Learning Objectives

After careful study of this chapter you should be able to do the following:
1. Make a schematic fraction transformationversus-
logarithm of time plot for a typical
solid–solid transformation; cite the equation
that describes this behavior.
2. 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.
3. 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.
4. Given the isothermal transformation (or continuous
cooling transformation) diagram for some
iron–carbon alloy, design a heat treatment that
will produce a specified microstructure.

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
-The transformation rate is the dependance of reaction progress on time
-Many phase transformations are important in the processing of materials
-Phase transformations usually involve some alteration of microstructure
-Simple phase transformations covered here are as follows:
1.Simple diffusion dependent transformations with no change in number or composition of phases
present(e.g. Pure species, allotropic, recrystallization, and grain growth)
2.Eutectoid type transformations that involve altering phase concentrations or number of phases
3.A diffusionless process that involves a metastable phase is produced (e.g. martensitic xfrm)

Kinetics of Phase Transformations

Usually at least one new phase created
Usually not instantaneous
Most often, new phase starts as small particles in the old phase, which then increases in size until
completion.
The progress of phase transformations may be broken into two distinct stages:
Nucleation (appearance of very small particles, or nuclei, of the new phase)
Growth (increase in size of nuclei, resulting in some or all of parent phase disappearing.

Nucleation
There are two types of nucleation: Heterogeneous and Homogeneous
Homogeneous nucleation occurs uniformly throughout parent phase, with even distribution of
nuclei
Heterogeneous nucleation occurs when nuclei occur preferentially at structural features (cracks,
scratches, impurities, insoluble stuff, dislocations, etc)

A process is spontaneous only if DeltaG is negative

The DeltaG in phase transformations is dependant on two factors
1. The free energy difference of the liquid and solid phases or volume free energy
DeltaGv
Is negative if temperature is below eq solidification temperature, and is represented by
DeltaGv*4/3(pi)r^3
2. The formation of the solid-liquid phase boundary also causes a difference in gibbs free
 energy
This term is represented by the boundary surface free energy, gamma, and the surface
area of the nucleus, or:
(gamma)*4(pi)r^2
Therefore, the total change of free energy is the sum of the two:
DeltaG=4/3*pi*r^3*DeltaGv+(gamma)*4*pi*r^2
A graph of free energy change of each of the terms alone and the final function shows the
DeltaG values to reach a maximum (DeltaG*) at some radius (r*), then decrease precipitously
This DeltaG* is the activation energy for the formation of a stable nucleus. It must be overcome for
a nucleus to truly form.
Since this DeltaG* is at a maximum on the curve, its derivative should equal zero
Thus:
d(DeltaG)/dr=4*pi*DeltaGv*r^2+8*pi*gamma=0
Solving this differential gives:
r*=(-2gamma)/DeltaGv
Substituting this r* into DeltaG(r) gives:
DeltaG*=16*pi/3*(gamma^3)/(DeltaGv)^2
If the DeltaHf (heat of fusion) is known, it can be shown that DeltaGv depends on temperature in:
DeltaGv=[DeltaHf*(Tmelt-T)]/Tmelt
Substitution shows:

If a DeltaG* value is known, n* is a function of temperature representing the number of stable

nuclei as follows:
n*=K1*e^(-DeltaG*/(k*T)
Where K1 is a function of the total number of nuclei in solid phase
Where k is boltzmann's constant: 1.38*10^-23
Another quantity, vd, is the frequency when liquid atoms attach themselves to the solid nucleus
It can be represented as a function of temperature and coefficient of diffusion:
vd=K2exp(-Qd/(k*T))
Where K2 is a T-independent constant
Where k is again boltzmann's constant
The rate of nucleation or nucleation rate Ndot can be expressed as follows:

Where K3 is the number of atoms on a nucleus surface.

Heterogeneous nucleation
At an interface(container wall, other solid phase, any preexisting surface or interface), the solid
nucleus spreads like a drop of water, with liquid surrounding it on the other side.
The system then has three infterfacial energies that exist at two phase boundaries:
(all vectors::) gamma(Solid-Liquid), gamma(Solid-Interface) and gamma(Interface-Liquid).
Gamma(SL) exists tangent to the solid surface at the point of contact with the preexisting surface
Gamma(SI) exists projecting from the outermost solid/surface contact inward towards the center
of the nucleus
Gamma(IL) exists starting at the same point as Gamma(SI) then extending (SI) in the opposite
direction
There also exists a “wetting angle,” theta, that is the angle between gamma(SL) and gamma(SI)
It can be shown the following is true:
gamma(IL)=gamma(SI)+gamma(SL)*cos(theta)
It can be derived:

Where S(theta) is a function of theta describing the shape of the nucleus (0<S<Unity)
IT CAN BE SHOWN:
DeltaG*het= DeltaG*hom*S(theta)

Nucleation Rate, when plotted versus change in T from Tm(DeltaT, degree of supercooling), shows
heterogeneous nucleation rate curve hitting a max some many degrees sooner than the
homogeneous

Growth
The growth rate, Gdot, can be shown to be a function of temperature:
Gdot=Cexp(-Q/(kT))
Where k is, naturally, boltzmann's constant
Where Q is the activation energy
Where C is a preexponential remainder of solving the diff eq
(both constant)
High T, Low rate → Few large, coarse phase particles (Slow nucleation, Fast Growth)
Low T, Fast rate → Many small, possibly “cored” nuclei (Fast nucleation, Slow Growth)

Kinetic considerations of solid-state transformations

The time dependance of rate is referred to as kinetics of a transformation.
This is often a key consideration in material heat treatments
In kinetic experiments, the % reacted is measured by either microscopic methods or by measuring
a physical property, like conductivity over a period of time
This can then be plotted, and also yields a function for the fraction of transformation, y:
y=1-exp(-kt^n)
This equation is often referred to as the Avrami Equation
By convention, the rate of a transformation is taken when half the time required for the
transformation has elapsed, t(0.5):
rate=1/(t(0.5))
Heat treatment is the easiest way to to induce phase transformations
During phase transformation, alloy → equilibrium defined by phase diagram
Rate of approach to equilibrium for solid systems is slow, true equilibrium rarely reached
Phase transformations occur at lower temperatures than equilibrium transformation when cooling
Phase transformations occur at higher temperatures than equilibrium transformation when heating
This phenomenon is referred to as supercooling and superheating
The degree of each depends upon the rate of temperature change, greater heat/cool → greater
superheating/supercooling
Kinetic information about a system is often more valuable than a knowledge of the final
equilibrium state

Microstructural and Property Changes in Iron-Carbon Alloys

Isothermal Transformation Diagrams
Pearlite
-Recall iron-iron carbide eutectoid reaction:
gamma(0.76wt%C) → cooling → alpha(0.022wt% C)+ Fe3C(6.70wt% C)
-Austentite has an intermediate carbon content, and cools to ferrite, with low carbon content, and
cementite, with a much higher carbon content
-Greater degrees of supercooling cause significantly shorter transformation times
-Plots of the time (s) it takes to start, 50%, and complete the transformation vs temperature yield
a very relevant diagram, as in figure 11.13
-These are called isothermal transformation diagrams.
-In Fe-C system, the widths of ferrite and cementite layers in pearlite vary according to
Temperatures
-At temperatures near the eutectoid, ferrite and cementite both form fairly thick layers
-As temperature decreases, layers progressively become thinner
-Pearlite with thick layers is called coarse pearlite, and forms on the right of the isothermal xfrm
diagram
-Pearlite with thin layers is called fine pearlite, and forms on the left of isothermal xfrm diagram
-Proeutectoid phases require more complex isothermal transformation diagrams
Bainite
-Bainite is another possible microconstituent of austenitic transformation
-Microstructure has ferrite and cementite phases (diffusion involved) and forms as needles or
plates, depending on formation temperature
-The microstrucural details of bainite are so fine electron microscope needed
-Bainite is represented in isothermal transformation diagrams that are an extension of the same
one as pearlite with different and always lower temperatures
-Bainite and Pearlite are competative in formation, and if one forms as part of an alloy, the other
cannot form without re-heating to austentite
Spheroidite
-Heating a bainitic or pearlitic alloy to just under eutectoid temperature for a long enough time will
cause spheroidite to form.
-Fe3C congregates in speroids amidst sea of ferrite (hence name)
-Cementite and Ferrite phase compositions unchanged by formation
-Added heat with const. T gives enough energy to aid diffusion, so Fe3C naturally tries to reduce
boundary surface area with ferrite
-Pearlitic/Bainitic steel can partially transform to spheroidite, and over a long enough period of
time, would likely occur in all such steels
Martensite
-Formed by austentized alloy being cooled rapidly (i.e. quenched) to low temperatures within
degrees of ambient
-Nonequilibrium single-phase structure.
-The short time period makes diffusion processes negligible; any diffusion causes other species to
form
-This is a polymorphic transformation of FCC austentite going to body-centered tetragonal
martensite
-Carbon found as interstitial impurities on edges of tetragonal
-Many steels can retain martensitic structures at room temperature indefinately
-Can also be found in other alloy systems and is characterized largely by diffusionless transforms
-Appears as horizontal line on isothermal transformation diagrams, and called an athermal
transformation
-Steels where carbon is the main alloying component are called plain carbon steels
-Steels with appreciable quantities of alloying compenents other than carbon called alloy steels

Continuous Cooling Transformation Diagrams

Constant cooling processes shift the start and completion curves of regular transformation
diagram right, and often down.
Such diagrams called Continuous Cooling Transformation (CCT) Diagrams
Mechanical Behavior of Iron-Carbon Alloys
-Cementite is harder but more brittle than ferrite.
Pearlite
-It would follow that pearlite, being a mixture of the two, will yield a harder and stronger material,
-but decrease the ductility (compared to ferrite)
-Fine pearlite is stronger and less ductile than Coarse pearlite
-Cementite layers bind and restrict ferrite layers, as though reinforcing the ferrite
-In fine pearlite, more phase layers mean more phase boundaries where this can occur, increasing
the strength accordingly.
-Also, fine pearlite has many more grain boundaries than coarse, boundaries dislocations must
pass through for plastic deformation