it occur at: 0.77wt%C 6.7wt%C
...727ºC ((cool it slowly)
y) 0.022wt%C
...below 727ºC (“undercool” it!)
T(°C)
1600
Adapted from Fig.
9 21 Callister
9.21, C lli t 66e. (Fig.
(Fi
1400 L 9.21 adapted from Binary
Alloy Phase Diagrams,
γ+L 2nd ed., Vol. 1, T.B.
1200 γ L+Fe3C Massalski (Ed.-in-Chief),
ASM International,
International
austenite Materials Park, OH, 1990.)
1000
α Eutectoid: γ+Fe3C
ferrite
α+

800 Equil.
q cooling:
g Ttransf. = 727ºC Fe3C
727°C
γ

ΔT α+Fe3C
600
cementite
Undercooling by ΔT: Ttransf. < 727ºC
0.022

0.77

6.7
400
0 1 2 3 4 5 6
0

6
(Fe) Co, wt% C
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NUCLEATION AND GROWTH
• Reaction rate is a result of nucleation and growth
of crystals.
100
Nucleation rate increases w/ ΔT
% Pearlite Growth
regime Growth rate increases w/ T
50 Nucleation
regime Adapted from

0 t50 log (time) Fig. 10.1, Callister 6e.

• Examples:
pearlite
γ colony γ γ

T just below TE T moderately below TE T way below TE


Nucleation rate low Nucleation rate med . Nucleation rate high
Growth rate high Growth rate med. Growth rate low

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PEARLITE MORPHOLOGY
Two cases:
• Ttransf just below TE • Ttransf well below TE
--Larger
g T: diffusion is faster --Smaller T: diffusion is slower
--Pearlite is coarser. --Pearlite is finer.

μm
10μ
Adapted from Fig. 10.6 (a) and (b),Callister 6e. (Fig. 10.6 from R.M. Ralls et al., An Introduction to
Materials Science and Engineering, p. 361, John Wiley and Sons, Inc., New York, 1976.)

- Smaller ΔT: - Larger ΔT:


colonies are colonies are
larger
g smaller

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EX: COOLING HISTORY Fe-C SYSTEM
• Eutectoid composition, Co = 0.77wt%C
• Begin at T > 727C
• Rapidly cool to 625C and hold isothermally.
T(°C)
Austenite (stable)
TE ((727°C))
700

Adapted from Fig.


Pearlite 10.5,Callister 6e.
(Fig 10.5
(Fig. 10 5 adapted from
600 H. Boyer (Ed.) Atlas of
γ γ γ Isothermal
Transformation and
γ γ γ γ Cooling Transformation
0%

10
50

Diagrams, American
500
0%
%

Society for Metals,


pe

1997, p. 28.)
arl
ite

1 10 102 103 104 105 time (s)

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OTHER PRODUCTS: Fe-C SYSTEM (1)
• Spheroidite:
--α crystals with spherical Fe3C α
--diffusion
diffusion dependent. ((ferrite))
--heat bainite or pearlite for long times
--reduces interfacial area (driving force) Fe3C
• Isothermal Transf. Diagram
g (cementite)
800 Austenite (stable)
T(°C) A
TE
P
600 100% spheroidite 60 μm
Spheroidite (Adapted from Fig. 10.10, Callister,
6e. (Fig. 10.10 copyright United
100% spheroidite States Steel Corporation, 1971.)
400 A B
Ad t d ffrom Fi
Adapted Fig. 10 9 Callister
10.9, C lli t 66e.
(Fig. 10.9 adapted from H. Boyer (Ed.) Atlas of
Isothermal Transformation and Cooling
Transformation Diagrams, American Society for
200
10
0%

Metals, 1997, p. 28.)


50

0%
%

10-1 10 103 105 time (s)


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OTHER PRODUCTS: Fe-C SYSTEM (2)
• Martensite:
--γ(FCC) to Martensite (BCT)
(involves single atom jumps)
x
Fe atom potential
x x
sites x x C atom sites
x (Adapted from Fig.
10 11 Callister,
10.11, C lli t 6 6e.

• Isothermal Transf. Diagram


800 Austenite (stable)
T(°C)
T( C) A TE
P (Adapted from Fig. 10.12, Callister,
600 6e. (Fig. 10.12 courtesy United
S States Steel Corporation.)
Adapted
from Fig.
Fig B
10.13, 400 A
10
• γ to M transformation..
Callister 6e. 0% -- is rapid!
0%
50

0% -- % transf. depends on T only.


%

200 M+A 50%


M+A 90%
M+A
10-1 10 103 105 time (s)
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TTT diagram for eutectoid steel
QUENCHING
Stable
H d
Hardness RC 65 austenite

γ ⎯⎯ ⎯ ⎯
⎯→ α '
rapid
p coolingg

α’: mart
martensite
n t (M)

Extremely rapid, no
C
C-curves

unstable
Ms : Martensite start austenite
temperature Ms
A+M
Mf : Martensite finish Mf
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temperature M
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Martensitic transformation
Amount of martensite formed
does not depend upon
time, only on temperature.

Atoms move only a fraction of


atomic distance during the
transformation:
f i
1. Diffusionless
( llong-range diffusion)
(no diff i )

2. Shear
(one-to-one correspondence
BCT
between γ and α’ atoms)
3. No composition change
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Martensitic transformation (contd.)

BCT unit cell

c
= 2 = 1.414
a
BCT unit cell of α’ (martensite)

c
Expand = 1.00 − 1.20
a
~ 12%
Contract 0% Con. 20 % Con.
~ 20% (BCC)

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Martensitic transformation (contd.)

Hardness of martensite as a function of C content

dness, RC 60

40
Hard

20

0.2 0.4 0.6 Wt % Carbon →

Hardness of martensite depends mainly on C content and


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not on other alloying additions
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Slow Cooling

Time in region
indicates amount of
microconstituent!

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Medium Cooling

Cooling Rate, R, is
Change in Temp /
Time °C/s

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Fast Cooling

This steel is very


hardenable… 100%
Martensite in ~ 1
minute of cooling!

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COOLING EX: Fe-C SYSTEM (1)
• Co = Ceutectoid Rapid Hold Rapid Hold Rapid
• Three histories... cool to: for: cool to: for: cool to:

350°C 104s Troom 104s Troom


Case I 250°C 102s Troom 102s Troom
800 Austenite (stable)
650°C 20s 400°C 103s Troom
T(°C) A
P
600
S
A B
400
100%A 10 100%B
0 % Adapted
Ad t d
0%
50

from Fig.
0%
%

200 M + A 10.15,
M+A 50% Callister 6e.
90%
M+A 100% Bainite
10-1 10 103 105 time (s)
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COOLING EX: Fe-C SYSTEM (2)
• Co = Ceutectoid Rapid Hold Rapid Hold Rapid
• Three histories... cool to: for: cool to: for: cool to:

350°C 104s Troom 104s Troom


Case II 250°C 102s Troom 102s Troom
800 Austenite (stable)
650°C 20s 400°C 103s Troom
T(°C) A
P
600
S
A B
400
0% 10 Adapted
Ad t d
0%
100%A from Fig.
50

0% 10.15,
%

200 M + A Callister 6e.


50%
M+A 90%
M+A M + trace of A
10-1 10 103 105 time (s)
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COOLING EX: Fe-C SYSTEM (3)
• Co = Ceutectoid Rapid Hold Rapid Hold Rapid
• Three histories... cool to: for: cool to: for: cool to:

350°C 104s Troom 104s Troom


Case III 250°C 102s Troom 102s Troom
800 Austenite (stable)
T(°C) 650°C 20s 400°C 103s Troom
A
100%A 50%P, 50%A
600 P
S
A B
400 50%P, 50%B
50%P, 50%A 10
0% Adapted
Ad t d
0%
50

from Fig.
0%
%

200 M + A 10.15,
M+A 50% Callister 6e.
90%
M+A 50
10-1 10 103 %P 105 time (s)
,5
0%
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TEMPERING
Heating of quenched steel below the eutectoid
t
temperature,
t h
holding
ldi f for a specified
ifi d ti
time f
followed
ll dbby
ar cooling.


α ⎯⎯ ⎯ ⎯→ α + Fe3C
tempering
T<TE

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Dr. Ray Taheri Last revision: Sept. 01, 2009 Page 76
Tempering (contd.)

α+Fe3C PEARLITE

A distribution of fine particles of Fe3C in α matrix


known as TEMPERED MARTENSITE.
MARTENSITE

Hardness more than fine pearlite, ductility more


than martensite.
martensite

Hardness
H d ss andddductility
tilit controlled
t ll d bby ttempering
m i
temperature and time.
Higher T or t ->> higher ductility
ductility, lower strength
4-Nov-09
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Problems in Quenching Quench Cracks

High rate of cooling:


surface
f cooler
l than
h interior
i i

Surface forms martensite before the interior

Austenite martensite Volume expansion


p

When interior transforms, the hard outer


martensitic shell constrains this expansion
leading to residual stresses

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Solution to Quench cracks

Shift
f the C-curve to the right
g (higher
( g times))

More time at the nose

Slower quenching (oil quench) can give


martensite

But how to shift the C-curve to higher times?

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Dr. Ray Taheri Last revision: Sept. 01, 2009 Page 80
By
y alloying
y g

All alloying elements in steel


(Cr, Mn, Mo, Ni, Ti, W, V) etc shift the C-curves
to the right.
E
Exception:
i Co
C

Substitutional
b lddiffusion
ff of
f alloying
ll elements
l is
slower than the interstitial diffusion of C

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Plain C steel Alloy steel

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Hardenability
y

Ability or ease of hardening a steel by formation of


martensite using as slow quenching as possible

Alloying elements in steels shift the C-curve to


the right

Alloy steels have higher hardenability than plain


C steels.
steels

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Hardnenability
y Hardness

Ability or ease of Resistance to plastic


hardening a steel d f
deformation
ti as
measured by indentation

Only applicable to steels Applicable to all materials

Alloying additions increase the hardenability of


steels but not the hardness.

C increases both hardenability and hardness of


steels.

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High Speed steel

Alloy steels used for cutting tools operated at high


speeds

Cutting at high speeds lead to excessive heating of


cutting tools

This
h is equivalent
l to unintended
d d tempering off the
h
tools leading to loss of hardness and cutting edge

Alloying by W gives fine distribution of hard WC


particles which counters this reduction in hardness
hardness:
such steels are known as high speed steels.
4-Nov-09
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T holding

AT A
Q
T N
time
Annealing
g Furnace cooling
g RC 15

Normalizing Air cooling RC 30


Quenching Water cooling RC 65

Tempering Heating after quench RC 55


Austempering Quench to an inter- RC 45
4-Nov-09
mediate temp and hold
Dr. Ray Taheri Last revision: Sept. 01, 2009 Page 86
MECHANICAL PROPERTIES

• Martensite

Ductilitty
Strength

• Tempered martensite
• Bainite
• Fine pearlite
• Coarse pearlite
• Spheroidite pearlite

• Can control the formation of specific phases and


microstructure so that desired properties result

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MECHANICAL PROP: Fe-C SYSTEM
(1)
• Effect of wt%C Pearlite (med)
Pearlite (med) Cementite
ferrite (soft) (hard)
Adapted from Fig. 9.27,Callister Co<0.77wt%C Co>0.77wt%C Adapted from Fig. 9.30,Callister
6e. (Fig. 9.27 courtesy Republic 6e. (Fig. 9.30 copyright 1971 by
Steel Corporation.) Hypoeutectoid Hypereutectoid United States Steel Corporation.)

Hypo Hyper H
Hypo H
Hyper
TS(MPa) %EL

zod, ft-lb)
1100 80
YS(MPa) 100
Adapted from Fig.
10.20, Callister 6e.
900 (Fig. 10.20 based on
hardness data from Metals

ct energy (Iz
40 Handbook: Heat
700 Treating, Vol. 4, 9th
50 ed., V. Masseria
(Managing Ed.),
500 American Society for
0

Impac
Metals, 1981, p. 9.)
300
0
0.5 1
0.77

0.77
0 0.5 1
wt%C wt%C
• More wt%C: TS and YS increase, %EL decreases.

4-Nov-09 Dr. Ray Taheri Last revision: Sept. 01, 2009 Page 88
MECHANICAL PROP: Fe-C SYSTEM
(2)
• Fine vs coarse pearlite vs spheroidite
Hypo Hyper 90 Hypo Hyper
320

y (%AR)
fine spheroidite
dness

pearlite 60
240 coarse
Brinell hard

Ductility
pearlite
spheroidite
160 30 coarse
pearlite
fine
B

80 pearlite
0
0 0.5 1 0 0.5 1
wt%C wt%C
Adapted from Fig.
Fig 10 21 Callister
10.21,
• Hardness: fine > coarse > spheroidite 6e. (Fig. 10.21 based on data from
Metals Handbook: Heat Treating,
• %AR: fine < coarse < spheroidite Vol. 4, 9th ed., V. Masseria
(Managing Ed.), American Society
for Metals,, 1981,, pp
pp. 9 and 17.))

4-Nov-09
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MECHANICAL PROP: Fe-C SYSTEM
(3)
• Fine Pearlite vs Martensite:

ness
Hypo Hyper

600
martensite
Brinell hardn

Adapted from Fig.


10.23, Callister 6e. (Fig. 10.23
400 adapted from Edgar C.
Bain, Functions of the Alloying
Elements in Steel, American
B

S i t for
Society f Metals,
M t l 1939,
1939 p. 36
36;
200 and R.A. Grange, C.R.
fine pearlite Hribal, and L.F. Porter, Metall.
Trans. A, Vol. 8A, p. 1776.)
0
0 05
0.5 1
wt%C
• Hardness: fine pearlite << martensite.

4-Nov-09 17
Dr. Ray Taheri Last revision: Sept. 01, 2009 Page 90
TEMPERING MARTENSITE
• reduces brittleness of martensite,
• reduces internal stress caused by quenching.
TS(MPa)
YS(MPa)
1800

1600 TS
Adapted from Adapted from
YS

9 μm
Fig. 10.25, 1400 Fig. 10.24,
Callister 6e. Callister 6e.
((Fig.
g 10.25 ((Fig.
g 10.24
adapted from
1200 60 copyright by
Fig. furnished United States
courtesy of 1000 50
%AR %AR Steel
Republic Steel 40 Corporation,
Corporation.) 800 1971.)
30
200 400 600
Tempering T (°C)
• produces extremely small Fe3C particles surrounded by α.
α
• decreases TS, YS but increases %AR
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Austempering

B i it
Bainite

Short needles of Fe3C


embedded in plates of
ferrite

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1
2

6
5

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Cool down to 600 C and hold for 4 s

Cool down to 450 C and hold for 10 s

Cool down to 300 C and hold for 800 s

Q
Quench
h

Final structure consist of:


50% pearlite
25% upper Bainite
12.5% lower Bainite
12.5% Martensite

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Stable austenite

Annealing:
coarse
pearlite
Normalizing:g
fine pearlite

unstable
austenite

4-Nov-09
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Design question
What will be a suitable tempering temperature and
time for a 1080 water q
quenched p
plain carbon steel to
have maximum 230000 psi tensile strength?

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At 425 C for 17 min.
min
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Example 1 Design of a Heat Treatment for an Axle
A heat treatment cycle
y is needed to p
produce a uniform
microstructure with minimum hardness of 200 BHN and
minimum ductility of 35 in a 1050 steel axle.
©2003 Brooks/Cole, a division off Thomson Learning, Inc. Thomsson Learning™ is a trademark useed herein
under license.

Figure 1 The TTT


diagrams for (a) a 1050
and (b) a 10110 steel.

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4-Nov-09
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Dr. Ray Taheri


Last revision: Sept. 01, 2009
Page 119
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Figure 2 (a) The


eutectoid portion of
the Fe-Fe3C phase
diagram. (b) An
©2003 Brooks/Cole, a division of Thomson L

expanded version of
the Fe-C diagram,
adapted from
severall sources.

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SOLUTION
1. Austenitize the steel at 770 + (30 to 55) = 805oC to
825oC, holding for 1 h and obtaining 100% γ.
2. Quench the steel to 600oC and hold for a minimum of 10 s.
Primary ferrite
f begins
b to precipitate from
f the
h unstablebl
austenite after about 1.0 s. After 1.5 s, pearlite begins to
grow, and the austenite is completely transformed to
ferrite and pearlite after about 10 ss. After this treatment,
treatment
the microconstituents present are:
⎡ (0.77 − 0.5) ⎤
Primary α = ⎢ ⎥ ×100 = 36%
⎣ (0.77 − 0.022) ⎦
⎡ (0.5 − 0.0218) ⎤
Pearlite = ⎢ ⎥ ×100 = 64%
⎣ (0.77 − 0.022) ⎦
3. Cool in air-to-room temperature, preserving the
equilibrium amounts of primary ferrite and pearlite. The
microstructure and hardness are uniform because of the
isothermal anneal.

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Example 2: Design of a Quench and
Temper
p Treatment

A rotating shaft that delivers power from an electric motor is


made ffrom
om a 4340 steel.
steel Its yield
ield st
strength
ength sho
should
ld be at least
200,000 psi, yet it should also have at least 40% AR. Design a
heat treatment to heat treat this part.

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Learning, Inc. Thomson Learningg™ is a trademark used herein unnder license.

Figure 2 (a) The


eutectoid portion of
the Fe-Fe3C phase
diagram. (b) An
©2003 Brooks/Cole, a division of Thomson L

expanded version of
the Fe-C diagram,
adapted from
severall sources.

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©2003 Brookks/Cole, a division of Thomson L
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Dr. Ray Taheri


Last revision: Sept. 01, 2009
Page 129
SOLUTION
1. Austenitize above the A3 temperature of 760oC for 1 h.
An appropriate temperature may be 760 + 55 = 815oC.
2 Oil quench
2. q ench rapidly
apidl to room
oom temperature.
tempe at e Since the Mf is
about 250oC, martensite will form.
3. Temper by heating the steel to 420oC. Normally, 1 h will
b sufficient
be ffi i t if the
th steel
t l is
i nott too
t thick.
thi k
4. Cool to room temperature.

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©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning™ is a trademark used herein under license.

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Example : 3
Determination of Heat Treating
Temperatures
Recommend temperatures for the process annealing,
annealing, normalizing, and spheroidizing of 1020,
1077,
0 , and
a d 10120
0 0 (1.2
( %C) steels.
s ee s

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Cole, a division of Thomson Learrning, Inc. Thomson Learning™ iis a trademark used herein underr license.
©2003 Brooks/C

Figure 1 (a) The eutectoid portion


of the Fe-Fe3C phase diagram. (b)
An expanded version of the Fe-C
diagram, adapted from several
sources.

4-Nov-09
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SOLUTION
From Figure 1, we find the critical A1, A3, or Acm,
temperatures for each steel. We can then specify the heat
treatment based on these temperatures.

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Equivalent Carbon

AISI 860
Carbon, C 0.280 - 0.330 %
Chromium Cr
Chromium, 0 500 %
0.500
Iron, Fe 97.0 %
Manganese, Mn 0.800 %
Molybdenum, Mo 0.200 %
Nickel, Ni 0.550 %

Phosphorous, P <= 0.0350 %

Silicon, Si 0.230 %

Sulfur, S <= 0.0400 %

Ec=0
0.65
65
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4-Nov-09
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Figure 2. Increasing
carbon reduces the
Ms and Mf
temperatures in
plain-carbon steels.
p

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Figure 3 Producing
complicated structures
by interrupting the
isothermal heat
treatment of a 1050
steel.

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Page 141
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Last revision: Sept. 01, 2009
Page 142
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©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning™ is a trademark used herein under license.

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©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning™ is a trademark used herein under license.

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Application
pp of Hardenability
y

† Jominy test - The test used to evaluate hardenability.


hardenability An
austenitized steel bar is quenched at one end only, thus
producing a range of cooling rates along the bar.
† Hardenability curves - Graphs showing the effect of the
cooling rate on the hardness of as-quenched steel.
† Jominy distance - The distance from the quenched end of
a Jominy bar.
bar The Jominy distance is related to the
cooling rate.

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©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning™ is a trademark used herein under
license.

Figure. The set-up for the Jominy test used for


determining the hardenability of a steel.

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C 0.38 - 0.43
Cr 0.7 - 0.9
Cole, a division of Thomson Learrning, Inc. Thomson Learning™ iis a trademark used herein underr license.

Fe Balance
Mn 0.6 - 0.8
Mo 0.2 - 0.3
Ni 1.65 - 2
P 0.035 max
Si 0 15 - 0.3
0.15 03
S 0.04 max

EC=0.88 Wt.%
©2003 Brooks/C

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Example Design of a Wear-Resistant Gear
A gear made from 9310 steel, steel which has an as-quenched
as quenched
hardness at a critical location of HRC 40, wears at an excessive
rate. Tests have shown that an as-quenched hardness of at
least HRC 50 is required at that critical location.
location Select an
appropriate steel to satisfy hardness criterion.

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SOLUTION
From the Figure, a hardness of HRC 40 in a 9310 steel
corresponds to a Jominy distance of 10/16 in. (10oC/s). If we
assume the same Jominy distance, the other steels shown in
Fi
Figure have
h the
th following
f ll i h d
hardnesses att th
the critical
iti l llocation:
ti
1050 HRC 28 1080 HRC 36 4320 HRC 31
8640 HRC 52 4340 HRC 60
In Table 12-1, we find that the 86xx steels contain less alloying
elements than the 43xx steels; thus the 8640 steel is probably
l
less expensive
i th
than the
th 4340 steel
t l and
d might
i ht b
be our b
bestt
choice. We must also consider other factors such as durability.

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Example Design of a Quenching Process

Design a quenching process to produce a minimum hardness of


HRC 40 at the center of a 1.75 in. diameter 4320 steel bar.

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Last revision: Sept. 01, 2009
Page 169
Figure 2. The

for several steels.


hardenability curves
©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning™ is a trademark used herein under license.

Figure 1. The Grossman chart used to determine the


hardenability at the center of a steel bar for different
quenchants.
h t

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SOLUTION
Several quenching media are listed in Table 12
12-2
2. We can find
an approximate H coefficient for each of the quenching media,
then use Figure 1 to estimate the Jominy distance in a 1.75-in.
diameter bar for each media. Finally, we can use the
hardenability curve (Figure 2) to find
f the hardness in the 4320
steel. The results are listed below.

The last three media, brine or agitated water, are satisfactory.


Using an unagitated brine quenchant might be least expensive,
since no extra equipment is needed to agitate the quenching
bath However
bath. However, H2O is less corrosive than the brine quenchant.
quenchant

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Surface Treatments

† Selectively Heating the Surface - Rapidly heat the


surface
f off a medium-carbon
di b steel
t l above
b the
th A3
temperature and then quench the steel.
† Case depth - The depth below the surface of a steel at
which
hi h h
hardening
d i occurs by
b surface
f hardening.
h d i
† Carburizing - A group of surface-hardening techniques
by which carbon diffuses into steel.
† Cyaniding - Hardening the surface of steel with carbon
and nitrogen obtained from a bath of liquid cyanide
solution.
† Carbonitriding - Hardening the surface of steel with
carbon and nitrogen obtained from a special gas
atmosphere.

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Nitriding is a surface-hardening heat treatment that introduces nitrogen into the surface of steel at a
temperature range (500 to 550°C, or 930 to 1020°F), while it is in the ferrite condition. Thus, nitriding is
similar to carburizing in that surface composition is altered, but different in that nitrogen is added into
f it instead
ferrite i t d off austenite.
t it Because
B nitriding
it idi ddoes nott iinvolve
l h heating
ti iinto
t th
the austenite
t it phase
h fi
field
ld and
da
subsequent quench to form martensite, nitriding can be accomplished with a minimum of distortion and
with excellent dimensional control.

Thee mechanism
ec a s o of nitriding
d g is
s ge
generally
e a y known,
o , bu
but the
e spec
specific
c reactions
eac o s that
a occu
occur in d
different
e e ssteels
ee s a
and
d
with different nitriding media are not always known. Nitrogen has partial solubility in iron. It can form a
solid solution with ferrite at nitrogen contents up to about 6%. At about 6% N, a compound called gamma
prime (γ’), with a composition of Fe4N is formed.

At nitrogen contents greater than 8%8%, the equilibrium reaction product is ε compound
compound, Fe3N. N Nitrided
cases are stratified. The outermost surface can be all γ’ and if this is the case, it is referred to as the white
layer. Such a surface layer is undesirable: it is very hard profiles but is so brittle that it may spall in use.
Usually it is removed; special nitriding processes are used to reduce this layer or make it less brittle. The ε
zone of the case is hardened by the formation of the Fe3N compound, and below this layer there is some
solid solution strengthening from the nitrogen in solid solution.
Principal reasons for nitriding are:

•To obtain high surface hardness


•To increase wear resistance
•To improve fatigue life
•To improve corrosion resistance (except for stainless steels)
•To obtain a surface that is resistant to the softening effect of heat at temperatures up to the nitriding
temperature

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Figure 1. (a) Surface hardening by localized heating. (b)


Only the surface heats above the A1 temperature and is
quenched
que c ed to martensite.
a te s te

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Figure 2. Carburizing of a low-carbon steel to produce a


high-carbon, wear-resistant surface.

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Example
Design of Surface-Hardening Treatments
for a Drive Train
Design the materials and heat treatments for an automobile
axle and drive gear.

©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning™ is a trademark used
herein under license.

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SOLUTION
The axle might be made from a forged 1050 steel containing
a matrix of ferrite and pearlite. The axle could be surface-
hardened, perhaps by moving the axle through an induction
coil to selectively heat the surface of the steel above the A3
temperature (about 770oC). After the coil passes any
particular
ti l llocation
ti off th
the axle,
l the
th cold
ld interior
i t i quenches
h the
th
surface to martensite. Tempering then softens the martensite
to improve ductility.
Carburize a 1010 steel for the gear. By performing a
gas carburizing process above the A3 temperature (about
860oC), we introduce about 1.0% C in a very thin case at the
surface of the gear teeth. This high-carbon case, which
transforms to martensite during quenching, is tempered to
control the hardness.

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Example
Structures of Heat-Affected Zones
Compare
p the structures in the heat-affected zones of
welds in 1040 and 4340 steels if the cooling rate in the
heat-affected zone is 9 oC/s.

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SOLUTION
The cooling rate in the weld produces the
following structures:
1040: 100% pearlite
4340: Bainite and martensite
The high hardenability of the alloy steel reduces
the weldability, permitting martensite to form
and embrittle the weld.

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Dr. Ray Taheri Last revision: Sept. 01, 2009 Page 183
©2003 Brooks/Cole, a ddivision of Thomson Learning, Innc. Thomson Learning™ is a traddemark used herein under licensee.
Weldability of Steel

Figure 1. The
development of the
heat-affected zone
in a weld: (a) the
structure at the
maximum
temperature, (b)
the structure after
cooling
li in
i a steel
t l off
low hardenability,
and (c) the
structure after
cooling in a steel of
high hardenability.

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Super
p q question 1
Several bar stocks in different diameters made of 8620 alloy are
available. In order to increase the hardness and tensile strength of the bar
we needd to
t applyl a quenching
hi process (either
( ith in
i water
t or oil).
il) Determine
D t i
the maximum diameter of the bar in order to have a minimum hardness
of 40 HRC at the center and minimum hardness of 55 HRC at 0.1 mm
below the surface? The carburizing process should not take more 3
hours. Design a complete heat treatment process to accomplish required
hardness criteria.

− 20000
C = 6.688 × 10 −3 P exp( )
RT
P: Pressure in Pa

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18 mm

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AISI 8620
C b
Carbon, C 0 180 - 0.230
0.180 0 230 %
Chromium, Cr 0.500 %
Iron, Fe 97.0 %

Ec=0.55
=0 55
Manganese, Mn 0.800 %
Molybdenum, Mo 0.200 %
Nickel, Ni 0.550 %

Phosphorous, P <= 0.0350 %

Sili
Silicon, Si 0 230 %
0.230

Sulfur, S <= 0.0400 %

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Step 1:
Determine the equivalent diameter of the bar in order to get the requited
hardness at the center.

Step 2:
Realize the fact that the carbon content of the alloy is not enough to give the
sufficient hardness at the surface or slightly below
below.

Step 3:
Determining which alloy gives the sufficient hardness at the surface.

Step 4:
St 4
Finding the suitable Austeniting temperature for the alloy, depending of the
carbon content.

Step
p 5:
Applying the second Fick law and find the required surface carbon content.

Step 6:
Finding the required pressure to accomplished the carburizing process.

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Super
p q question 2
Determine the minimum carbon content, maximum diameter, and quench medium for 86
series round bar alloy in order to get the minimum hardness of 45 HRC at the center.
Required hardness at 00.5R
5R is 50 HRC
HRC. Available alloys are:
8610, 8620, 8630, 8640, 8650 and 8660.

Is there a more realistic engineering approach to this problem?

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8650
(0.5 wt% C)

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8650
(0.5 wt% C)

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Alloy Equivalent distance from Equivalent distance from HRC Diameter
quenched end (0.5R) mm quenched end (C) mm

8620 - - - -

8630 4 6 44 29

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8650
(0.5 wt% C)

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Alloy Equivalent distance from Equivalent distance from HRC Diameter
quenched end (0.5R) mm quenched end (C) mm

8620 - - - -

8630 4 6 44 29

8640 11 13 45 57

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8650
(0.5 wt% C)

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Alloy Equivalent distance from Equivalent distance from HRC Diameter
quenched end (0.5R) mm quenched end (C) mm

8620 - - - -

8630 4 6 44 29

8640 11 13 45 57

8650 20 27 47 100

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8650
(0.5 wt% C)

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Alloy Equivalent distance from Equivalent distance from HRC Diameter
quenched end (0.5R) mm quenched end (C) mm

8620 - - - -

8630 4 6 44 29

8640 11 13 45 57

8650 20 27 47 100

8660 32 >32 >48 >100

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8650
(0.5 wt% C)

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Alloy Equivalent distance from Equivalent distance from HRC Diameter
quenched end (0.5R) mm quenched end (C) mm

8620 - - - -

8630 - - - -

8640 11 13 45 25

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Example
The following five alloys are available in form of round bar in
variety of diameters.
diameters We are asked to design a gear in which
the minimum hardness at the center will be 40 HRC.
Moreover, the hardness at approximately 5 mm below the
surface should be between 47-50 HRC. Also determine the
quenching environment.

1040
5140
8640
4140
4340

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5
15 20
32

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Therefore, 1040 is not a good candidate because the maximum allowable
diameter is 25 mm and the hardness at 0.75 R, 3.125 mm below surface, is
about 47HRC, too low, when quenched in water.

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5
14 20
32

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65

2.5
7.5

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Therefore, 5140 is not a good candidate because the maximum allowable
diameter is 65 mm and the hardness at 0.75 R, 8.125 mm below surface, is
about 51 HRC, too high, when quenched in water.

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51140 is a good candidate because the maximum allowable diameter , oil
quenched,
h d iis 44 mm andd the
th hardness
h d att 0.75
0 75 R,
R 5.5
5 5 mm below
b l surface,
f is
i
about 46 HRC . As a result with a great level of confidence, we can say at
5mm below the surface the hardness is around 47 HRC.

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Example:
p
What would be the suitable carbon content of a 86 series alloy quenched in 
water, if the hardness  of a cylindrical piece throughout the first 17mm from 
the center should be between 45‐50 HRC. The diameter range should be 50‐
100 mm.

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3
6

14 32
10
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Alloy Distance from Jominy Distance from Jominy
end, 45 HRC end, 50 HRC
8620 6 3
8630 14 10
8460 45 32

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X

65

30

12

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04, 2009 Dr. Ray Taheri Last revision: Sept. 01, 2009 Page 227
Alloy Distance from Required Distance Diameter Distance from
the Jominyy end from the Jominyy , jjominyy ends
(center) mm 50 HRC at 17 mm
8620 6 4 30 3
8630 14 10 65 12
8460 45 32 >100 -

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Examples

The design criteria for a differential axle  used in a heavy duty pickup truck  are 
as follows:
as follows:

1‐ Minimum hardness throughout the component: 45 HRC
2‐ Maximum hardness at center: 50 HRC
3‐ Range of diameter: 55‐70 mm
4‐ Minimum surface hardness 55 HRC 
5‐ Quenching Medium: water 

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X

Too soft /

6 15 46

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4 15 23
11

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Minimum hardness Criterion

Alloy Min distance from Jominy


end (mm), 45 HRC
8620 Too soft
8630 6
8640 15
8660 46
1040 4
5140 11
4140 23
4340 50

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Minimum hardness on the surface

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Alloy Min distance from Jominy
end (center) mm
8620 Too soft
8630 6 (too soft at the ssurface)
rface)
8640 15
8660 46
1040 4
5140 11
4140 23
4340 50

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X

Too soft /

33

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7
2 16

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Alloy Max distance from
Jominy end (mm) center
8640 10
8660 33
1040 2
5140 7
4140 16
4340 50

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Wednesday, November
04, 2009 Dr. Ray Taheri Last revision: Sept. 01, 2009 Page 238
Alloy Max distance from Min allowable diameter
Jominy end (mm) center (mm)
8640 10 50
8660 33 100<
1040 2 Too small
5140 7 30
4140 16 71
4340 50 100<

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3

Wednesday, November
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Question Three:
The design criteria for a gear used in an excavation  drill  gearbox  are as 
follows:
1‐ Minimum hardness  throughout the component: 45 HRC
2‐ Maximum hardness at center: 50 HRC
3‐ Range of diameter: 55‐60 mm (find the maximum allowable diameter)
4‐ Maximum heat treatment time: 3.5 hours
5‐ Minimum hardness  0.1 mm below the surface: 64 HRC
6 Quenching medium: Agitated water
6‐ Quenching medium Agitated water
7‐ Available alloys: 8610, 8620, 8630, 8640, and 8660
8‐ Relationship between pressure and carbon content  given as follow:
− 20000
C = 6.688 × 10 −3 P exp(( )
P: in Pascal  RT
9‐ Allowable range of pressure: 150 psi
10‐ Maximum achievable temperature: 940 C°
p
Assumption: Disregard  the effect of alloying elements on carbon diffusion 
coefficient and process. 
Select the appropriate material and design a suitable process. 

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11 32
3

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6

Wednesday, November 04,


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13

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65

6 15

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AISI 8640
C b
Carbon, C 0 180 - 0.230
0.180 0 230 %
Chromium, Cr 0.500 %
Iron, Fe 97.0 %

Ec=0.75
=0 75
Manganese, Mn 0.800 %
Molybdenum, Mo 0.200 %
Nickel, Ni 0.550 %

Phosphorous, P <= 0.0350 %

Sili
Silicon, Si 0 230 %
0.230

Sulfur, S <= 0.0400 %

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Wednesday, November 04,
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Wednesday, November
04, 2009 Dr. Ray Taheri Last revision: Sept. 01, 2009 Page 249