Ferrous Alloys

Abhishek Gupta
Assistant Professor, AKGEC
Ghaziabad
Syllabus
Allotropic Transformation of Pure Iron

Liquid
Temperature, °C

1535°
δ (delta) iron (BCC)
1401°
γ (gamma) iron (FCC)
nonmagnetic

910°
α (alpha) iron (BCC)
nonmagnetic
768°
α (alpha) iron (BCC)
magnetic

Time
Cooling Curve of Pure Iron
 The Iron – Carbon Diagram
• It is a map of the temperature at which different
phase changes occur on very slow heating and
cooling in relation to Carbon, is called Iron- Carbon
Diagram.
• Iron- Carbon diagram shows
– the type of alloys formed under very slow
cooling,
– proper heat-treatment temperature and
– how the properties of steels and cast irons can
be radically changed by heat-treatment.
 Ferrite
• Ferrite is known as α solid solution.
• It is an interstitial solid solution of a small amount
of carbon dissolved in α (BCC) iron.
• Stable form of iron below 912 deg.C
• The maximum solubility is 0.025 % C at 723°C and
it dissolves only 0.008 % C at room temperature.
• It is the softest structure that appears on the
diagram.
 Pearlite
• Pearlite is the eutectoid mixture
containing 0.80 % C and is formed
at 723°C on very slow cooling.
• It is a very fine plate like or lamellar
mixture of ferrite and cementite.
• The white ferritic background or
matrix contains thin plates of
cementite (dark).
 Austenite
• Austenite is an interstitial solid solution of
Carbon dissolved in γ (F.C.C.) iron.
• Maximum solubility is 2.0 % C at 1130°C.
• High formability, most of heat treatments begin
with this single phase.
• It is normally not stable at room temperature.
But, under certain conditions it is possible to
obtain austenite at room temperature.
 Cementite
• Cementite or iron carbide, is very hard, brittle
intermetallic compound of iron & carbon, as
Fe3C, contains 6.67 % C.
• It is the hardest structure that appears on the
diagram, exact melting point unknown.
• Its crystal structure is orthorhombic.
• It is has
– low tensile strength (approx. 5,000 psi), but
– high compressive strength.
 Iron carbide beyond 6.67% carbon
Iron Carbide, Fe3C
⬤ The compound dissociates into iron and
Temperature, °C

carbon, if given the opportunity:

Fe3C = Fe + 3C

⬤ Fe3C is a metastable compound, because

such decomposition takes a very long time
at room temperature.
⬤ Because of the presence of Fe3C, this
diagran is not a true equilibrium diagram.
6.67

Iron Fe3C Carbon

wt. % carbon
 Ledeburite
• Ledeburite is the eutectic
mixture of austenite and
cementite.
• It contains 4.3 percent C and is
formed at 1130°C.
 Martensite
Martensite - a super-saturated solid solution of carbon
in ferrite.
It is formed when steel is cooled so rapidly that the
change from austenite to pearlite is suppressed.
The interstitial carbon atoms distort the BCC ferrite into
a BC-tetragonal structure (BCT).; responsible for the
hardness of quenched steel
Final iron – iron carbon diagram
 Various Features of Fe-C diagram
Phases present
Reactions L
α ferrite
Peritectic L + δ = γ δ BCC structure
BCC structure Ferromagnetic
Eutectic L = γ + Paramagnetic Fairly ductile
Fe3C
Eutectoid γ = α + Fe3C γ austenite Fe3C cementite
FCC structure Orthorhombic
Non-magnetic Hard
ductile brittle

Max. solubility of C in ferrite=0.022%

Max. solubility of C in austenite=2.11%

 Three Phase Reactions
• Peritectic, at 1492 deg.C, with low wt% C
alloys (almost no engineering importance).
• Eutectic, at 1130 deg.C, with 4.3wt% C, alloys
called cast irons.
• Eutectoid, at 723 deg.C with eutectoid
composition of 0.8wt% C, two-phase mixture
(ferrite & cementite). They are steels.
 δ -iron + L
Peritectic
· Point
Temperature, °C

austenite

The Peritectic Reaction @ 1492 C

Delta-iron 0.10%C + Liquid 0.50%C cooling Austenite 0.18%C

Fe wt. % carbon heating Fe3C
 Eutectic
liquid
Temperature, °C

Point
·
austenite + cementite

The Eutectic Reaction @ 1130 C

cooling
Liquid 4.3%C ( Austenite 2.0%C + Cementite 6.67%C )
heating
Ledeburite (an eutectic mixture)
Fe wt. % carbon Fe3C
Temperature, °C

austenite Eutectoid
Point
·
ferrite + cementite

The Eutectoid Reaction @ 723 C

Austenite cooling ( Ferrite

Fe 0.8%C wt. % carbon 0.025%C + CementiteFe C )
6.67%C
3
heatingPearlite (an eutectoid mixture)
 The Iron-Iron Carbide Diagram
The diagram shows three horizontal lines which indicate
isothermal(constant temperature) reactions (on
cooling / heating):
• First horizontal line is at 1492°C, where peritectic
reaction takes place:
Liquid + δ ↔ austenite
• Second horizontal line is at 1130°C, where eutectic
reaction takes place:
liquid ↔ austenite + cementite
• Third horizontal line is at 723°C, where eutectoid
reaction takes place:
austenite ↔ pearlite (mixture of ferrite &
cementite)
Micro structure of eutectoid steel
Micro structure of hypo-eutectoid steel
Micro structure of hyper-eutectoid steel
Complete microstructure diagram of iron – iron carbon diagram
 Alloying Steel with more Elements
• Teutectoid changes: • Ceutectoid changes:

The diagram shows how the The diagram shows how the
eutectoid temperature changes eutectoid concentration changes
with change in wt% alloying with change in wt% alloying
elements. elements.
 Diffusion
“The movement of particles in a solid from
an area of high concentration to an area of
low concentration, resulting in the uniform
distribution of the substance.”

During diffusion molecules move from an

area of high concentration to an area of low
concentration.

They are said to move down a

concentration gradient.

The material that undergoes the transport

is known as diffusant or permeant or
penetrant.
Diffusion is a passive process which means that no energy is needed.

Molecules diffuse until they are evenly spaced apart and equilibrium is reached.
 STEADY STATE Diffusion
Molecule diffuse spontaneously from region of higher concentration to region of lower
concentration until diffusion equilibrium is established.

Rate of diffusion independent of time.

Flux proportional to concentration gradient =

 STEADY STATE Diffusion

The flux J is expressed as either in number of atom per unit time.

Steady state diffusion means that J does not depend upon time.

In this case fick‘s 1st law hold that flux along direction “x”
 MECHANISM of Diffusion
Mechanisms:
Gases & Liquids – random (Brownian) motion.

Solids – vacancy diffusion or interstitial diffusion.

I. Vacancy diffusion: Only adjacent atoms can move into a vacancy.

Vacancy moves in opposite direction of atomic motion. Rate depends on
concentration of vacancies.
 MECHANISM of Diffusion
II. Inter diffusion: Atoms tend to migrate from regions of high conc. to
regions of low concentration.
smaller atoms can diffuse between atoms. Initially After some time
•Atom can move into any adjacent empty interstitial position (usually
smaller atoms).
•Rate depends on concentration of interstitial atoms.
(Usually faster than vacancy diffusion).
Interstitial Diffusion
Diffusion of carbon in Iron
is interstitial diffusion
 TTT DIAGRAM
• T.T.T. shows relation between temperature &
time taken for decomposition transformations to
take place in a metal when the transformation is
isothermal.
• Assess decomposition of austenite in a heat
treatable steel.
• Provides information for the process of austenite
decomposition under non-equilibrium conditions.
(Transformation of austenite to the time &
temperature conditions.)
 DIFFERENCE BETWEEN IRON-CARBON & TTT
• Study of Fe-C diagram shows study of cooled steels under
non-equilibrium conditions.
• Doesn’t involve reaction condition during heat treatment of
steel.
• It only shows phases & resulting microstructure
corresponding to equilibrium conditions.
• Fixing to austenitizing temperature & predicting phases
eventually obtained at given % of C & temperature.
• Microstructure & properties of steel depends upon rate of
cooling.
• As cooling rate increases transformation temperatures are
lowered & metastable (non-equilibrium) phases are formed.
• At a very high rate of cooling of steel produces Martensite
(non-equilibrium phase)
 STEPS TO CONSTRUCT TTT DIAGRAM
• Obtain large number of relatively small specimens. Place the sample in
a molten salt bath held at the austeniting temperature of 1080°C.
Specimen are kept in a salt bath for a long period of time to form
complete austenite.
• When austenitized, specimen is transferred to other salt bath at
temperature of 810°C.
• After specimen react isothermally, quenched in cold water/ iced brine.
• As the specimen is quenched in cooled water, isothermal reaction
stops & remaining austenite suddenly transforms into martensite.
• Reaction curve forms when large no. of specimen isothermally reacted
for varying time periods.
• Finally data obtained from a series of isothermal reaction curves (TTT)
for the whole temperature range of austenite instability for a given
composition of steel.
TIME-TEMP-TRANSFORMATION plot
• The transformation rate is inversely proportional to time at any temperature.

• Tangent to C-curves (TTT Curves) gives us the cooling rate.

• Based on the above curves the time required to transformation of

Austenite-pearlite can be determined.

• TTT diagram denotes that it is drawn at different cooling rates, hence it is not
recorded as an equilibrium diagram as Iron carbon diagram.
TIME-TEMP-TRANSFORMATION plot
(fine and coarse pearlite)
Summary of all the phases