Heat Treatment of

Steel Alloys
YELLOW ALERT
 Heat Treatment of Steel Alloys

Diffusive vs. Displacive Transformations of

Pure Iron (Fe)
Role of Dissolved Carbon in Fe
Transformations
Heat Treatment of Steel Alloys
Diffusion Process
 Other diffusion
mechanisms
Grain
boundary

Interstitial
diffusion
Surface
Diffusive Transformation of FCC to BCC in Pure Fe
Above 914° C pure Fe is face centered cubic (FCC).
Below 914° C the thermodynamically stable phase of pure
Fe is body centered cubic (BCC).
Note that the speed of the “interface” in this
transformation is zero at 914° C.

Less thermal energy

Increasing driving force

Speed of the
interface
Why this shape?

Temperature
 Nucleation in the Diffusive Transformation of
f.c.c.-> b.c.c. in Pure Fe

Nucleation is very
important
The more nuclei : The
more Volume
Transformed
In a diffusive
transformation:
– Volume
transforming per
second
increases
linearly with the
number of
nuclei.
 Grain Boundary
Nucleation
The grain boundaries in the f.c.c. pure Fe
are the most common site for
nucleation of the b.c.c. phase.
 Homogeneous vs.
Heterogeneous Nucleation
The critical radius,
r*het, of a
heterogeneous heterogeneous
nucleus is much
larger than the
homogeneous
critical radius, r*hom,
of a homogeneous Crystal radius
nucleus of the same
phase.
For the same critical
radius the Absolute temperature

heterogeneous
nucleus contains far
fewer atoms.
 Diffusive
Transformation of
f.c.c b.c.c. in Pure Fe
The overall rate of transformation depends both on
nucleation and growth
The semi-schematic diagram below shows that the rate of
transformation starts below the equilibrium temperature,
914°C, and increases until approximately 700°C.
The slowing rate of diffusion dominates below 700°C.
 Time-Temperature-Transformation
(TTT) Diagram

The standard practice to

display diffusive
transformations is with
the “Time-Temperature-
Transformation” (TTT)
diagram. It is also
known as the
“Isothermal-
Transformation”
diagram or “C-curve”.
The TTT diagram for the
diffusive f.c.c.->b.c.c.
transformation of pure
Fe is shown at the right.
 The two curves are related

Consider the 1% transformation line (1% of the fcc to transform to bcc)

1) The transformation rate is zero both at 914 and –273 C so the time required
for the transformation is infinite at these temperatures

2) The transformation rate is a maximum at 700 C so the time for the 1% transformation
must be a minimum at 700 C
 Displacive Transformation of f.c.c. ->
b.c.c. in Pure Fe

If we quench f.c.c. Fe from

914°C at a rate of about
105°Cs-1, we expect to
prevent the diffusive
The TTT diagram for the
diffusive f.c.c.->b.c.c.
transformation from
taking place.
In reality, below 550°C the
Fe will transform to b.c.c.
by a displacive
transformation.
 Martensite Plates form in f.c.c. Lattice

The displacive transformation

of f.c.c. -> b.c.c. in pure Fe
is shown schematically.
Lens shaped crystals of b.c.c.
Fe nucleate at the grain
boundaries of the f.c.c. Fe
and grow out into the f.c.c.
crystal.
The lens shaped crystals stop
when they hit the next grain
boundary.
This kind of transformation is
called a Martensitic
Transformation.
Martensite transformation
 Complete TTT Diagram for Pure Fe

The is shown below. The “Ms” stands for “Martensite

Start Temperature” and the “Mf” stands for
“Martensite Finished Temperature”.
If a sample is cooled fast enough to prevent the diffusive
transformation from taking place, then martensite will
be formed as schematically shown at the left.
Martensite Transformation in Steels
 The Martensite in Steel is Not Cubic

The crystal structure of 0.8% Carbon martensite is

shown below.
To make room for the carbon atoms the lattice
stretches along on crystal direction. This produces
a face centered tetragonal unit cell.
Note that only a small proportion of the labelled sites
actually contain a carbon atom.
BCT formation
 Fe-C Interstitial Solid Solution in Austinite

The Carbon atoms fit into interstitial spaces in the FCC

Austinite structure schematically shown below.
Note the distortion of the Fe atoms [0.258-nm diameter]
around the Carbon atoms [0.154-nm diameter] since the
voids are 0.104-nm diameter.
 Fe-C Interstitial Solid Solution in Ferrite &
Martensite
The Carbon atoms cannot fit into interstitial spaces in the BCC
ferrite structure like they can in the FCC Austinite and
produce a BCT ( schematically shown below).
Note in the BCT the Carbon atoms force the unit cell to be
alongated in the c-direction. The largest interstitial void in
BCC iron has a diameter of 0.072-nm.
Isothermal Transformation
Experiments
 An Example
(Assume a Eutectoid Low Carbon Steel)
(a) Water-quench to room Temperature.
(b) Hot-quench at 690°C & hold 2 hr; water-quench

(c) Hot-quench at 610°C Pearlite

& hold 3 min; water-quench Pearlite
(d) Hot-quench at 580°C
& hold 2 sec; water-quench
Bainite
(e) Hot-quench at 450°C &
hold 1 hr; water-quench

50% pearlite + 50 martensite

All martensite
Another one...
Formation of Bainite
Perlite + Martensite
Bainite + Martensite
Martensite
 Hypoeutectoid Phase Diagram

If a steel with a composition x% carbon is cooled from the

Austenite region at about 770 °C ferrite begins to form. This is
called proeutectoid (or pre-eutectoid) ferrite since it forms
before the eutectoid temperature.
Hypoeutectoid Isothermal
Transformation Curve
 Quenched & Tempered
Steel Alloys

Heat Treatment of Steel Alloys (Tempering)

Microstructure of Fe-C Martensites
Mechanical Properties of Fe-C Martensites
Microstructural Changes in Martensite with
Tempering
Tempering
Tempering is the process of heating a martensitic steel at
a temperature below the eutectoid transformation
temperature. This makes it “softer” and more
“ductile”.
Microstructure of Fe-C Martensites
Mechanical Properties of Fe-C
Martensites
 Microstructural Changes in
Martensite with Tempering

Martensite is a metastable structure, and it decomposes

when reheated.
In lath martensites of low-carbon plain-carbon steels
there is a high dislocation density, and these
dislocations provide lower energy sites for carbon
atoms than there regular interstitial positions. This
process can take place between 20° and 200°C.
 Microstructural Changes in
Martensite with Tempering

For martensitic plain-carbon steels with more than 0.2% carbon

tempering produces Cementite, Fe3C.
The shapes are diffenent at different temperatures. The important
point is that the Fe matrix returns to its BCC form found in Ferrite.
The electron micrographs below show the microstructure for two
treatments.
 Variation of Hardness with
Tempering Treatment

The curves below show the reduction of hardness for various

treatments of a quenched low-carbon plain-carbon steel with
0.35% carbon.
Martempering
Austempering
Typical Mechanical Properties &
Applications of Plain-Carbon Steels