10.

1 Iron-Carbide Phase Diagram - STEELS

3SP3 – Gordana A. Cingara
 Polymorphism
Iron - Carbide Phase Diagram

Iron (Fe) is polymorphic:

α - BCC at: T < 914oC
γ - FCC at: 914oC < T < 1394oC
δ - BCC at: 1394oC < T < 1538oC
T oC

1536

1394

914

2
Gordana Cingara 3SP3
 Iron - Carbide Phase Diagram

d 
L

g
g +Fe3C

a 

P
Fe Fe3C
Steel Cast Iron
3
Gordana Cingara 3SP3
 Steel - phases
• a solid solution - FERRITE
- Interstitial solid solution
- BCC, max solubility of carbon - 0.022 wt% C
- Soft
• g solid solution - AUSTENITE
- Interstitial solid solution
- FCC, max solubility of carbon - 2.11% C
• d solid solution (BCC, 0.09%C)

• Fe3C (iron carbide) – CEMENTITE

- Interstitial compound with 6.7% C
- Ororhombic
- Hard & brittle
Gordana Cingara 3SP3 4
 Interstitial space (solubility of C in Fe)

FCC - octahedral interstitial space

Large, accommodates an atom of 0.052 nm
in radius

BCC - octahedral
interstitial space C
(very small) -
accommodates an atom Fe
0.035 nm in radius.

FCC interstitial space is larger!

Austenite can accommodate more carbon than ferrite.
5
Iron - Carbide Phase Diagram

On the basis of carbon content it is

common practice to divide the iron-carbon
diagram into two parts:

• Steels: < 2.14% C

• Cast iron: > 2.14% C

Gordana Cingara 3SP3 6

 Iron - Carbide Phase Diagram

dd

L+d

g gg+Fe
+Fe3C C
3

g +Fe3C

a 

a +P P+Fe3C
P a+ Fe3C
Fe Fe3C
Steel Cast Iron

7
 Iron - Carbide Phase Diagram

Equilibrium reactions

1. Peritectic reaction at 14930C:

Liquid + d  austenite (g)

2. Eutectic reaction at 1147oC:

Liquid  austenite (g) + cementite (Fe3C)

3. Eutectoid reaction at 727oC:

Austenite (g)  Ferrite (a) + Cementite

Gordana Cingara 3SP3 8

3. Eutectoid reaction at 727oC,:
Austenite (g)  Ferrite (a) + Cementite
eutectoid mixture
PEARLITE
2.14

gg
Austenite
Austenite

a+g g+Fe3C

a+g g+Fe3C A1 727

0.76

a P
a+P P+Fe3C

9
Gordana Cingara 3SP3
g Eutectoid
composition
g

0.76
a a + P P+Fe3C

P
a
P

10
Gordana Cingara 3SP3
Eutectoid Transformation of Austenite to Pearlite
a
Austenite grain boundary a
a g
g
a Pearlite growth
a
a

Pearlite microstructure

• Nucleation and growth

• Heterogeneous nucleation at the g grain boundaries
• Pearlite colony grow into only one of the two g grains
• Diffusion of carbon during pearlite growth 11
W. Callister, Materials Science & Engineering, 8th Ed.
 Transformation of hypoeutectoid steel
on slow cooling

g
a
P
g+a g+Fe3C

0.76

a P

a+P P+Fe3C
• Primary ferrite
• Eutectiod ferrite - ferrite in a+Fe3C

a pearlite Source: Callister W.D., Rethwisch D.G,

Materials Science and Engineering (2009)

12
 Iron - Carbon Phase Diagram
Transformation of hypereutectoid steel on slow cooling

a+g g+Fe3C
Fe3C

P
P
a+P P+Fe3C

Hypereutectoid
13
Gordana Cingara 3SP3
 Lever rule - Example 1
Calculate the amounts of ferrite and cementite present in pearlite?

a R 
0.022
0.022  S  6.67 Source:W.
Callister, Materials
a + Fe3 C
0.76 Science &

P Engineering, 8th

a+P
Ed.
P+Fe3C

Fe
Co=0.76 %C Fe3C
14
 Example 1 - Solution

Calculate the amounts of ferrite and cementite present in

pearlite.

Since pearlite must contain 0.76% C, using the lever rule (3 points
in red - please see the previous slide):

awt% = S/R+S = (6.67 - 0.76) / (6.67 - 0.022) = 0.887

0.887 x100 = 88.7%

Fe3Cwt% = R/R+S = (0.76-0.022) / (6.67 - 0.022) = 0.113

0.113 x 100 = 11.3%

15
 Lever rule - Example 2a!
Calculate the amounts of ferrite and pearlite in a steel with 0.52% carbon,
T=650oC?
awt% = S/R+S

Pwt% = R/R+S

g+Fe3C
g


a
0.022 0.76
R
S
a+P P+Fe3C a + Fe3 C

CFe
o=0.52 %C Fe3C
16
 Example 2a - Solution
Calculate the amounts of ferrite and pearlite in the steel with
0.52% carbon. In this case, Co = 0.52 , is in the a +P region.

awt% = S/R+S = (0.76-0.52) / (0.76-0.022) = 0.24/0.738

=0.325 0.325 x100 = 32.5%
Pwt% = 100 - 32.5 = 67.5%
Pwt% = R/R+S = (0.76-0.52) / (0.76-0.022) = 0.675
0.675 x100 = 67.5%

a Primary ferrite
P

17
 Lever rule
Example 2b!
Amounts of eutectoid FERRITE and CEMENTITE in a steel with 0.52%
carbon, T=650oC?
• Steel with 0.52%C
• T= 600 C


Lever rule
a wt% = S/(R+S)
 g +Fe3CFe3C wt% = (R/R+S)


a
R S
a+P P+Fe3C
P a + Fe3 C

CFe
o=0.52 %C Gordana Cingara 3SP3 Fe3C
18
 Example 3
Calculate the amounts of ferrite and pearlite in the steel 1015.

0.022 0.76

a+P P+Fe3C

Co=0.15%C
awt% = (0.76 -0.15) / (0.76-0.022) = 0.61/0.738 = 0.8266, awt% = 83%

Pwt% = (0.15-0.022) / (0.76-0.022) = 0.128/0.738 = 0.1734, Pwt% = 17%

19
 Classification of Steels
Steels are arbitrarily divided into five groups:
1. Plain carbon steels
2. Alloy steels (referred to as low-alloy)
3. Stainless steels
4. Tools steels
5. Special-purpose steels

The first four of these groups are well defined by

Designation Systems developed by:

• The American Iron and Steel Institute (AISI)

• The Society of Automotive Engineers (SAE)

Gordana Cingara 3SP3 20

 Plain Carbon Steel

• The lowest cost

• Should be considered first in most
applications

Classification:
• Low Carbon: < 0.3 % C
• Medium Carbon: 0.3 - 0.6 %C
• High Carbon: 0.6 - 0.95 % C

Gordana Cingara 3SP3 21

1. Designation - Plain Carbon and Low Alloy
Steels - based on composition

The AISI designation is a four digit number:

steel 1040

22
The first two digits indicate the content
• 1st digit - the main alloying element ,showing the type of the steel
• 2nd digit indicates the secondary alloying element(s)
1xxx - carbon (10 – plain carbon steel)
2xxx - Nickel steels
3xxx - Nickel-chromium steels
4xxx - Molybdenum steels
5xxx - Chromium steels
6xxx - Chromium-vanadium steels
7xxx - Tungsten-chromium steels
8xxx – Nickel –cromium-molybdenum
9xxx - Silicon-manganese steels

 3rd and 4th digits –

the weight percent of carbon multiplied by 100

Example:
• 1060 - plain carbon steel with 0.6 wt% C
23
 1040 plain carbon steel with 0.4 wt% C

Micrograph of medium-carbon 1040 steel

Showing ferrite grains (white) and pearlite (dark)
(Etched in 4% picral followed by 2% nital.)
Source: 2002 ASM Int.
Metallographer’s Guide:
Irons and Steels Gordana Cingara 3SP3 24
Micrograph of low-carbon 1010 steel Micrograph of high-carbon 1095 steel
showing a matrix of ferrite grains (white) and showing a matrix of pearlite and some grain-
pearlite (dark). boundary cementite.

Source: 2002 ASM Int.

Metallographer’s Guide:
Irons and Steels
Gordana Cingara 3SP3 25
1. Plain Carbon and Low Alloy Steels

Gordana Cingara 3SP3 26

The effects of other alloying elements

The eutectoid temperature The eutectoid composition

can be affected! can be affected!

Source: W. Callister, Materials

Science & Engineering, 8th Ed.
Gordana Cingara 3SP3 27
10.2. Heat Treatment of
Steels
Representing both time and T transformation during the heat treatment
of steels by:

TTT - TIME-TEMPERATURE-
TRANSFORMATION DIAGRAMS

 IT - Isothermal Transformation diagrams

 CCT - Continuous Cooling Transformation diagrams

Gordana Cingara 3SP3 29

a) Isothermal Transformation Diagrams IT
Transformation of austenite to pearlite occurs isothermally
(at constant temperature)!

2.14

Eutectoid reaction:
g Austenite (g)  Ferrite (a) + Cementite (Fe3C)

Austenite PEARLITE

g+Fe3C
a+g A1 727
0.76
Transformation or decomposition of
P austenite is involved in all basic heat
treating processes!

Gordana Cingara 3SP3 30

(G.A Cingara)
 IT Diagrams
The steps to determine an IT diagram:
•Transformation of austenite to pearlite occurs isothermally (at the
constant temperature)!
1. Prepare a large number of thin samples cut of the same bar.
2. Place the samples in a furnace (T>727OC) long enough to
produce austenite.
3. Place the sample in a molten salt bath which is held at a
constant T (< 727OC).
4. After varying time intervals in the salt bath, quench each
sample in cold water.

Furnace at temperature Salt bath for isothermal Cold water tank at

above 727OC transformation at some room temperature
temperature below
727O C 31
Gordana Cingara 3SP3)
IT Diagrams • Steel - eutectoid composition, 0.76 wt% C
• Begin at T > 727°C (eutectoid T)
• Rapidly cool to 625°C and hold isothermally
T(°C) Austenite (stable) 727C)
700 Austenite
(unstable)

600 Pearlite

500

g g
g g
400 g g

1 10 10 2 10 3 10 4 10 5
Time (s) Adapted:W. Callister, Materials
• Beginning of transformation line Science & Engineering, 8th Ed.

• Ending of transformation line

• 50% of transformation - dashed line
• The area left of the beginning line  unstable g
Gordana Cingara 3SP3
(G.A Cingara) 32
IT diagram for the steel of eutectoid composition
g
727 A1

g Coarse Pearlite

PEARLITE
Fine Pearlite

Upper Bainite

BAINITE Upper bainite (~ 300-5000C)

Lower bainite (~200-3000C)
g Lower
Bainite

Ms - Martensite begins to form

Martensite
Adapted:W. Callister, Materials
Science & Engineering, 8th Ed.
33
Gordana Cingara 3SP3
(G.A Cingara)
 IT Diagrams

(a) At temperatures just below the eutectoid, COARSE

PEARLITE is formed - diffusion rates are relatively high.
(b) With decreasing T, the FINE PEARLITE is formed
(diffusion rate decreases!). Adapted:W. Callister, Materials
Science & Engineering, 8th Ed.
Gordana Cingara 3SP3
(G.A Cingara) 34
 IT Diagram

Pearlite Morphology

T just below 727OC: T well below 727oC

• Larger T • Smaller T
• Diffusion is faster • Diffusion is slower
• Pearlite is COARSER • Pearlite is FINER

- Smaller T: - Larger T:

colonies are colonies are
larger smaller

Gordana Cingara 3SP3 35

 IT Diagram
BAINITE

Microstructure (laths with long rods of Fe3C in a ferrite matrix)

• Diffusion controlled transformation

• Bainite is tough, harder and stronger than pearlite!
36
Gordana Cingara 3SP3
 IT diagram for an eutectoid steel

A1

PEARLITE

Hardness
BAINITE

Martensite

Steel 1080 containing 0.79% C and 0.76% Mn (effect of Mn later);

A-austenite, F-ferrite, C-Cementite.
Note the HARDNESS on the right! 37
Gordana Cingara 3SP3
 IT Diagrams

Isothermal
Transformation diagram
for the steel of eutectoid
composition

38
Gordana Cingara 3SP3
 IT Diagram
Isothermal Transformation diagram for
the steel of eutectoid composition and
isothermal heat treatments :

a) Rapidly cool to 350oC, hold

104 s and quench to room
temperature.

b) Rapidly cool to 250oC, hold

100 s and quench to room
temperature.

c) Rapidly cool to 650oC, hold

20 s, rapidly cool to 400oC,
hold for 103 s and quench to
room temperature.
39
Gordana Cingara 3SP3
 IT Digram Involving Hypoeutectoid Composition

A1 g+a
2.14

a + P (Ferrite+Pearlite)
g
Austenite

Hardness
g+a A1 727

0.76

a+P
a P

Hypoeutectoid Steel: 0.35% C and 0.37% Mn. Af - the highest

temperature at which ferrite can form; A-austenite, F-
ferrite, C-cementite. Note the HARDNESS on the right!
40
Gordana Cingara 3SP3
(G.A Cingara)
IT Diagram Involving Hypereutectoid Composition

g+Fe3C
2.14
A1

g P+Fe3C

Austenite

Hardness
g+Fe3C BAINITE
a+g A1 727

0.76

a P
a+P P+Fe3C

Hypereutectoid Steel: 1.13% C and 0.3% Mn. A-austenite,

F-ferrite, C-cementite.
Consider C0=1.13 wt% C Note the HARDNESS on the right!
41
Gordana Cingara 3SP3
(G.A Cingara)
 b) Continuous Cooling
Transformation Diagrams
CCT

2.14

g
Austeni Cooling austenite with
te
A1 72 various cooling rates!
7

P
a + P+Fe3
P C

Gordana Cingara 3SP3

42
(G.A Cingara)
b) Continuous Cooling Transformation Diagrams- CCT
• Very slow cooling – coarse
pearlite

• Faster cooling – fine

pearlite
CCR

• CRITICAL cooling rate -

tangent to the nose
(minimum cooling rate
producing martensite; any
slower rate will form some
softer product)

• Rapid quench – rapid

enough to avoid
transformation in the nose
region (it remains g until the
Ms line is reached)

Source: S. Avner, Introduction

toPhysical Metallurgy (1974)
Gordana Cingara 3SP3 43
 CCT
Quenching - high
cooling rate!

CCR

Critical cooling rate

(CCR): minimum
cooling rate that will
produce a totally
MARTENSITE structure
(tangent to the nose)
Gordana Cingara 3SP3
44
 CCT
CCT diagram for an alloy
steel (4340)

Several superimposed
cooling curves
demonstrating dependence
of the final microstructure
of this steel on the
transformations that occur
during cooling.

Adapted:W. Callister, Materials

Science & Engineering, 8th Ed. Gordana Cingara 3SP3
(G.A Cingara) 45
 IT diagram for an alloy
steel 4340
A- Austenite
B – Bainite
P – Pearlite
M – Martensite
F – Proeutectoid Ferrite

•CCT and IT for the

same steel – different
(different kinetics of reactions)!

Adapted:W. Callister, Materials

Science & Engineering, 8th Ed.
Gordana Cingara 3SP3 46
(G.A Cingara)
 MARTENSITE

• Quenching - high cooling rate!

• Diffusionless transformation!
• No change in chemical composition

• Martensitic steels are the hardest/strongest but also

the most brittle!

Gordana Cingara 3SP3

47
 MARTENSITE formation
(CCT)
8 00 Austenite (stable)
T(°C) A
TE • Critical cooling rate
P (CCR) - minimum cooling
6 00
S
rate that will produce
4 00 A B totally MARTENSITE
structure
0%
2 00 M+A 50%
M+A
M+A
9 0% • The percent of austenite
10-1 10 103 105 time (s) transformed depends
only on the cooling rate!
Austenite (FCC) transforms
into martensite (BCT)

Adapted:W. Callister, Materials

Gordana Cingara 3SP3 Science & Engineering, 8th Ed.
48
 MARTENSITE
• Body-centered tetragonal structure (BCT)
• Crystallography of martensitic transformation:

Bain Distortion: FCC  BCT

• Carbon atoms are inherited from the austenite, which

would normally proceed to BCC, are not able to go to
completion.

• Cooperative movement of all atoms (formed by a shear

transformation instead of by nucleation and growth
• Carbon atoms strain the lattice into the BCT
• In any given steel only a very small percentage of the
possible positions are ever filled.
Gordana Cingara 3SP3
49
Martensite

Volume change:
V = Vmartensite - Vaustenite = ~ 4 %

BCT / FCC  c/a = 1.414

• During the decomposition of

austenite there is a net volume
increase
• Creation of internal stresses
that can grow and nucleate
cracks upon quenching

Gordana Cingara 3SP3

 Crystallography of martensitic transformation
Bain distortion: FCC lattice transforms to a BCT martensite!

Fe
C

BCT – martensite
- can be assumed to be an
intermediate structure between
The BCT cell is outlined in the FCC in the normal phases of iron – fcc
(a), and shown alone in (b).
and bcc.
The Bain distortion converts (b) to (c)
Gordana Cingara 3SP3 51
Martensite microstructure

• The needle-like structure of martensite

• White areas - retained austenite.
Source: W. Callister, Materials
Gordana Cingara 3SP3 Science & Engineering, 8th Ed. 52
 Martensite structure
Two major morphologies:
• Lath Martensite (<0.6%C - low & medium C steels;
extremely high dislocation density)
• Plate martensite (> 1%C – high C steels; twinned)

Lath martensite in an Fe-0.2%C. Plate martensite in an 1095 steel

A packet of laths is outlined with arrows. 500X (0.97%C, 1.05%Mn, 0.25%Si, and 0.2%Cr).
Unetched areas are retained austenite. 1000X
53
Gordana Cingara 3SP3
 Martensite
HRC

The properties of
martensite are a
function of its
carbon content, C%

Effect of carbon content of steel on

the hardness of martensite
Gordana Cingara 3SP3
ND TD

RD

~0.1 mm

Ferrite 
Martensite 
TiN-inclusion

Dual Phase Steel DP780

Avramovic-Cingara G., Wilkinson D.S., Jain M.K.: Microstructure and

Damage Mechanisms in Dual Phase Steels DP600 and DP780, Auto
21 Workshop, Waterloo University, (2006)
 Dual Phase Steels (Dofasco)
DP600 DP780

MARTENSITE
Light microscopy, special etching method:
Martensite – brown
Ferrite - white;
Bainite - black Avramovic-Cingara G., Saleh Ch.A.R., Jain M.K., Wilkinson D.S,
Metallurgical Transactions A, Vol. 40A, (2009) pp. 3117-27. 56
Summary

Adapted:W. Callister, Materials

Science & Engineering, 8th Ed.

Gordana Cingara 3SP3 57

(G.A Cingara)
TEMPERING

G. Cingara 3SP3
 TEMPERING
Heat treatment of a martensitic steel at a temperature
just below the eutectoid temperature in the range of
250-650 ºC for a specified amount of time.

The purpose:
• To relieve residual stresses
• To improve the ductility and toughness

Reheating of martensite promotes decomposition

(diffusion processes produce more stable and less
brittle structure)

G. Cingara 3SP3
SUMMARY - Transformation products during quenching
and tempering of a eutectoid steel
Spherodite
AUSTENITE or hold at 650-
705oC
HRC=5-10
650-705oC
Coarse Pearlite
HRC=15

Medium Pearlite
HRC=30 400-650oC

Fine Pearlite
HRC=40 Tempered
Martensite
Bainite
HRC=40-60 200-400oC

Martensite
HRC=64

G. Cingara 3SP3
 Spherodite - TEMPERING
• Spherodite is formed when a pearlitic or bainitic steel is
heated up to a temperature just below the eutectoid (7270C) and
left at this T for a sufficiently long time (18-24 h);
• or - temepring a martensite!
• Formed by carbon diffusion!
• Very SOFT

Cementite as spherelike
particles in a ferrite
matrix
Source: W. Callister, Materials
Science & Engineering, 8th Ed.

G. Cingara 3SP3
TEMPERING
The effect of tempering
temperature on the
mechanical properties
of 1050 steel

G. Cingara 3SP3
 Surface Hardening
• Numerous industrial applications require a hard
wear-resistant surface called the case, and a
relatively soft, tough inside called core.

• Forming a thin layer of harder metal ("case") at the

surface

 The objective of surface hardening is to produce

a hard surface, while maintaining the overall
toughness and soft steel core.

Gordana Cingara 3SP3 63

 2. CARBURIZING
• Increasing the surface concentration of carbon
• For some applications, it is necessary to harden the
surface of a steel above of its interior.
• Steel exposed to an atmosphere rich in gas (CH4), at
elevated T.
• ~ 0.5 - 1 mm thick layer

The GEAR – carburizing example Fe + 2CO → Fe(C) + CO2

64
G. Cingara 3SP3
 Carburizing, or Case Hardening
OBJECTIVE: to produce a surface which is resistant
to wear while maintaining the overall toughness and
strength of the steel core.

• Carburizing of a low carbon steel to produce a

high-carbon, wear resistant surface.

• Quenching to form martensite at the surface.

65
G. Cingara 3SP3 65
 Carburizing
• The case will appear as a light martensite zone followed by
darker transition zone.
• Approximately 0.5 - 1 mm thick layer

The GEAR –
carburizing example
A properly carburized, hardened, and
tempered gear. (Etched in 2% nital.)

66
G. Cingara 3SP3
66
 Example – Design of surface hardening

Sketch
of axle and gear
assembly

D.R. Askeland, The Science and Engineering of

Materials, Thompson-Brooks, 2003

Heat Treatment of Steels (600-451 - G. Cingara), Week 7: Surface Hardening 67

 Example - Solution

AXLE
• The axle might be made from a forged 1050 steel (ferrite & pearlite)
• Surface hardening
• Induction hardening – selectively heat the steel above A3 T (~770oC)
• Quenching
• Tempering

Heat Treatment of Steels (600-451 - G. Cingara), Week 7: Surface Hardening 68

 Example - Solution
GEAR
• The gear might be made from a 1010 steel
• Gas carburizing
• T above A3 (~860oC)
• Carbon content ~1.0% in a very thin case
• Quenching – martensite
• Tempering

Heat Treatment of Steels (600-451 - G. Cingara), Week 7: Surface Hardening 69