Solidification, Phase

Diagrams and Phase

Transformation
 Solidification
Solidification is the process of phase transformation of metals and alloys from the
liquid to the solid state. During this process, the atoms arrange themselves in an orderly
three dimensional pattern.
The mechanism of solidification proceeds by the formation of stable nuclei in the
liquid metal followed by the growth of nuclei into the crystal with the formation of
grain structure.
Nucleation
Nucleation is the beginning of phase transformation and is indicated by the appearance of
a small cluster of atoms or molecules to form the basic crystal structure or small solids
called nuclei.
The formation of small crystals in molten metal takes place in two mechanisms-
homogeneous and heterogeneous nucleation.
Homogeneous or self nucleation: The formation of nuclei within its own melt without the
aid of impurity or foreign particles is called homogeneous or self nucleation.
This nucleation occurs in perfectly homogeneous materials such as pure(aluminium,
copper, etc) molten metals.
During the nucleation, the molten metal must be cooled below its freezing temperature.
 Nucleation occurring at any part of liquid or molten metal is identical and group of
atoms form small zones.
 The atoms in a molten liquid bond together to form a small crystal called embryo. This
embryo grows into a nucleus with the addition of atoms.
In pure metals, this takes place by super cooling and the nucleation of super cooled
grain is governed by the following two factors:
1. The free energy available from the solidification process, which depends on the
volume of the particle formed
2. The energy required forming a solid-liquid interface, which is dependent on the
surface area of the particle
Heterogeneous nucleation: the formation of nuclei within its own melt with the help of
foreign substances or substrates is known as heterogeneous nucleation.
The phase transformation takes place with the help of impurities, which lower the free
energy.
 since large amount of under-cooling does not takes place in industrial casting process,
nucleation should be heterogeneous and not homogeneous.
In molten metal, usually impure particles will reduce the liquid-solid interface energy
and helps in nucleation and thereby reduce the amount of super-cooling.
If the metal is to solidify on a foreign substrate, it is essential that the surface of the
substract should be wet by a liquid metal. Once this condition is satisfied, next the
liquids solidify easily on the substract.
When angle of contact θ is small, interface between solid and substrate has a low surface
energy.
Hence, the total free energy for formation of stable nucleus is also decreased and critical
radius of the nucleus will be smaller.
 Growth Mechanism
 Once the solid nuclei of a phase form (in a liquid or another solid phase), growth begins
to occur as more atoms become attached to the solid surface.
 The nature of the growth of the solid nuclei depends on how heat is removed from the
molten material.
In the solidification process, two types of heat must be removed: the specific heat of the
liquid and the latent heat of fusion.
The specific heat must be removed first, either by radiation into the surrounding
atmosphere or by conduction into the surrounding mold, until the liquid cools to its
freezing temperature.
 Therefore, when solid crystals form from a liquid, heat is generated! This type of heat is
called the latent heat of fusion. The latent heat of fusion must be removed from the solid-
liquid interface before solidification is completed. The manner in which we remove the
latent heat of fusion determines the material’s growth mechanism and final structure of a
casting.
Planer growth:
When a well-inoculated liquid (i.e., a liquid containing nucleating agents) cools under
equilibrium conditions, there is no need for undercooling since heterogeneous nucleation
can occur. Therefore, the temperature of the liquid ahead of the solidification front (i.e.,
solid-liquid interface) is greater than the freezing temperature. The temperature of the
solid is at or below the freezing temperature. During solidification, the latent heat of
fusion is removed by conduction from the solid liquid interface.
 Any small protuberance that begins to grow on the interface is surrounded by liquid
above the freezing temperature (Figure). The growth of the protuberance then stops until
the remainder of the interface catches up. This growth mechanism, known as planar
growth, occurs by the movement of a smooth solid-liquid interface into the liquid.
Dendritic Growth :
When the liquid is not inoculated and the nucleation is poor, the liquid has to be
undercooled before the solid forms (Figure). Under these conditions, a small solid
protuberance called a dendrite, which forms at the interface, is encouraged to
grow since the liquid ahead of the solidification front is undercooled
 As the solid dendrite grows, the latent heat of fusion is conducted into the
undercooled liquid, raising the temperature of the liquid toward the freezing
temperature.
 Cooling curves
The phase diagrams are usually constructed from the data of cooling curve obtained by
plotting falling temperature versus time for small selected alloys, which are allowed to
cool under equilibrium condition.
If a plot is drawn between temperature and time at a constant composition, the resulting
cooling curve shows a change of slope when a phase change occurs.
Cooling curve for pure metals:
The pure metals melt and solidify at the same temperature which may be termed as
melting point or freezing point. These metals are cooled under equilibrium conditions
from the molten state till they solidify.
In second graph, the horizontal line corresponds to the solidifying or melting
temperature of a single component system at a constant pressure.
In real systems, a certain amount of under cooling occurs before the solidification starts.
That is the melt is maintained in a metastable state at a temperature below the freezing
point.
Cooling curve for binary alloy:
In binary system, during the freezing period, temperature does not remain
constant, rather it drops along the line till the whole mass is solid and cool to
room temperature as shown in first graph.
At the room temperature, the alloy is homogeneous in the solid state similar to in
the liquid state.
In some binary alloy system(second graph), the liquid metal cools along the curve
AB until the temperature reaches point B. at point B, one component in excess
will crystallize and the temperature will drop along BC as indicated in graph. At C
, the residue liquid reaches eutectic composition and the two components
crystallize simultaneously from the eutectic mixture. The temperature remains
same until the whole mass is solid between points C and D. from D to E metal
cools to room temperature.
 Phase Diagrams
Phase diagrams are an important tool in the armory of an materials scientist
In the simplest sense a phase diagram demarcates regions of existence of various
phases.
Phase diagrams are also referred to as “Equilibrium Phase Diagrams”
Solubility Limit:
For many alloy systems and at some specific temperature, there is a maximum
concentration of solute atoms that may dissolve in the solvent to form a solid
solution; this is called a solubility limit. The addition of solute in excess of this
solubility limit results in the formation of another solid solution or compound that
has a distinctly different composition.
Example: sugar and water
phase
Physically distinct, chemically homogenous and mechanically separable region of a
system (e.g. gas, crystal, amorphous...).
 Gases
Gaseous state always a single phase
→ mixed at atomic or molecular level.
 Liquid
1. Liquid solution is a single phase
→ e.g. NaCl in H2O.
2. Liquid mixture consists of two or more phases
→ e.g. Oil in water (no mixing at the atomic/molecular level)
 Solids
 In general due to several compositions and crystals structures many phases are possible.
 For the same composition different crystal structures represent different phases.
E.g. Fe (BCC) and Fe (FCC) are different phases.
 For the same crystal structure different compositions represent different phases.
E.g. in Au-Cu alloy 70%Au-30%Cu & 30%Au-70%Cu are different phases.
Gibbs Phase Rule
The phase rule connects the Degrees of Freedom, the number of Components in a system
and the number of Phases present in a system via a simple equation.
To understand the phase rule one must understand the variables in the system along with
the degrees of freedom.
We start with a general definition of the phrase: “degrees of freedom”.
Degrees of Freedom: A general definition
In response to a stimulus the ways in which the system can respond, corresponds to the
degrees of freedom of the system.  F – Degrees of Freedom
 C – Number of Components
For a system in equilibrium : F = C  P + 2  P – Number of Phases
 The ‘2’ comes from– Pressure & T
One-Component phase diagrams
The simplest and easiest type of phase diagram to understand is that for a one-
component system, in which composition is held constant this means that pressure
and temperature are the variables. This one-component phase diagram (or unary
phase diagram) [sometimes also called a pressure–temperature (or P–T) diagram]
is represented as a two-dimensional plot of pressure versus temperature.
This type of phase diagram and demonstrate its interpretation using as an example
the one for H2O
 Binary Isomorphous Systems
A binary phase is a two component system. Binary phase diagrams are most commonly
used in alloy designing.
The simplest binary system is the Cu-Ni which exhibits complete solubility in liquid and
solid state.
The line above which the alloy is liquid is called the liquidus line. At temperature
just below this line crystals of α solid solution start forming.
The line below which solidification completes is called solidus line. Hence, only
α solid solution exists at any temperature below the solidus line.
The intermediate region between liquidus and solidus lines is the two-phase
region where liquid and solid coexist.
It can be noted that the two metals are soluble in each other in the entire range of
compositions in both liquid and solid state. This kind of system is known as
‘Isomorphous’ system.
Interpretation of Phase Diagrams
For a binary system of known composition and temperature that is at equilibrium, at least
three kinds of information are available:(1) the phases that are present,(2) the compositions
of these phases,and (3) the percentages or fractions of the phases. The procedures for
making these determinations will be demonstrated using the copper–nickel system using
graphs in last slide.
Phase present: one just locates the temperature –composition point on the diagram and
notes the phases with which the corresponding phase field is labeld.
Determination of phase composition: The first step in the determination of phase
compositions is to locate the temperature–composition point on the phase diagram.
Different methods are used for single- and two-phase regions. If only one phase is
present, the procedure is trivial: the composition of this phase is simply the same as the
overall composition of the alloy.
For an alloy having composition and temperature located in a two-phase region, the
situation is more complicated. In all two-phase regions, one may imagine a series of
horizontal lines, one at every temperature; each of these is known as a tie line, or
sometimes as an isotherm
These tie lines extend across the two-phase region and terminate at the phase
boundary lines on either side.
 To compute the equilibrium concentrations of the two phases, the following
procedure is used:
1. A tie line is constructed across the two-phase region at the temperature of the
alloy.
2. The intersections of the tie line and the phase boundaries on either side are noted.
3. Perpendiculars are dropped from these intersections to the horizontal composition
axis, from which the composition of each of the respective phases is read.
Determination of Phase Amounts: The relative amounts (as fraction or as
percentage) of the phases present at equilibrium may also be computed with the aid of
phase diagrams. Again,the single- and two-phase situations must be treated separately.
The solution is obvious in the single phase region: Since only one phase is present,
the alloy is composed entirely of that phase; that is, the phase fraction is 1.0 or,
alternatively, the percentage is 100%.
If the composition and temperature position is located within a two-phase region,
things are more complex. The tie line must be utilized in conjunction with a
procedure that is often called the lever rule which is applied as follows:
1. The tie line is constructed across the two-phase region at the temperature of the
alloy.
2. The overall alloy composition is located on the tie line.
3. The fraction of one phase is computed by taking the length of tie line from the
overall alloy composition to the phase boundary for the other phase, and dividing
by the total tie line length.
4. The fraction of the other phase is determined in the same manner.
5.If phase percentages are desired, each phase fraction is multiplied by 100. When
the composition axis is scaled in weight percent, the phase fractions computed using
the lever rule are mass fractions—the mass (or weight) of a specific phase divided
by the total alloy mass (or weight).The mass of each phase is computed from the
product of each phase fraction and the total alloy mass.
Lever rule:
For example, fraction solid, fs is given by

Similarly fraction liquid, fl

Development of microstructure in isomorphous alloys
Equilibrium Cooling:

At this point it is instructive to examine the

development of microstructure that occurs
for isomorphous alloys during
solidification.We first treat the situation in
which the cooling occurs very slowly, in
that phase equilibrium is continuously
maintained.
Nonequilibrium Cooling:

 The reason for this is that with changes in

temperature, there must be readjustments in the
compositions of the liquid and solid phases in
accordance with the phase diagram.
 These readjustments are accomplished by diffusional
processes—that is,diffusion in both solid and liquid
phases and also across the solid–liquid interface. In
asmuch as diffusion is a time-dependent
phenomenon , to maintain equilibrium during cooling,
sufficient time must be allowed at each temperature
for the appropriate compositional readjustments
 Diffusion rates are especially low for the solid phase
and, for both phases, decrease with diminishing
temperature. In virtually all practical solidification
situations, cooling rates are much too rapid to allow
these compositional readjustments and maintenance
of equilibrium; consequently, microstructures other
than those previously described.
Mechanical Properties of Isomorphous Alloys
Iron-carbon Phase Diagrams
A portion of the iron–carbon phase diagram is presented in Figure. Pure iron,
upon heating, experiences two changes in crystal structure before it melts. At
room temperature the stable form, called ferrite, has a BCC crystal structure.
Ferrite experiences a polymorphic transformation to FCC austenite at 912°C. This
austenite persists to 1394°C, at which temperature the FCC austenite reverts back
to a BCC phase known as δ ferrite, which finally melts at 1538°C. All these
changes are apparent along the left vertical axis of the phase diagram.
The composition axis in Figure, extends only to 6.70 wt% C;at this concentration
the intermediate compound iron carbide,or cementite(Fe3C),is formed,which is
represented by a vertical line on the phase diagram.
Development of microstructure in iron-carbon alloy
Phase Transformation
Metastable Versus Equilibrium States
• The rate of approach to equilibrium for solid systems is so slow.
• Equilibrium conditions are maintained only if heating or cooling is carried out at
extremely slow and unpractical rates.
• For other than equilibrium cooling, transformations are shifted to lower
temperatures than indicated by the phase diagram.(super cooling)
• For heating, the shift is to higher temperature(super heating)
• For many technologically important alloys, the preferred state or microstructure is
a metastable one
• Intermediate between the initial and equilibrium states
• It thus becomes imperative to investigate the influence of time on phase
transformations.
 Austenite to pearlite
In interpreting this diagram, note first that the eutectoid
temperature is indicated by a horizontal line; at
temperatures above the eutectoid and for all times, only
austenite will exist, as indicated in the figure. The
austenite-to-pearlite transformation will occur only if an
alloy is supercooled to below the eutectoid; as indicated by
the curves, the time necessary for the transformation to
begin and then end depends on temperature. The start and
finish curves are nearly parallel, and they approach the
eutectoid line asymptotically. To the left of the
transformation start curve, only austenite (which is
unstable) will be present, whereas to the right of the finish
curve, only pearlite will exist. In between, the austenite is
in the process of transforming to pearlite, and thus both
microconstituents will be present.
Isothermal Transformation Diagrams(TTT Diagram)
With superimposed isothermal heat treatment curve