Chapter 4

Phase Transformation & Metals

Alloys
Outline
• Basic concept of phase transformation – Types of transformation &
Stages.

• Time Temperature Transformation (TTT) curve (Isothermal) &

Continuous Cooling Transformation (CCT) curve (continuous cooling)
transformation of Iron-Carbon alloy – microstructure-properties
correlations.

• Microstructure development.

• Types of metals & metal alloys – ferrous & non-ferrous, properties and
applications.

• Metal fabrication – forming, casting & miscellaneous.

• Thermal processing and heat treatment of metal alloys.

What is Phase Transformation???
• Phase transformations is an important phenomena in material processing
which involves the alteration of microstructure, with or without
significantly changing the number or composition of phases present.
• at least one new phase is formed – different structure and/or different
chemical/physical properties compared to parent phase.
• Simple diffusion dependent
transformation – no change in
number or composition of phase
present – example melting of ice into
water or cooling of CO2 gas into dry
CO2.

• Complex diffusion dependent

transformation - alteration in phase
composition and often the number of
phase – example eutectic or eutectoid
transformation where the composition
of Fe and C will be changed.

• Diffusionless transformation –
metastable phase, interphase
transformation – example martensite
to tempered martensite – changes in
microstructure and properties.
• The process of phase transformations:

• Nucleation of new phase(s) – formation of stable, small particles

(nuclei) of the new phase(s). Nuclei often formed at grain boundaries,
impurities or defects which is capable of growing.

• Growth – this nuclei increase in size – some/all parent phase will

disappear.

• Complete transformation achieved if the growth of these new phase

particles is allowed to proceed until equilibrium fraction is attained.

• Phase transformation does not happen instantaneously. Diffusion

dependent phase transformations can be rather slow and the final
structure often depend on the rate of cooling/heating.

 slow nucleation rate - few nuclei - large crystals

 rapid nucleation rate - many nuclei - small crystals

• Two types of nucleation : homogenous and heterogeneous

• Homogenous - nuclei of new phase form uniformly throughout the

parent phase.

• Heterogeneous – nuclei form preferentially at structural in

homogeneities such as container surface, insoluble impurities, grain
boundaries, dislocation and etc.
• The growth in phase transformation begins when the nuclei of new phase
exceeds certain critical size r* and become a stable nucleus.

• Nucleation and growth occur simultaneously upon the formation of stable nucleus
– numerous new nuclei formed as the existing nuclei undergo growth stage.

• Growth continuous until 2 or more nucleus are large enough and collide at the
boundary (grain boundary) – growth stops.
Rate of phase transformations
• The rate of transformation induced by cooling is a product of the nucleation rate
and growth rate.

• If ΔT is low (close to TT) – nucleation rate is low and growth rate is high - resulting
in coarse microstructure with large grains.

• If ΔT is high (large gap to TT) – strong undercooling, high nucleation rate and low
growth rate result in fine structure with small grains.
E.g.: Transformation of austenite to pearlite at Eutectoid temperature (Tm) – 540-727°C

5
Kinetic consideration of solid state transformation
• The time dependence of solid-state phase transformations at a fixed
temperature is often described in terms of the time dependence of the
fraction of transformation (y):

Rate = 1 / t0.5
• This time dependence of the fraction of transformation follows the Avrami
equation:
y  1  exp( ktn )
Where k and n are time-independent constant for the particular transformation.

• Temperature has a strong effect on the kinetics of the phase transformation and.
Therefore on the rate of the phase transformation.
• E.g. recrystallization of pure copper at different temperature.

Rate = 1 / t0.5

Rate (135°C) >> rate (113°C) >>

rate (88°C)

-at 135°C – coarse structure,

-at 88°C – fine structure
• Phase transformation in metal alloy – varying the temperature, composition or
external pressure – however, heat treatment (temperature) is the most utilized
– by heating or cooling a given metal alloy.

• During phase transformation – removal of excess energy supplied to get back

to equilibrium state.

• However, the rate to reach equilibrium very slow that true equilibrium structure
or properties rarely achieved.

• As the result, for equilibrium cooling – transformation shifted to lower

temperature than indicated by phase diagram (supercooling).

• For equilibrium heating – transformation shifted to higher temperatures

(superheating).

• The more rapid heating or cooling, the greater the supercooling or

superheating.
• For example the iron-carbon eutectoid reaction takes place at 727 °C but
typically displaced 10 to 20 °C below the equilibrium transformation
temperature.
• Thus in many applications, the preferred microstructure or properties is a
metastable one – which having an intermediate properties between initial and
equilibrium state.
 Possible Transformations of steel

Martensite
T Martensite
Strength

Ductility
bainite
fine pearlite
coarse pearlite
spheroidite
General Trends
Time Temperature
Transformation(TTT) curves
 Iron-Iron Carbide phase diagram Eutectic
L →  + Fe3C
Peritectic L
L+→ 1493ºC

L+ 
0.1 %C  2.06 1147ºC

Eutectoid  + Fe3C
 →  + Fe3C
723ºC


0.025 %C  + Fe3C
T →

Fe Fe3C
0.16 0.8 4.3 6.7
%C →
WHAT ARE TTT CURVES
• T (Time) T(Temperature) T(Transformation) diagram is a plot of
temperature versus the logarithm of time for a steel alloy of definite
composition.

• It is used to determine when transformations begin and end for an

isothermal (constant temperature) heat treatment of a previously
austenitized alloy

• TTT diagram indicates when a specific transformation starts and

ends and it also shows what percentage of transformation of
austenite at a particular temperature is achieved.
http://education.sptech.xyz/tttdiagram.html
 Time- Temperature-Transformation (TTT) Curves – Isothermal
Transformation Diagram

800 Eutectoid temperature

723 Austenite Coarse
Pearlite
600 Fine
Eutectoid steel

500 Pearlite + Bainite

T →

400 Bainite

300  Ms
Austenite
Not an isothermal 200
transformation
Mf
100
Martensite
0.1 1 10 102 103 104 105
t (s) →
The dependance of transformation to temperature and time can be
analyzed best using the diagram below:

2 solid curves are plotted:

 one represents the time

required at each
temperature for the start
of the transformation;

 the other is for

transformation
completion.

 The dashed curve

corresponds to 50%
completion.
 Different types of Time- Temperature-Transformation
(TTT) Curves

 Three types of curves are there depending on the carbon content of steel:

► TTT for hypereutectoid steel

► TTT for eutectoid steel
► TTT for hypo eutectoid steel
Continuous Cooling
Transformation(CCT) curves
Isothermal heat treatments are not the most practical due to rapidly
cooling and constant maintenance at an elevated temperature – time
consuming and high production cost.

Most heat treatments for steels involve the continuous cooling of a

specimen to room temperature.

TTT diagram (dotted curve) is modified for a CCT diagram (solid curve).

For continuous cooling, the time required for a reaction to begin and end is
delayed.

The isothermal curves are shifted to longer times and lower temperatures.
 In the above figure moderately rapid and slow cooling curves are
superimposed on a continuous cooling transformation diagram of a
eutectoid iron-carbon alloy.

 The transformation starts after a time period corresponding to the

intersection of the cooling curve with the beginning reaction curve and
ends upon crossing the completion transformation curve.

 Normally bainite does not form when an alloy is continuously

cooled to room temperature; austenite transforms to pearlite before
bainite has become possible

The austenite-pearlite region (A---B) terminates just below the nose.

Continued cooling (below Mstart) of austenite will form martensite
 For continuous cooling of
a steel alloy there exists
a critical quenching rate
that represents the
minimum rate of
quenching that will
produce a totally
martensitic structure.

 This curve will just miss

the nose where pearlite
transformation begins
Microstructure Development (E.g. Cu-Ni system)
Equilibrium Cooling Cu-Ni System
• Cooling occurs at slow rate T(ºC)
L (liquid) L: 35wt%Ni
and phase equilibrium is
continuously maintained.
• Solidification in the solid + 130 0
L: 35 wt% Ni
A
B
liquid phase occurs gradually : 46 wt% Ni
35 46
upon cooling from the 32 C
liquidus line. 43
D
24 L: 32 wt% Ni
• The composition of the solid 36
and the liquid change : 43 wt% Ni
120 0 E
gradually during cooling (as L: 24 wt% Ni
can be determined by the tie-  : 36 wt% Ni
line method.) (solid)
• Nuclei of the solid phase
form and grow to consume 110 0
all the liquid at the solidus 20 30 35 40 50
line. C0 wt% Ni
Microstructure Development (E.g. Cu-Ni system)
Nonequilibrium Cooling

• Fast cooling (quenching)

• Diffusion in the solid state is very slow.

– Outer layer (surface) solidify first followed by slow cooling of inner

layers. Outer layer has the equilibrium composition but as the solid
formed the composition of the inner layer changes.

– Formation of layered (cored) grains and the invalidity of the tie-line

method to determine the composition of the solid phase.

• The tie-line method still works for the liquid phase, where diffusion is
fast.
Microstructure Development (E.g. Cu-Ni system)

• Slow rate of cooling: • Fast rate of cooling:

Equilibrium structure Cored structure

Uniform C:
35 wt% Ni First  to solidify:
46 wt% Ni
Last  to solidify:
< 35 wt% Ni
Development of Microstructure (E.g. Fe-C system)

• Microstructure depends on
composition (carbon content)
and heat treatment.
• In the discussion below we
consider slow cooling in which
equilibrium is maintained.

Schematic representations of the

microstructures for an iron-carbon alloy
of eutectoid composition (0.76 wt% C)
above and below the eutectoid
temperature
0.76
Development of Microstructure (E.g. Fe-C system)

• When alloy of eutectoid composition (0.76 wt % C) is cooled

slowly it forms pearlite, a lamellar or layered structure of two
phases: α-ferrite and cementite (Fe3C).

• The layers of alternating phases in pearlite are formed for the same
reason as layered structure of eutectic structures: redistribution of
C atoms between ferrite (0.022 wt%) and cementite (6.7 wt%) by
atomic diffusion.

• Mechanically, pearlite has intermediate properties between soft,

ductile ferrite and hard, brittle cementite.
Development of Microstructure (E.g. Fe-C system)
• In the micrograph, dark areas are Fe3C layers, light phase is α-ferrite

Photomicrograph of a eutectoid
steel showing the pearlite
microstructure consisting of
alternating layer of -ferrit and
Fe3C
Schematic representation of the
formation of pearlite from austenit;
direction of carbon diffusion
indicated by arrows
 • Transformation occur upon cooling from
eutectoid temperature (727°C) – austenite
(C) transformed into ferrite (low C) phase
and cementite (high C) phase.

• Different microstructure developed

Austenite depending on the transformation
temperature:

Ferrite (i) 540 - 727°C – austenite to pearlite.

(ii) 215 - 540°C – austenite to bainite.

Cementite
(iii) 0 - 215°C – austenite to martensite

(quenching).
• Austenite can transform into various products depending on the
composition and cooling rates.

Rapid cooling /
Slow
Moderate quenched
cooling
cooling

• Morphology of parent austenite (grain size) decides the morphology of

products and thus its properties.
Properties, applications, processing & heat treatment of metal

ISSUES TO ADDRESS...

 How are metal alloys classified and what are their common
applications?

 What are some of the common fabrication techniques for metals?

 What heat treatment procedures are used to improve the mechanical

properties of metal alloys?
Classification of Metal Alloys
Metal Alloys

Ferrous Nonferrous

Steels
Steels Cast Irons
Cast Irons
<1.4 wt% C
<1.4wt%C 3-4.5 wt%C
3-4.5 wt% C

T(ºC) microstructure: ferrite,

1600 graphite/cementite

1400 L
+L
1200  1148ºC L+Fe3C
austenite Eutectic:
1000 4.30

+Fe3C
800 727ºC Fe3C
ferrite Eutectoid: cementite
600 0.76 +Fe3C
400
0 1 2 3 4 5 6 6.7
(Fe)
Co , wt% C
Ferrous Alloys
 Iron-based alloys: Steels (< 1.4wt% C) & Cast Irons (3 – 4.5 wt% C).
 Important engineering construction materials especially Fe-C alloy.
 Highly demand due to:
 Low cost and abundant within earth crust.
 Easier to be produced.
 Good strength, toughness and ductility – can be tailored / modified.
 Versatile – wide range of mechanical and physical properties.

 Can be alloyed and heat treated to modify properties:

 Alloying with mainly C or other elements such as Cr, Mo, Ni, V etc –
achieve specific microstructure & properties.
 Heat treatment – e.g. quenching to produce martensite from austenite
which can be tempered into much ductile and high strength tempered
martensite.
Cast Irons
• Ferrous alloys with > 2.1 wt% C
▫ more commonly 3 - 4.5 wt% C (brittle)
• Low melting – relatively easy to cast (1150 – 1300 oC)

• Cementite decomposes to ferrite + graphite

Fe3C  3 Fe () + C (graphite)

• 5 main types – Gray, ductile, white, malleable &

compacted graphite.
Types of Cast Iron
Gray iron
• graphite flakes
• weak & brittle in tension
• stronger in compression
• excellent vibrational dampening
• wear resistant

Ductile iron
• add Mg and/or Ce
• graphite as nodules not flakes
• matrix often pearlite – stronger but
less ductile
Types of Cast Iron (cont.)
White iron
• < 1 wt% Si
• pearlite + cementite
• very hard and brittle

Malleable iron
• heat treat white iron at 800-900ºC
• graphite in rosettes
• reasonably strong and ductile
Types of Cast Iron (cont.)

Compacted graphite iron

• relatively high thermal conductivity
• good resistance to thermal shock
• lower oxidation at elevated
temperatures
Limitations of Ferrous Alloys
1) Relatively high densities

2) Relatively low electrical conductivities

3) Generally poor corrosion resistance

• Cu Alloys • Al Alloys
Brass: Zn is subst. impurity -low r: 2.7 g/cm3
(costume jewelry, coins, -Cu, Mg, Si, Mn, Zn additions
corrosion resistant) -solid solution or precipitate
Bronze : Sn, Al, Si, Ni are -strengthened (structural),
subst. impurities aircraft parts
(bushings, landing & packaging)
gear) • Mg Alloys
NonFerrous
Cu-Be: -very low r: 1.7g/cm3
precip. hardened Alloys -ignites easily
for strength -aircraft, missiles
• Ti Alloys
• Refractory metals
-relatively low r: 4.5 g/cm3
-high melting T’s
vs 7.9 for steel • Noble metals -Nb, Mo, W, Ta
-reactive at high T’s -Ag, Au, Pt
-space applic. -oxid./corr. resistant
 Metal Fabrication Methods (ii)

FORMING CASTING MISCELLANEOUS

• Casting- mold is filled with molten metal

– metal melted in furnace, perhaps alloying elements added, then
cast in a mold
– common and inexpensive
– gives good production of shapes
– weaker products, internal defects & stress
– good option for brittle materials – hardly flow and sharp cooling
temperature (cool faster).
 Metal Fabrication Methods (ii)

FORMING CASTING MISCELLANEOUS

(a) Sand Casting

• (large and complex
parts, e.g., auto engine • Mixture of sand and wax (foundry sand)
used as mold material - withstand T
blocks), wrench and
>1600ºC
hammer and is inexpensive and easy to mold
• To create mold - pack sand around to
form a desired shape.
Sand Sand • Molten metal cast onto the mold and let
to cool.
molten metal
• Upon solidification, mold opened or
braked to release the product.
 Metal Fabrication Methods (ii)

FORMING CASTING MISCELLANEOUS

(b) Investment Casting

(low volume, complex shapes
e.g., jewelry, turbine blades)
• Stage I — Mold formed by pouring wax I
plaster of paris around wax pattern.
Plaster allowed to harden.
• Stage II — Wax is melted and then II
poured from mold—hollow mold
cavity remains.
• Stage III — Molten metal is poured
III
into mold and allowed to solidify.
 Metal Fabrication Methods (ii)

FORMING CASTING MISCELLANEOUS

(c) Die Casting (d) Continuous Casting

-- high volume production -- simple shapes
-- for alloys having low melting (e.g., rectangular slabs,
temperatures & low viscosity cylinders)

molten

solidified
 Metal Fabrication Methods (iii)

FORMING CASTING MISCELLANEOUS

• Powder Metallurgy • Welding

(metals w/low ductilities) (when fabrication of one large
part is impractical)
pressure
filler metal (melted)
base metal (melted)
fused base metal
heat
heat-affected zone
area unaffected unaffected
contact piece 1 piece 2
densify

point contact densification

at low T by diffusion at
higher T
 Thermal Processing of Metals
Annealing: Heat to Tanneal, then cool slowly.

• Stress Relief: Reduce • Spheroidize (steels):

stresses resulting from: Make very soft steels for
- plastic deformation good machining. Heat just
- nonuniform cooling below Teutectoid & hold for
- phase transform. 15-25 h.

• Full Anneal (steels):

Types of Make soft steels for
good forming. Heat
Annealing to get , then furnace-cool
to obtain coarse pearlite.
• Process Anneal:
Negate effects of
• Normalize (steels): Deform
cold working by
steel with large grains. Then heat
(recovery/
treat to allow recrystallization
recrystallization)
and formation of smaller grains.
 A

a) Full Annealing

b) Quenching A
B

c) Tempering

b)
a)
c)
Influences of Quenching Medium & Specimen Geometry
• Effect of quenching medium:

Medium Severity of Quench Hardness

air low low
oil moderate moderate
water high high

• Effect of specimen geometry:

When surface area-to-volume ratio increases:
-- cooling rate throughout interior increases
-- hardness throughout interior increases

Position Cooling rate Hardness

center low low
surface high high
Precipitation Hardening
• Hardening or strengthening of metal alloys due to formation of
precipitated particles.
• Very small amount of alloying component that form hardened
precipitate structure during phase transformation.

• Al-Cu – Cu precipitate in Al phase (alloy strengtening).

• Cu-Be – Be hardening in Cu phase (alloy hardening).
Other example: Cu-Sn, Mg-Al
 Summary
• Phase transformation – process that involves alteration of parental phase into at
least 1 new phase having an altered microstructure, chemical or physical
properties.
- occurs in 2 stages: nucleation (Homogeneous & Heterogeneous) & growth.

• TTT and CCT curves on phase transformation of Fe-C (steel) – Austenite (γ

ferrite) into (α ferrite + Fe3C) – eutectic, eutectoid and peritectic transformation.

• Microstructure development – effect of cooling on microstructure and properties.

• Slow cooling – isotropic, coarse & equilibrium structure, soft & ductile properties.
• Rapid cooling – anisotropic, fine but cored structure, strong & brittle properties.

• Steel microstructure development (Fe-C phase diagram):

• Austenite – Pearlite (540 – 727°C isothermal or slow cooling),
• Austenite – Bainite (215 – 540 °C isothermal or moderate cooling),
• Austenite – martensite (0 – 215 °C rapid cooling / quenched)
• Martensite – tempered martensite (diffusionless transformation) through
tempering process.
 Summary
• Metal – Ferrous & Non-ferrous (i.e. with or without Fe).
• Ferrous alloys – Steels (<1.4 wt% C) & Cast irons (3 - 4.5 wt% C)
• Steels – low, medium, or high carbon (low alloy steel) & stainless steel (high
alloy)
• Cast iron – gray, ductile, white, malleable & compacted graphite iron.
- Limitations: high density, low electrical conductivity & low corrosion resistance.

• Non-ferrous alloys (No Fe):

- Al, Mg, Cu & Ti alloys; refractory alloys; and noble metals.

• Metal fabrication techniques:

-- forming – forging, extrusion, stamping, rolling & drawing.
-- casting – sand, investment, die & continuous.
-- joining – powder press & welding.

• Heat treatment – annealing (stress relieve, spheroidize, full anneal, normalizing &
process anneal), quenching, tempering & precipitate hardening.