Engineering Materials II

Chapter One
Phase Transformations
Introduction to Phase
Transformations

Pressure–temperature phase diagrams of H2O and CO2.

 Learning Objectives
After completing this chapter, you should be able to:

 Make a schematic fraction transformation versus-logarithm of time plot for a typical

solid–solid transformation; cite the equation that describes this behavior.

 Briefly describe the microstructure for each of the following microconstituents that
are found in steel alloys: fine pearlite, coarse pearlite, spheroidite, bainite,
martensite, and tempered martensite.

 Cite the general mechanical characteristics for each of the following

microconstituents: fine pearlite, coarse pearlite, spheroidite, bainite, martensite,
and tempered martensite. Now, in terms of microstructure (or crystal structure),
briefly explain these behaviors.

 Given the isothermal transformation (or continuous cooling transformation) diagram

for some iron–carbon alloy, design a heat treatment that will produce a specified
microstructure.

Engineering Materials II 2
 Introduction
 Phase transformations occur when phase boundaries (the red curves) on phase
diagrams are crossed as temperature and/or pressure is changed.
H2O pressure–temperature phase diagram CO2 pressure–temperature phase diagram

Ice melts (transforms to liquid water) upon Upon passing across the solid-gas phase
heating, which corresponds to crossing the boundary of the CO2 phase diagram, dry ice
solid-liquid phase boundary, as (solid CO2) sublimes (transforms into
represented by the arrow on the H2O gaseous CO2). The arrow delineates this
phase diagram. phase transformation.

Engineering Materials II 3
 Introduction
 The development of microstructure in both single- and two-phase alloys
ordinarily involves some type of phase transformation (an alteration in the
number and/or character of the phases)

 Phase transformation need time, and cooling rate greatly modify the
phase transformation.
 Most phase transformations do not occur instantaneously, consideration
is given to the dependence of reaction progress on time, or the
transformation rate.
 Modified phase diagrams are introduced from iron-carbon alloys for two-
phase microstructure that permit determination of the microstructure
that results from a specific heat treatment.
Engineering Materials II 4
 Basic Concepts
 A variety of phase transformations are important in the
processing of materials, and usually they involve some
alteration of the microstructure.

Three classifications of phase transformations:

a) Simple diffusion-dependent transformation, there is no
change in either the number or composition of the phases
present. This type includes;
 solidification
 allotropic transformation (αγ)
 recrystallization and grain growth

Engineering Materials II 5
 Cont …
b)Diffusion-dependent
transformation, this type includes;


change in number of phases

changes in compositions

The final microstructure
consists of two phases.
Eutectoid reaction
(γ  pearlite)

Engineering Materials II 6
 Cont …
c) Diffusionless transformation;

 a metastable phase is produced

 a martensitic transformation

Engineering Materials II 7
 The Kinetics of Phase Transformations
 With phase transformations, normally at least one new phase is formed
that has different physical/chemical characteristics and/or a different
structure than the parent phase.

 Most phase transformations do not occur instantaneously. Rather, they

begin by the formation of numerous small particles of the new phase(s),
which increase in size until the transformation has reached completion.

 The progress of a phase transformation may be broken down into two

distinct stages: Nucleation and Growth.

 Nucleation involves the appearance of very small particles, or nuclei of the

new phase (often consisting of only a few hundred atoms), which are
capable of growing.

 During the Growth stage these nuclei increase in size, which results in the
disappearance of some (or all) of the parent phase.

Engineering Materials II 8
 The Kinetics of Phase Transformations

During the cooling of a liquid, solidification (nucleation) will
begin only after the temperature has been lowered below the
equilibrium solidification (or melting) temperature Tm. This
phenomenon is termed supercooling (or undercooling).


The driving force to nucleate increases as T increases.


Small supercooling  slow nucleation rate - few nuclei - large
crystals


Large supercooling  rapid nucleation rate - many nuclei - small
crystals Engineering Materials II 9
 Nucleation
 In the context of solidification, the term nucleation refers to the formation of
the first nanocrystallites from molten material.
 For example, as water begins to freeze, nanocrystals, known as nuclei,
form first.
 Nucleation is the process whereby nuclei (seeds) act as templates for crystal
growth.
 In a broader sense, the term nucleation refers to the initial stage of formation
of one phase from another phase.
 When a vapor condenses into liquid, the nano-scale sized drops of liquid
that appear when the condensation begins are referred to as nuclei.
 Depending on the site at which nucleating events occur nucleation can be
 Homogeneous type, nuclei of the new phase form uniformly throughout
the parent phase: requires considerable supercooling.
 Heterogeneous type: nuclei form preferentially at structural
inhomogeneities, such as container surfaces, insoluble impurities, grain
boundaries, dislocations, and requires slight supercooling.
Engineering Materials II 10
 Homogeneous Nucleation
 First consider the solidification of a pure material,
Assumptions
 the nuclei of the solid phase form in the interior of the liquid as
atoms cluster together so as to form a packing arrangement
similar to that found in the solid phase.
 Each nucleus is spherical and has a radius r.

Engineering Materials II 11
 Homogeneous Nucleation
 We expect a material to solidify when the liquid cools to just below its
freezing (or melting) temperature, because the energy associated with
the crystalline structure of the solid is then less than the energy of the
liquid.
 This energy difference between the liquid and the solid is the free
energy per unit volume ∆Gv
 Its value will be negative if the temperature is below the
equilibrium solidification temperature.
 It is the driving force for solidification.

 When the solid forms, however, a solid-liquid interface is created.

 A surface free energy γsl is associated with this interface.
 is positive;
 Thus, the total change in energy is the sum of these values,
4
G  r 3 Gv  4r 2 
3
Engineering Materials II 12
 Free energy function of nucleus radius
 These volume, surface, and total free energy contributions are plotted
schematically as a function of nucleus radius in Figures 10.2a and 10.2b.
 Here (Figure 10.2a) it will be noted that for the volume the free energy
(which is negative) decreases with the third power of r.
 Furthermore, for the surface free energy values are positive and increase
with the square of the radius.

Engineering Materials II 13
 Free energy function of nucleus radius
 The curve associated with the sum of both terms (Figure 10.2b) first
increases, passes through a maximum, and finally decreases.

 In a physical sense, this means that as a solid particle begins to form as

atoms in the liquid cluster together, its free energy first increases. If this
cluster reaches a size corresponding to the critical radius r*, then growth
will continue with the accompaniment of a decrease in free energy. the
particle is termed a nucleus.

 On the other hand, a cluster of radius less than the critical radius will shrink
and redissolve. This subcritical particle is an embryo.

 A critical free energy, ∆G*, occurs at the critical radius and, consequently, at
the maximum of the curve in Figure 10.2b.

 This ∆G* corresponds to an activation free energy, which is the free energy
required for the formation of a stable nucleus. Equivalently, it may be
considered an energy barrier to the nucleation process.
Engineering Materials II 14
Homogeneous Nucleation & Energy Effects

Surface Free Energy- destabilizes

the nuclei (it takes energy to make
an interface)

DGs
g = surface tension

DGT = Total Free Energy

= DGS + DGV

Volume (Bulk) Free Energy –

stabilizes the nuclei (releases energy)
DGV
𝑣𝑜𝑙𝑢𝑚𝑒 𝑓𝑟𝑒𝑒𝑒𝑛𝑒𝑟𝑔𝑦
DGv=
𝑢𝑛𝑖𝑡 𝑣𝑜𝑙𝑢𝑚𝑒
r* = critical nucleus: nuclei < r* shrink; nuclei>r* grow (to reduce energy)
Engineering Materials II 15
How to determine the critical radius and energy?
 Because r* and G* appear at the maximum on the free energy–
versus–radius curve of Figure 10.2b, derivation of expressions for
these two parameters is a simple matter.

Volume Free Energy Change

 The volume free energy change is the driving force for the
solidification transformation, and its magnitude is a function of
temperature.

where Hf is the latent heat of fusion (i.e., the heat given up during solidification),
and Tm and the temperature T are in Kelvin.

Now substitute this value in r* and G* and find values of total free energy

Engineering Materials II 16
 Volume Free Energy Change and Temperature
 At the thermodynamic melting or freezing temperatures, the
probability of forming stable, sustainable nuclei is extremely small.
 Therefore, solidification does not begin at the thermodynamic melting
or freezing temperature.

 If the temperature continues to decrease below the equilibrium

freezing temperature, the liquid phase that should have transformed
into a solid becomes thermodynamically increasingly unstable.

 Because the temperature of the liquid is below the equilibrium

freezing temperature, the liquid is considered undercooled.

 The undercooling (∆T) is the difference between the equilibrium

freezing temperature and the actual temperature of the liquid.

 As the extent of undercooling increases, the thermodynamic driving

force for the formation of a solid phase from the liquid overtakes the
resistance to create a solid-liquid interface.
 The number of stable nuclei n* (having radii greater than r*) is a function of
temperature.
Engineering Materials II 17
 Effect of Temperature on Total Free Energy
2 2Tm 1
r*  r* (  )( )
Gv H f Tm  T

H f (Tm  T )
Gv 
Tm

163 163Tm2 1
G*  G* ( 2
)
3( Gv ) 2 3H f (Tm  T ) 2

 Thus, from these two equations, both the critical radius r* and the
activation free energy G* decrease as temperature T decreases.
Engineering Materials II 18
 Effect of temperature on total free energy
The bulk free energy reduction is a function of
Gv  f (T ) undercooling
Tm Turnbull approximation
Decreasing G*

 16 3 Tm2
G  
T 3 T 2 H 2
g
a sin
cre
In

Decreasing r*
G →

r
Engineering Materials II → 19
 Examples
 Calculate the size of the critical radius and the number of atoms in the critical
nucleus when solid copper forms by homogeneous nucleation. Comment on
the size of the nucleus and assumptions we made while deriving the equation
for the radius of the nucleus.

Engineering Materials II 20
 Number of stable nuclei n*
 G 
n* K1ecp (
KT
where the constant K1 is related to the total
number of nuclei of the solid phase.
 For the exponential term of this expression,
changes in temperature have a greater effect
on the magnitude of the G* term in the
numerator than the T term in the
denominator. Consequently, as the
temperature is lowered below Tm, the
exponential term in this equation also
decreases such that the magnitude of n*
increases. This temperature dependence (n*
versus T) is represented in the schematic plot
of Figure 10.4a. Engineering Materials II 21
 The Kinetics of Phase Transformation
 Another temperature-dependent
parameter is also important for
nucleation: rate of diffusion, the
frequency atoms from the liquid
attach to the solid nucleus.
𝑄𝑑
𝑣 𝑑 =𝐾 2 exp ⁡( − )
𝑘𝑇
 this diffusion effect is related to the
frequency at which atoms from the
liquid attach themselves to the solid
nucleus, vd.
 A diminishment of temperature
results in a reduction in vd
22
Engineering Materials II 22
 The Kinetics of Phase Transformation
 The clustering of atoms by short-range diffusion during the
formation of nuclei is another important temperature-dependent
step involved in and also influences nucleation.
 The influence of temperature on the rate of diffusion (i.e.,
magnitude of the diffusion coefficient, D) is given in chapter 5.
Furthermore, this diffusion effect is related to the frequency at
which atoms from the liquid attach themselves to the solid
nucleus, vd.
 The dependence of vd on temperature is the same as for the
𝑄𝑑
𝑣 𝑑 =𝐾 2 exp ⁡( − )
diffusion coefficient—namely, 𝑘𝑇
Engineering Materials II 23
 Nucleation rate
 The nucleation rate (which has units of nuclei per unit volume per
second). This rate is simply proportional to the product of n* and
vd that is,
 G * Q 
N K 3 n * vd K1 K 2 K 3  exp( ) exp(  d )
 kT kT 

where Qd is a temperature-independent parameter—the activation energy for

diffusion— and K2 is a temperature-independent constant, and K3 is the number of atoms
on a nucleus surface.
Engineering Materials II 24
 Heterogeneous Nucleation
 Heterogeneous nucleation occurs much more often than
homogeneous nucleation.

 Heterogeneous nucleation forms at preferential sites such as

phase boundaries, surfaces (of container, bottles, etc.) or
impurities like dust. At such preferential sites, the effective
surface energy is lower, thus diminishes the free energy barrier
and facilitating nucleation.

 Surfaces promote nucleation because of wetting – contact angles

greater than zero between phases facilitate particles to nucleate.
 The free energy needed for heterogeneous nucleation is equal to
the product of homogeneous nucleation and a function of the
contact angle (θ)

Engineering Materials II 25
 Heterogeneous Nucleation
 The barrier energy needed for heterogeneous nucleation
is reduced (see the plot below).
 The wetting angle determines the ease of nucleation by
reducing the energy needed.

Engineering Materials II 26
 Growth
 The growth step in a phase transformation begins once an embryo
has exceeded the critical size, r*, and becomes a stable nucleus.

 Note that nucleation will continue to occur simultaneously with

growth of the new phase particles; of course, nucleation cannot
occur in regions that have already transformed to the new phase.

 Furthermore, the growth process will cease in any region where

particles of the new phase meet, because here the transformation
will have reached completion.

 Growth of the nucleus normally occurs by long-range diffusion and

redistribution of atoms. Diffusing atoms must be detached from their
original locations (perhaps at lattice points in a solid solution), move
through the surrounding material to the nucleus, and be
incorporated into the crystal structure of the new phase.
Engineering Materials II 27
 Growth Rate
 The growth rate is determined by the rate of diffusion, and its
temperature dependence is the same as for the diffusion coefficient.
where Q (the activation energy)
and C (a preexponential) are
independent of temperature.

Engineering Materials II 28
 Kinetic Considerations of Solid-state Transformations
 The temperature dependences of nucleation, growth, and
transformation rates are the basic parameters in this case.

 The time dependence of rate is also an important consideration,

often in the heat treatment of materials.

 With many kinetic investigations, the fraction of reaction that has

occurred is measured as a function of time while the
temperature is maintained constant.

 Transformation progress is usually ascertained by either

microscopic examination or measurement of some physical
property (such as electrical conductivity) whose magnitude is
distinctive of the new phase.
Engineering Materials II 29
 Kinetics
 The overall rate, or kinetics, of the transformation process
depends on both nucleation and growth.

 If more nuclei are present at a particular temperature, growth

occurs from a larger number of sites and the phase
transformation is completed in a shorter period of time.

 At higher temperatures, the diffusion coefficient is higher,

growth rates are more rapid, and again we expect the
transformation to be completed in a shorter time, assuming an
equal number of nuclei.

Engineering Materials II 30
Engineering Materials II 31
 Rate of transformation

 Incubation is followed by rapid growth as atoms diffuse to the

growing nucleus.
 Near the end of the transformation, the rate again slows as the
source of atoms available to diffuse to the growing precipitate is
depleted.
 The rate of a transformation is taken as the reciprocal of time
required for the transformation to proceed halfway to completion,
t0.5. = t0.5

32
Engineering Materials II
 Effect of Temperature
 In many phase transformations, the material undercools below the
temperature at which the phase transformation occurs under
equilibrium conditions.

 Because both nucleation and growth are temperature-dependent, the

rate of phase transformation depends on the undercooling (∆T).

 The rate of nucleation is low for small undercoolings (since the

thermodynamic driving force is low) and increases for larger
undercoolings as the thermodynamic driving force increases at least up
to a certain point (since diffusion becomes slower as temperature
decreases).

 At the same time, the growth rate of the new phase decreases
continuously (because of slower diffusion), as the undercooling
increases. Engineering Materials II 33
Thank You

Engineering Materials II 34