21.

Heat Treatment of Metals

 Questions
• Does heating a metal or allow always result
in reducing the strength and hardness of
the metal (due to stress relief, grain
growth, reducing dislocation density)?

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 Learning Objectives
• To identify non-equilibrium phases generated during heat
treatment of steel (martensite, bainite, spheroidite), and
to identify the relative ranking of physical properties of
the phases.
• To use a Time-Temperature Transformation (TTT) diagram
and Isothermal Heat Treatment Curve to identify what
phases are generated during quenching.
• To describe the difference between quenching and
tempering vs. precipitation hardening to alter physical
properties.

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 Heat Treatment
• Why do we heat treat materials?
– To produce specific properties, such as yield strength (hardness),
ductility and toughness, achieved through manipulation of the
microstructure.
– To relieve stresses caused by dislocations and grain boundaries – e.g
from cold working or quenching
– To use non-equilibrium heating and cooling to create microstructures
which do not appear on the phase diagram (i.e. meta-stable phases),
some of which may have highly desirable properties

• Temperature and time will affect the microstructure and

properties of the material.
– The mechanical properties of an alloy that has been heat treated can
be altered significantly if it is re-heated.
– E.g welding, machining, moderate elevated temperature over time.

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 Heat Treatment - Reference Page
There are a range of treatments involving heating/cooling or holding at a prescribed
temperature and controlled cooling. For reference, a few terms for this topic:
• Austenitize - hold at temperature high and long enough to convert to austenite Heating will generally
phase (for Fe-C alloys) decrease hardness
and internal
dislocations, while
• Anneal - hold above its recrystallization temperature, followed by a relatively
increasing ductility and
slow cooling procedure (equilibrium cooling, aka furnace cooling).
toughness.

• Quench - rapidly cool in water or oil to create strong but brittle microstructures
• Temper - hold at moderate temperature after quenching to regain ductility and Rapid cooling will
toughness generally increase
hardness and internal
dislocations, while
• Stress Relief - hold at temperature below recrystallization temperature to
reducing ductility and
relieve stresses from cold working or quenching
toughness.

For Precipitation
• Precipitation hardening / “solutionizing” - hold at elevated temperature so that hardness and ageing,
new particles nucleate and form to strengthen the alloy (Al-alloys and Ni-alloys) heating has the
• Ageing - same as precipitation hardening, but at lower temperatures (often opposite effect -
ambient temps) for much longer times (Al-alloys and Ni-alloys) heating increases
hardness and internal
microstructures, and
These processes can sometimes overlap in their outcomes. reduces ductility and
toughness.

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 Example - Quenching and Tempering Steel

1. Austenitize 1
• Heat to a temperature region where 727°
100% Austenite is formed C
• Hold to allow complete transformation Temperature
2
3
2. Quench (normally use water or oil)
• Rapidly form new, harder microstructures.

23°C
3. Temper
• Reheat to 200 - 550°C Time
• Decreases hardness, regain some
ductility.

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 Isothermal Transformation Diagrams -
Example - Quenching Eutectoid Steel
• The rate of transformation of the austenite
to pearlite is dependent on temperature
• This temperature dependence can be

Percent austenite
plotted as % transformation vs. log. time

Percent pearlite
• Data was collected for each curve, after
rapid cooling of 100% austenite to the
lower temperature.
• Temperatures further from the eutectoid
isothermal temp have faster transformation
times (i.e. lower temperatures result in
faster quenching, shorter transformation
times).
• For these curves, the temperature during
quenching was held constant throughout
the entire process (isothermal process) This Percent transformation from Austenite to
is not the conventional process – it is more Pearlite when quenching at different holding
typical to have the material continuously temperatures. Fe-C is at the eutectoid
cooled down to much lower temperatures composition (0.76 wt% C)
(not discussed in this course).

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 Time-Temperature Transformation (TTT) diagram
Example – Quenching Eutectoid Steel
• It is more convenient to represent multiple
temperatures on one Time-Temperature
Transformation (TTT) diagram
• From each isothermal transformation
diagram, extract the start time, 50%
completion time, and end time.
• Transfer these three times to the 3
curves on the TTT diagram.
• Repeat at different temperatures.
Many experiments needed!

• NB: Temperatures below 5200C result in

non-equilibrium cooling, which generates
new microstructures (discussed later in this
lecture)

• NB: These examples are only for one

composition of steel (in this case the
eutectoid composition, o.76% Carbon).
Other compositions will have different
values and curve shapes.

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 Time-Temperature Transformation (TTT) Diagram,
with an overlaid Isothermal Heat Treatment Curve ( cuve ABCD)

Slow cooling gets thicker layers – Coarse Pearlite

Fast cooling gets thinner layers – Fine Pearlite

Good example of how to use Isothermal Heat Treatment Curve -

(Example Problem 10.3 from Callister) – will be included in Problem Set 4
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 Bainite – same composition as pearlite
(a - ferrite and Fe3C), but in needle-like form
• Remember that carbon must diffuse
(move) in order to form distinct
pearlite layers (low C composition in
a-Ferrite, high C in Fe3C)

• BUT if the sample is quenched to a

sufficiently low temp, there is less
time for diffusion to occur.

• Instead of layers/lamellae, new

Bainite region
structures which look like thin needles
of Fe3C in a ferrite matrix will form.
This phase is called Bainite.

• In this TTT diagram, Bainite forms

when the quench temperature is held
between 210 and 520oC.

• Question - what happens at even

lower temperatures?

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10 - UPDATED
 Martensite – a harder, more brittle microstructure
formed by very rapid cooling
• If the temperature is cooled fast and low
enough (plunged into water), there is no
time for diffusion, and Ferrite and
Cementite do not have time to form at all
(so no pearlite, no bainite)

• A new supersaturated and unstable

structure is formed, called Martensite.

• The lattice gets “stuck” between FCC and

BCC, with carbon getting into the structures

• This is a Body Centred Tetragonal (BCT)

structure, or in terms of lattice parameters,
an elongated cube with unequal side lengths
(a ≠ c)

• Some of the initial Austenite may stay

“locked in place” as Austenite (the M + A
region on the TTT diagram)

• Martensite is a relatively common structure

formed during Steel Heat-Treatment
quenching.
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 Martensite

Above:
Body Centred Tetragonal structure for
Martensite, a ≠ c. Spheres indicate
locations of iron, X indicate possible
locations of carbon (not all are occupied)

Right (from Callister):

Photomicrograph showing martensitic
microstructure. The needle-shaped grains
are the martensite phase, and the white
regions are austenite that failed to transform
during the rapid quench.
24.6 m
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Characteristics of Martensite Transformation
• Occurs by a non-diffusional process (i.e. atoms do not have to move or diffuse to
different locations to form layers, just move into BCT crystal positions), so the
transformation occurs extremely fast - i.e. at the speed of sound
• Transformation occurs at quenching temperatures well below eutectoid
temperature.
• Martensite in steel is very hard (high y) and extremely brittle (little or no
ductility). Until very recently, not useful as an engineering material
• Martensite can be be tempered to get a useful steel material (reduced hardness,
but much greater ductility)
• Some modern applications use untampered Martensite (ultra-high strength
steels).
• “Martensitic / diffusionless transformations” (cooling so fast that atoms cannot
diffuse) can occur in other metals as well.

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 Tempering Martensite
• Heat the martensite for 1 hour at 200-550 oC
• During tempering, two things occur:
– BCT (a´) phase transforms to BCC (a) phase (i.e. lattice parameter
now changes so that a = c)
– A very fine distribution of Fe3C particles (precipitates) are formed
in an a matrix
– This creates a structure with high hardness (although not as hard
as untemperated martensite), but with greater ductility
• If we hold at temperature for too long the steel will
become “soft” and very ductile (turns into a material
equivalent to spheroidized steel, discussed later in this
lecture)

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 Martensite before and after Tempering

24.6 m 2 m
• Quenched • Tempered
• 564°C
• small particles Fe3C cementite
• matrix is a ferrite 15
Hardness of Tempered and Untempered
Strength and ductility (% reduction in area)
Martensite vs. Fine Pearlite at different
of Tempered Martensite at different
carbon compositions
tempering temperatures
 Annealing Processes
• Annealing refers to a heat treatment with the following stages:
1. Heat to the desired temperature.
2. Hold or “soak” at that temperature to allow for any
necessary transformation or solutionizing reactions to
occur.
3. Followed by slow controlled cooling to maintain
consistency of the temperature in the material

• Control of both Heating and Cooling is important

– Poor control can lead to temperature gradients throughout
the part.
– Temperature gradients can induce internal stresses that may
lead to warping and cracking.

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 Annealing of Ferrous Alloys
Several different annealing procedures for steels:

• Normalizing
– Cooled in air.
– Gives a good combination of strength and ductility
• Full Annealing
– Used for low or medium carbon steels that will be machined or plastically deformed.
– Furnace turned off, both steel and furnace cool together.
– Result: Course Pearlite, Soft and ductile.
• Spheroidizing
– Used for medium and high carbon steels that have coarse pearlite that may still be too
hard to machine or deform.
– Heated just below eutectoid (700°C) for 15 – 25 hours.
– Coalescence of Fe3C to form spheroid particles

Also, industry has some highly specific definitions for procedures at specific temp ranges.
An example: http://www.riheattreating.com/heat-treating-specialties.html
Spheroidite – formed by tempering pearlite.
• Start with Pearlite.
• Raise the steel to a high temperature for a
sufficiently long time
• Keep below 727 oC
• The Fe3C (cementite) layers evolve into
a dispersion of spheres throughout the
metal. There is an overall reduction in
surface area.
• The continuous phase is the a ferrite
• Reduced strength, but ductility is greatly
increased
• It looks similar to tempered martensite, but
these are much larger spheres (30 um vs 1
um), and a different material phase in the
sphere shape (cementite vs. martensite) 30 m

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• Note that for Spheriodite, hardness is reduced, but ductility increases substantially.
 Precipitation Hardening – strengthening alloys at
elevated temperatures
• Small uniformly dispersed second phase particles within the original matrix
phase can enhance strength and hardness.
• This can be achieved by an appropriate heat treatment – for some alloys, this
occurs when the solid is super-saturated with a solute atom at room
temperatures, but which can be precipitated out at elevated temperatures
which have sufficient diffusion rates.

• Precipitation hardening is also called “Age hardening” because the strength

develops over time.
• Major strengthening mechanism for alloys of Al, Fe, Ni, Cu
• Need appreciable solid solubility of one alloying component (several %) in the
other.
• Also require a large decrease in solid solubility at T , e.g. Cu in Al
• The strength and hardness can peak and start to diminish if the ageing
process goes for too long, since the small particles can become larger and
have an overall reduction in dislocation boundaries.
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 Precipitation Hardening

Precipitation hardening will only

occur in alloys that:
1. show appreciable solid solubility
1.
of one alloying component (several
%) in the other.
2.
2. show a solubility limit that
rapidly decreases in concentration
of one major component with
temperature reduction (in this
particular diagram, the fraction of B
in the a phase reduces as the
temperature decreases from To to
T2 )

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 Example: Heat Treatment of Aluminum Alloy -
Precipitation Hardening
1. Solution Heat Treatment
• Form a single phase solid solution.
2. Quench
• Enters into 2-phase region of phase
diagram, but does not form a hardened
martensitic-type microstructure. Instead,
it creates a metastable supersaturated
solid solution at room temperature.
3. “Age”
• Elevate the temperature again, and
generate a distribution of very small
precipitates.

Identical shape to the Quench-Temper cycle

for steel, but a very different mechanism and
the opposite result (tempering steel makes it
less hard and more ductile)

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 Microstructural Changes During Ageing
• Some alloys age at room temperature
over a period of time (Natural Ageing),
while some need elevated temperature
(Artificial Ageing)
• Example: Theoretical alloy with
components A and B, at composition C0
• Raise temperature to T0 to generate the
a solid.
• Rapidly cool to T1 which forms the a
solid supersaturated with B atoms (this
is a metastable configuration) AT THIS
POINT, THERE IS NO b FORMED – there
is only a with B atoms interspersed, but
no actual b-phase anywhere.
• Aged at T2 to generate the formation of
very small b precipitates (1 to 10 nm)
• The character of b precipitates and
strength and hardness depend on T2,
and the holding time at T2

24 - UPDATE
 Example - Precipitation Hardening in Al-Cu

• Precipitation hardening has

been most widely studied
in Al-Cu alloys
• a phase is a substitutional
solid solution of Cu in Al
•  phase is an intermetallic
compound CuAl2

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 Example - Precipitation Hardening in Al-Cu
(cont)
• Start with a composition
~4% Cu
• Solution treat the alloy at
550 oC so that all material is
in the a phase
• Water quench to generate
the a phase supersaturated
with Cu atoms
• Age at 120-260 oC to form
precipitates of  in the a
matrix.

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Strengthening Curve During Precipitation Hardening

Overaged Coarsening of preciptates

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 Ageing Curves
(example - 2014 Al Alloy, 4 different temperatures)
• Strengthening process is
accelerated if temperature is
increased, but often cannot
reach the same maximum value
as slower lower-temperature
ageing.

• Some of these ageing processes

can take weeks or longer at
elevated temperatures!

• Ideally the temperature and

time for precipitation heat
treatment should be designed
to produce a hardness or
strength in the vicinity of the
maximum.

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Precipitation Hardening
Al-Cu Alloy
• Solution treat to obtain a single
phase a ( phase dissolves)
– FCC (No change)
• Quench to prevent formation of
precipitates (Supersaturated at
R.T.)
– FCC
– Low strength
• Age to form zones or precipitates
– strength increases, peaks and
then decreases
Quenching and Tempering
Steel
• Austenitize to form single phase 
– Fe3C dissolves
– BCC  FCC
• Quench to prevent Fe3C formation
and transform  to martensite
– FCC  BCT
– high strength, very brittle
• Temper to precipitate very fine
Fe3C
– strength decreases
– ductility increases
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 Example: Replacing steel sheet panels
on automobiles with aluminum alloys

• Steel
– Typically a 0.05 wt% carbon,  = 7.8g/cm3, y = 250 MPa
• Aluminum (Al-Mg-Si) Alloy 6061
–  = 2.8g/cm3
Example - 2008
– Forms precipitates of Mg2Si Cadillac CTS hood
– Strength
• as quenched, y = 60 MPa
• after natural ageing, y = 150 MPa (still too soft)
• after a 1 hour, 180oC paint bake cycle, y = 250 Mpa
• Problems
1. Relatively poor formability of Al Alloys
2. Would like higher strength

Reference for Aluminum sheet for automotive - www.mdpi.com/1996-1944/7/7/5047/pdf

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 Review – Different mechanisms for
strengthening metals and alloys
1. Grain Size reduction (lec 11, 13, 14)
2. Cold Working (lec 13)
3. Solid Solution Hardening (lec 14)
4. Hardening due to Pearlite (lec 20, 21)
5. Quenching and Tempering (martensite) (lec 21)
6. Precipitation Hardening (lec 21)

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 Learning Objectives (review)
• To identify non-equilibrium phases generated during heat
treatment of steel (martensite, bainite, spheroidite), and
to identify the relative ranking of physical properties of
the phases.
• To use a Time-Temperature Transformation (TTT) diagram
and Isothermal Heat Treatment Curve to identify what
phases are generated during quenching.
• To describe the difference between quenching and
tempering vs. precipitation hardening.

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 Updates to slides since initial
posting
• Page 24 – added text highlighting the
supersaturation requirement before precipitation
hardening.

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