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MM 231
Phase Equilibria & Microstructures
Learning Outcomes
Development of new alloys for specific applications.
Fabrication of these alloys into useful configurations.
Design and control of heat treatment procedures for specific
alloys that will produce the required mechanical, physical, and
chemical properties.
Solving problems that arise with specific alloys in their
performance in commercial applications, thus improving product
predictability.
Basic knowledge on thermodynamics and kinetic factors
controlling solid state phase transformations in metals and alloys.
Diffusional and diffusionless solid state phase transformations.
Understand
the
processes
by
which
solid
state
phase
Grading Policy:
Assignment (min 4)
5%,
Quizzes
15%,
(min 6)
10%,
30 %
&
Final Exam
40%
LECTURE 1:
Solid Solutions
Solution
???????
Solute + Solvent = Solution
Alloy
?????????
Mixing of atleast two metals
Solid Solutions
Solid Solution:
A solid solution is formed when two metals are
completely soluble in liquid state and also
completely soluble in solid state.
OR
when homogeneous mixtures of two or more kinds
of atoms (of metals) occur in the solid state, they
are known as solid solutions.
Solid Solutions
Question is .
How Solid Solution Forms
Solid Solution occurs in two distinct Types:
Solid Solutions
Substitutional Solid Solution:
If the atoms of the solvent or parent metal are replaced in the crystal lattice
by atoms of the solute metal then the solid solution is known as
substitutional solid solution.
For example, copper atoms may substitute for nickel atoms without
disturbing the FCC. Similarly Ag-Au FCC binary systems and the Mo-W BCC
binary system.
Solvent
Solute
Solid Solutions
In the substitutional solid solutions, the substitution can be either disordered
or ordered.
In disordered substitutional solid solution, the solute atoms have substituted
disorderly for the solvent atoms on their lattice site. In ordered substitutional
solid solution, the solute atoms have substituted in an orderly manner for the
solvent atoms on their lattice site.
Solvent
Solute
Solid Solutions
Ordering in Substitutional Solid solutions
As stated before substitutional solid solutions can be either ordered or random.
This depends on a thermodynamic parameter called enthalpy of mixing,Hmix
Gmix = Hmix - T Smix
Gmix is the Gibbs free energy change and Smix entropy of mixing.
For an ideal solution Hmix = 0.
If Hmix> 0, formation of like bonds (A-A or B-B) is preferred in a solid solution
between metals A and B. This is known as clustering.
If Hmix< 0, unlike bonds (A-B) are preferred. This leads to ordering which may
exist over short range or long range
Solid Solutions
Interstitial Solid Solution:
In interstitial solid solutions, the solute atom does not displace a solvent
atom, but rather it enters one of the holes or interstices between the solvent
atoms.
The atoms crowd into the interstitial sites, causing the bonds of the solvent
atoms to compress and thus deform.
Elements commonly used to form interstitial solid solutions include H, Li, Na,
N, C, and O. Normally, atoms which have atomic radii less than one angstrom
are likely to form interstitial solid solutions. Examples are atoms of carbon
(0.77 A), nitrogen (0.71 A), hydrogen (0.46 A), Oxygen (0.60 A) etc.
Carbon in iron (steel) is one example of interstitial solid solution.
Solvent
Solute
1.
2. Crystal Structure
3. Valancy
4. Electronegativity
Valency Rule :
A metal will dissolve a metal of higher valency to a greater extent than one
of lower valency. The solute and solvent atoms should typically have the
same valence in order to achieve maximum solubility.
For example in aluminium-nickel alloy system, nickel (lower valance)
dissolves 5 percent aluminium but aluminium (higher valence) dissolves
only 0.04 percent nickel.
LECTURE 2:
Useful Terminology
Phase
Component
System
Solubility Limit
Phase Equilibrium
Variables of system
Useful Terminology
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Phase a portion of a system that has uniform physical and
Useful Terminology
A single-phase system is called homogeneous systems
Homogeneous system:
The one whose chemical composition and physical properties are the same in all parts
of the system, or change continuously from one point to another.
A homogeneous system can be exemplified by
imagining a column of atmospheric air, which is a
mixture of a number of gases, mainly nitrogen and
oxygen. In a system of this kind, acted upon by the
force of gravity, both the composition of the system
and its physical properties will continuously change
from one point to another.
Useful Terminology
Heterogeneous system:
One consisting of two or more homogeneous bodies. The homogeneous
bodies of a heterogeneous system are referred to as phases. Each phase is
separated from other phases by interfaces, or boundaries, and in passing
over such a boundary the chemical composition of the substance or its
physical properties abruptly change.
An example of a heterogeneous system is water with
ice floating in it. This system has two homogeneous
bodies, water and ice. The chemical composition
of the two phases is the same, but their physical
properties differ drastically.
Useful Terminology
Solubility limit:
For almost all alloy systems, at a specific temperature, a
maximum of solute atoms can dissolve in solvent phase to form
a solid solution. The limit is known as solubility limit. In general,
solubility limit changes with temperature.
The same concepts apply to solid phases: Cu and Ni are
mutually soluble in any amount (unlimited solid solubility), while
C has a limited solubility in Fe.
If solute available is more than the
solubility limit that may lead to
formation of different phase, either
Mole Fractions
Useful Terminology
Component:
is either pure metal and/or compounds of which an alloy is
composed. The components of a system may be elements, ions or
compounds. They refer to the independent chemical species that
comprise the system.
System :
It can either refer to a specific body of material under consideration
or it may relate to the series of possible alloys consisting of the same
components but without regard to alloy composition.
Degree of freedom (or variance) F :
Equilibrium
Consider a map of the potential energy (vertical axis) of a system in
four different states:
Phase Diagrams
Equilibrium Diagrams
Represents phase relationships as a function of temperature, pressure and
composition (equilibrium phases and microstructure)
A phase diagram is a type of graph used to show the equilibrium conditions
between the thermodynamically-distinct phases; or to show what phases are
present in the material system at various T, p, and compositions
But many useful diagrams are constructed for constant pressure of 1
atmosphere, so only composition and temperature are variables
Phase diagrams provides us with information needed for the control of phase
and microstructure in the materials we make
P+F=C+1
Poi
Number of
nt Components
(C)
Number
of Phases
(P)
Degree of
Freedom
(F)
2 (T,P)
2 (T,P)
1 (T or P)
1 (T or P)
Cooling Curve
The melting temperature of any pure material (a one-component
system) at constant pressure is a single unique temperature.
The liquid and solid phases exist together in equilibrium only at this
temperature. When cooled, the temperature of the molten material
will steadily decrease until the melting point is reached.
At this point the material will start to
crystallise, leading to the evolution of
latent heat at the solid liquid
interface, maintaining a constant
temperature across the material.
Once
solidification
is
complete,
steady cooling resumes. The arrest in
cooling during solidification allows the
melting point of the material to be
identified on a time-temperature
curve.
Cooling Curve
Simplified Cooling Curve of Pure Copper
the
system
temperatures,
now
the
has
two
liquidus
system
compositions
the
over
liquidus
range
and
of
solidus
allowing
the
solidus
and
Phase Diagram
Eutectic Alloy
In Eutectic System, the two elements are completely soluble in all
proportions in the liquid state. On cooling two possibilities may arise
i-The two elements are completely insoluble in solid state
ii-The two elements are partly soluble in the solid state
Liquid (L)
Cooling
Heating
Cooling
+ (Possibility (ii)
Heating
Eutectic Alloy
These reactions takes place at fixed temperature, called eutectic
temperature, and the composition of participating phases is also fixed.
Gibbs phase rule can be applied to this equilibrium system.
All three phases coexist at a single temperature. This temperature is the
melting point of the eutectic alloy
The characteristic feature of eutectic alloy is,
It melts at fixed temperature just like a pure metal.
It have a good casting characteristics such as fluidity and minimum
porosity.
Eutectic Alloy
Fig:Partial Phase diagram for the Pb-Sn system, showing the limiting behavior at high and low
temperatures
The lower part replicates the sugar water behavior ; the solubility of Pb in Sn (and
Sn in Pb) increases with temperature.
Note: Solubilities of these elements in one another is low, especially Pb in Sn on
right of the diagram.
The upper part of the diagram shows the partition behavior from the melting points
of both pure elements.
Eutectic Alloy
Eutectic Alloy
Fig: The completed phase diagram for the Pb-Sn system, showing the
eutectic point
Thermodynamics dictates that liquid boundaries meet the horizontal line
at a single point, and the liquid field closes in a shallow V. At this
special composition, two solid phases and liquid of that composition can
co-exist. This point on the diagram is very important , and is known as a
eutectic point.
with
extremely
high
strength
Prediction of Phases
The phases that are present can be determined by locating the
temperature-composition point on the diagram and noting the phase(s)
present in the corresponding phase field.
30wt%Ni-70wt%Cu at 1315 C (2400 F)
Point lies totally within the liquid field, the alloy would
be a liquid.
The same alloy at 1095 C (2000 F), designated point c
within the solid solution, , field, only the single phase
would be present.
At alloy at 1190 C (2170 F)
(point b) would consist of a two-phase mixture of
Solid solution, , and liquid, L.
alloy is