Microstructure Simulation

Microstructure Simulations
B. Nestler, F. Wendler, A. Choudhury

December 17, 2011
Contents
1 30.10.10
19
1.1 Lecture 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
2 1.11.10
44
2.1 lecture 3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
3 1.11.10
55
3.1 Lecture 4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
4 1.11.10
66
4.1 lecture 5 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
5 1.11.10
74
5.1 lecture 6 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
6 1.11.10
79
6.1 lecture 7 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
6.2 Tasks to perform . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
Introduction to solidification
Microsstructure simulations
Content
Technical importance of solidification
General terms and basics in solidification
The role of heat extraction
Directional solidification
Special solidification techniques
Aim of computational materials science
Dendritic solidification
Eutectic solidification
Peritectic solidification
Monotectic solidification
Course outline
B. Nestler, A. Choudhury, F. Wendler
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Literature recommendations
A large part of this course is treated in [Kurz and Fisher, 1998] and
[Porter et al., 2009]. A good german textbook is [Gottstein, 2007].
Gottstein, G. (2007).
Physikalische Grundlagen der Materialkunde.
Springer Verlag Berlin Heidelberg.
Kurz, W. and Fisher, D. (1998).
Fundamentals of solidification.
Trans Tech Publications ltd, Switzerland Germany UK USA.
Porter, D. A., Easterling, K. E., and Sherif, M. Y. (2009).
Phase transformations in metals and alloys (third edition).
CRC Press, Taylor & Francis Group, Boca Raton, London, New York.
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General problem definition

During processing of materials an inhomogeneous microstructure evolves,
originating from the kinetics of the processes. This may lead to potentially weak
points and eventually failure.
In this lecture, there is a focus on metal solidification. Here crystal nucleation,
a necessary prerequisite to solidification, is a ubiquitous event. Glass, a
metastable phase, is formed only at extremely high cooling rates.
Modeling goal:
Understand microstructure evolution depending on different solidification
conditions. optimize processing parameters.
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Effect of microstructure - example

Microstructure formed after casting may have severe effects on mechanical
behaviour.
Example: Ingot casting of Al-7%Si alloy with subsequent ECAP processing
(severe plastic deformation)
J.M. Garcia-Infanta et al., Scripta Mater. 58 (2008) 138.

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Technical importance of solidification

Solidification is one of the most important
forming processes in materials science,
involved in the production of almost all
technical products. It is a very economic
metal forming process (espec. for complex
shaped pieces)
Solidification as a phase transition occurs
during
metal casting (ingot casting,
continuous casting)
metal welding, soldering
polymer injection moulding
growth of silicon single or poly- crystals
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Technical solidification processes (incomplete)

Casting
Welding
Soldering/Brazing
Rapid solidification
Directional solidification
continuous casting
ingot casting
investment casting
precision casting
die casting
arc-welding
resistance welding
laser/electron beam welding
melt-spinning
atomisation
Bridgman
Czochralski
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Some general terms used in the course

Overview, most of the terms will be filled with live during the following lectures.
Phase: A phase is a homogeneous part in a possibly heterogeneous
system (Gibbs1 ). Here we have solid (s ) and liquid (l ). Can be related to
the local atomic arrangement construction of order parameters.
Equilibrium: State of minimal free energy (G or F ). Phases in contact do

have enough time (locally) to reach this state.
Transition: may arise by changing a control parameter (temperature,
pressure ...), during which latent heat is released/absorbed.
1
Josiah Willard Gibbs, 1839 - 1903, american physicist, chemist and mathematician
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Solidification basics - casting

Casting of a melt of composition C0 and
temperature T into the mold.
Cooling: A heat flux q depending on heat
diffusivity k gives rise to undercooling T
of melt.
Then, due to the difference of chemical
potentials between s - l crystallization
starts, the speed of which is given by T .
For the (macro) flow of melt the viscosity
and liquid-vapour surface tension may
be important.
Kurz, Fisher, Fig. 0

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Solidified ingots - morphology

Melt is usually cooled from the
crucible wall
This results in growth, being
fastest parallel to the temperature
gradient G.
Mushy zone: the solid/liquid
contact region, in which all growth
determining kinetic processes take
place evolution of complicate
interface structure.
Density changes givr rise to
shrinkage and porosity.
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Solidified ingots - morphology II

Microstructure zones in cast ingot,
schematic
Aluminum ingot (5 cm)
H. K. D. H. Bhadeshia, University of Cambridge
Kurz and Fisher, Fig. 1.6
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The role of heat extraction
After casting the liquid metal, heat of different physical

origin must be extracted:
Heat related to the specific heat capacity
of one
R T2
phase: enthalphy decrease H = T1 CdT
Latent heat of fusion, released in the phase
transition: Hf
Later, we will use the specific latent heat hf = Hf /Vm (Vm : molar volume)
and specific heat capacity c = C /Vm .
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Solidification stages
After casting, three different steps in the
solidification can be observed in the cooling
curve:
Figure: Quasi 1-D experiment,

P. Thevoz et al., Metal Transact. 20 A (1989) 311
1. Cooling from pouring temperature,

nucleation starts after falling below
melting temperature Tm
2. Reheating to Tm (recalescence) due to
release of latent heat
3. After complete transformation to solid,
continued cooling sets on.
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Directional solidification - experiments

Experimental setup: Controlled solidification using optical microscopy
with transparent binary analog substances.
2D:
Figure: Eutectic growth in SCN - DC,
3D:
[Akamatsu et al., Journal of Crystal Growth 299 (2007) 418]
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Directional solidification - principles

Steady heat extraction at pulling velocities v small enough to reach steady state.
Growth rate (= v ) and temperature gradient G can be separately controlled. If
heat flux qext and temperature gradient are parallel:
0

Ts+z = T z
=
G
v
s +z
z 0 t s+z
But: due to different heat conductivity in solid/liquid and release of latent heat:
Gsolid 6= Gliquid
Experimental setup for
alloys:
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Directional solidification - technical applications

Production setup (schematic): Adjust
(and move) temperature field by
controlling current in electric coils.
Figure:
Al alloy - polycrystal [Tom Quested,

Microstructural kinetics group - Univ. of Cambridge.]
Figure:
Solar grade silicon, directionally

solidified using the Bridgman method [B. Ryningen].
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Special solidification methods - metal matrix composites

Gas pressure infiltration of melt into fibre matrix to produce composite
materials:
Figure: Steps of gas pressure infiltration: a)

porous preform preheating; b) immersion of
porous preform into the melt and inlet of
pressurized gas; c) infiltrated sample in
molten matrix and d) withdrawal of
infiltrated sample from melt.
[Institute of materials & machine mechanics, Slovakian academy of
sciences]
Figure: Pure Al matrix reinforced

by unidirectional carbon fibres (65
vol %)
[G. Requena et al., Composites: Part A, 40 (2009) 152.]
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Special solidification methods - Thixocasting

Processing of metals (mostly Al, Cu, Mg) resulting in granular semi-solids
with liquid vol. fractions of 30% - 60%.
Sample in solid state as

cast (a) and semi-solid (b) a
material with rheology like

butter.
[H. V. Atkinson, Prog. Mat. Sci. 50 (2005) 341.]
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What is the aim of computational materials science?

The macroscopic properties are a
a function of the microstructure
Dependence between the
microstructure and the mechanical
properties are generally
determined experimentally
The dependence of the processing
parameters and the microstructure
determined either
experimentally or through
mathematical modeling
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Why is study of solidification important to physicists and

engineers?
Gain an understanding of
the physics behind the
pattern and microstructure
formation
This would enable control
of processing parameters
Hence, the microstructure
and the corresponding
mechanical properties
[W. Losert et al., Phys. Rev. E 58(6) (1998) 7492.]
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Dendritic Solidification
Rather a ubiquitous type of front instability than a solidification mode
MOVIE
Succinonitrile-Aceton
[H. Esaka, J. Stramke and W. Kurz, Department of
Materials, Swiss Federal Institute of Technology
Lausanne, Switzerland]
Co-Cr alloy
[Labo des Micro-Analyses des Surfaces, Besancon]
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Dendritic Solidification - phase-field simulations

Solidification of pure Ni into undercooled melt (T = 130K , T / cp = 0.3)
with P. Galenko, D. Herlach, (DLR Koln),

E. Brener, H. Muller-Krumbhaar
(FZ
Julich)
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Eutectic Solidifications - Types and Instabilities
What is eutectic
growth/reaction;
L S1 + S2 ?
Below the eutectic

temperature the liquid is
unstable to decomposition
to two solids
What is the volume
fraction of the solid phases
growing together?
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Eutectic Solidification - Length Scales

What are the different
length scales for diffusion?
Is there a physical basis
for the choice of the length
scale?
Mechanical properties
function of the length scale
Is it possible to determine
this length scale as a
function of the processing
conditions?
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Eutectic Solidification - Instabilities

Is it possible to get coupled
growth over a whole range
of length scales?
What makes coupled
growth unstable?
What are the instabilities
for large scale
microstructure?
What are the instabilities
for small scale
microstructure?
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Peritectic Solidification
Reaction and Interesting Questions
What is the peritectic
reaction,L + S1 S2 ?
Why is peritectic reaction

important to study?
- Steels (Fe C)
- Superalloys in NiAl system

(Al3 Ni)
- Nb
- Perovskite (YBaCuO)
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Peritectic Solidification - Microstructures I

Island structures, Banded structures and coupled growth:
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Peritectic Solidification - Microstructures II
[R. Siquieri et al., J. Phys. Cond. Mat. 21 (2009) 464112.]
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Peritectic Solidification - Interesting questions?

Can two solid peritectic phases grow together?
How is it different from eutectic growth?
What are the patterns and instabilities in such microstructure?
What are the microstructures and the corresponding instabilities in
3D?
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Monotectic Solidification - Challenges, microstructures
What is the monotectic

reaction, L1 L2 + S?
Why is it interesting to
learn about this reaction?
- Lubrication phenomena
(oil-oil mixtures)
- Cu-Pb (Tmono = 935 ), Pb-Fe
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Monotectic Solidification - Microstructures
What are the

interesting
microstructures?
What are the
physics behind the
formation of each of
these
microstructures?
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Monotectic Solidification
What are the open questions?

Is nucleation important?
How is the phenomena of
fluid flow important?
No validated theory
existing until now
What are the instabilities?
(Rayleigh)
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Outline of the course

(Detailed sequence in handout)
1. Introduction to the process of solidification
2. Thermodynamics and Transport Phenomena, necessary to
understand the process
3. Introduction to phase-field modeling
4. Numerical Techniques
5. Theoretical Analysis, of Dendritic, Eutectic and Peritectic
Solidification
6. Verification of theoretical concepts through modeling
7. Outlook to the open questions and challenges
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1 30.10.10
1.1 Lecture 2
Classification of materials (mat. sci.)
Materials can be classified into the following basic classes,
metals
ceramics
polymers
composites.
The aim of studying the materials science is in general to understand the functioning
of the materials, their properties, the pathway to process materials and optimize performance, through an understanding of the correlation between the structure and the
performance. In order to perform this task, it is essential to gain insights into the thermodynamics of materials, which enables us to qualify and predict the equilibrium states
of a material given, a set of conditions.
Introduction to theromodynamics
Figure 1.1: What is a system? The diagram illustrates the structure of the system in relation
to the surroundings and the means of interaction.
1 30.10.10
20
microscopic state macroscopic state
Figure 1.2: The state of the system can be completely defined at two levels. One is at the
microscopic level called the microscopic state, which contains the information about
the mass, velocity and position of the particles. The other is at the contnuum scale,
called the macroscopic state of the system, defined by variable, pressure, volume
and temperature, where two variables are independent, and related to the third
through a state function
An example of a simple system consisting of 3 variables (2 indep.) can be for example

where the volume, V=V(P,T), which is a state function of the pressure and temperature
of the system. A characteristic of a state function is that for any reversible process, the
change of state describe by the state function depends only on the end states. This can
be seen as follows: Process from 1 2: volume change
V = V2 V1
= (Va V1 ) + (V2 Va )
| {z }
| {z }
P =const.=P1
T =const.=T2
1a2
V = V2 V1 =
V =
1b2
T2
T1
P2
P1
V
T
V
P
dT +
P2
P1
P1
dP +
T1
T2
T1
V
P
V
T
dP
(1)
dT
(2)
T2
P2
1 30.10.10
21
Figure 1.3: An exemplary process showing two reversible process from the start state (1) to
end state (2), through the routes 1 a 2 or 1 b 2.
This means that V=V(P,T) is a state function, as the integral does not depend on the
integration path. The same result is found integrating the complete/total differential of
V,
dV =
V
P
dP +
V
P
dT,
P
between the limits P2 , T2 and P1 , T1 .

Equation of state for an ideal gas
Robert Boyle (1660)
1
V
(T=const)
Alexandre-Ciser Charles (1787)
V T (P=const)
Joseph-Linis Gray-Lussac (1802)

Coefficient of thermal expansion
1
=
Vo
V
T
1
273
at
0 C
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22
good for gases with low boiling points

model: ideal gas =
V(T=0 K) = 0
gives,
1
273,15
absolute Zero of Temp. Scale Combination of (Boyle) and (Charles)
P0 V0 (T1 P0 ) = P V (T1 , P )
and
z }|0 { z }| {
V0 (P0 , T0 )
V (P0 , T )
=
T0
T
PV
P0 V 0
= const.
=
T
T0
(a)
()
(b)
Figure 1.4: (a)Variation of the state function along given isotherms, (b)Variation of state function relation V and T at given isobars.
Extensive / intensive state variables

Intensive state variables are independent of the system size (P,T), extensive variables
depend on size can be transformed into intensive variables by division through mass
0
(e.g. specific volume) or mole number (e.g. molar volume V = Vn ).
Phase diagrams, terms + examples A phase-diagram, shows the regions of stability of
the different phases in a given systems. Comlexity of the phase diagram depends on
ce-Water-Vapor
1 30.10.10
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no. of components (chemical compositions): chemical elements (Ni,Cu), stochiometric

compounnds (H2 O), and general categorization can be given as follows:
one-component (pure) system
binary system
ternary system
quaternary system
One-comp. system (20 repr.)
A one component system is characterized by two independent variables, T, P. An exemplary phase diagram
showing the stability regions of the phases solid, liquid and vapor
Ice-Water-Vapor
is shown in figure 1.5.
)
AOB liquid
within, COA s
one-phase eq.(system:homogeneous)
COB v
on the line AO :two phases (s/l) coexist
two - phase eq. (system: heterogeneous)
pressure- temp. relation for eq. of sol/liq H2 O
CO: saturation vapor pressure of solid
OB: saturation vapor pressure of liquid
Figure 1.5: Phase diagram of the ice-water system.
1 30.10.10
24
Two-component system additional degree of freedom, composition

The complete diagam is three dimensional consisting of the variables, C,T,P,V. At const.
pressure the diagram at (1 atm 1 bar) can be drawn as follows,
Figure 1.6: The phase diagram of a two component system.
example: system Al2 O3 -Cr2 O3 (1 atm)

at T < Tm (Al2 O3 )= 2050 C
T > Tm (Cr2 O3 )= 2265 C
and
completely
miscible in all proportions ((Al2 O3 , Cr2 O3 have similar crystalstructure and Al3+ , Cr3+
similar size)
single phase region, l,s
two-phase region, l+s equil.
At any temperature and given composition, the relative fractions of two phases in equilibrium are derived through the well known lever rule. This can be written as follows.
Let us say, that at the temperature T1 , the equilibrium compositions of the solid and
liquid are Cs and Cl respectively. Then, the fractions of solid and liquid must satisfy,
the following mass balance relation:
C = Cs fs + Cl fl ,
1 30.10.10
25
and since, there are only two phases in equilibrium, implies that fs + fl = 1. Using this
the following relation for the solid and the liquid fractions can be derived,
fs =
(C Cl )
.
Cs Cl
The first law of thermodynamics

The first law of thermodynamics is motivated from the basic concept of conservation of
energy. The sum total change of the internal energy U which is the combination of the
vibration, rotational and kinetic energies of the atoms, when a system goes undergoes a
change of state equals the difference between the total amount of heat transferred to the
body q and the work done by the body w. An expansive work is treated as work done
by the body. Conversely, a compressive work is treated as work done on the body w. A
differential change in the internal energy U can thus be written as,
dU = q w.
Please note: the differential sign on the internal energy U, which the operator on the
variables q and w. This signifies, a fundamental difference between a state function,
whose change is independent of the path of integration, while, the quantities, q and w
depend
on the path of integration. This can be immediately be appreciated from figure,
Work
1.7. For the three paths, a, b, c the change of state, U, is the same (U2 U1 ). However,
the work done, which is area under the curve is not.
Work
Figure 1.7: Three process paths taken by a fixed quantitiy of gas in moving from the state1 to
the state2.
1 30.10.10
26
For a cyclic process: 1 2 1
dU +
dU
= (U2 U1 ) + (U1 U2 ) = 0 =
dU
For a simple one-component system, the internal energy is competely defined by two
independent variables. If temperature and volume are chosen, then, the complete differential can be written as follows,
two
|
independent
{z
state variables U=U(V,T)

}
dU =
U
V
dV +
T
U
T
dT.
Examples of different processes:

T=const. - isothermal
P=const. - isobaric
V=const. - isochoric
( Q = 0 - adiabatic)
Constant - volume processes
W =
U = QV =
P dV = 0 dU = QV ,
chage of U = absorbed/rejected heat

Constant - pressure processes
W =
P dV = P
dV = P (V2 V1 )
U2 U1 = QP P (V2 V1 )
CV dT
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( U2 + P V2 ) ( U1 + P V1 ) = QP
|{z} |{z}
|{z} |{z}
-
all are state functions

In the above, all are state functions, hence, the resulting function is also a state function.
We define new state function H=U+PV : which is called the enthalpy of the system.
R2
At P= const. H2 -H1 = H = U + P V = QP = 1 CP dT
Heat capacity
The heat capacity, C, of a system is the ration of the heat added to or withdrawn from
the system to the resultant change in the temperature of the system. Thus,
C=
Q
; small
T
changes
T : C =
Q
dT
This concept is however useful when there is no phase change. When a phase change
occurs, the heat goes in the change of state while the tempersture stay constant, which
would result, in an infinite heat capacity by the above formula. Since, the state of
a simple system is defined by two independent variables, the measurement of the heat
capacity is completely defined, only when the variation of the another variables (pressure
or volume) is defined. This leads to the following definitiions of the heat capacities,
dU
CV =( Q
dT )V = ( dT )V
dH
CP =( Q
dT )P = ( dT )P
dU= CV dT
dH= CP dT
(const. volume)
(const. pressure).
C is extensive quantity, depending on system size (mass, volume, mole no.). One can
make it intensive by dividing through respective number of moles. This gives us molar
heat capacities,
cP = CnP ;
cV = CnV .
For, cP > cV , as additional heat is required to provide work during expansion of the
system,
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cp
cv
cp cv
with dU

U
T P

H
U
V
=
=
+P
T P
T P
T P

U
=
T V

U
V
U
=
+P
T P
T P
T V

U
U
=
dV +
dT
V T
T V

V
U
U
=
+
V T T P
T V
cp cv =
(1mole)

V
P + U
T P
V T
| {z }
| {z }

Joules experiment
U
To determine, the term V
, Joule performed the experiment, as shown in figure 1.8,
T
which involved filling a copper vessel with a gas at some pressure and connecting this
vessel via a stopcock to a similar but evacuated vessel. The two vessel system was
immersed in a quantity of adiabatically contained water and the stopcock was opened,
thus allowing free expansion of the gas into the evacuated vessel. After this expansion,
Joule could not detect any change in temperature of the system, As the system, was
adiabatically contained, and no work was performed and hence, from first law of thermodynamics, it follows that the total change ininternal
energy U = 0. From the total
U
differential of U , one can then work out that,
= 0.
V T
ideal gas:
This gives the following relation for gases:
U
V
= 0 CP CV = P
V
T
In addition for 1 mole of ideal gas,: PV=RT and hence cP cV =R
1 30.10.10
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Figure 1.8: Joules experiment
es experiment

V
The term P
represents work done in expanding gas against an constant external
T P
V
U
pressure P. The term V
represents the work done against internal cohesive
T T P
forces.

U
V

U
V
P
0 fo gases, but
for liquids, solids
Reversible adiabatic process
W =
P dV
only for reversible process
Q = 0 dU = W
(1 mole) = CV dT W = P dV

dU
CV =
dT V
RT
CV dT = P dV =
dV
V
T1
V1
CV ln
= R ln
T2
V2
1 30.10.10
30

T2
T1
CP
= ;
CV
T2
=
T1
CV
V1
V2
R
CP CV = R;
V1
V2
1
T2
T1
V1
V2
R
CV
cP
R
1=
=1
cV
CV
P2 V 2
P1 V 1
P2
P1
V1
V2
PV = const (adiabatic)
Reversible isothermal process, P, V (ideal gas)
dU = Q W
isothermal dT = 0 dU = 0 W = Q = P dV =
12
P
W
W = Q = RT ln
V2
V1
= RT ln
P1
P2
RT
dV
V
fixed1 2, 1 3
isothermal > W adiab
= Q isothermal(absorbed), U=const
U= -W
Second Law of Thermodynamics

In previous chapter, only extreme processes W=0 or Q=0 were studied. For W6=0
and Q6=0, is there a definite amount of work, which the system can do?
Here we need to,
identify two classes of processes - reversible and irreversible
introduce a state function, entropy S (gives the degree of irreversibility of a process)
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Figure 1.9: Decription of a isothermal process 1 2 at T=1000K, while process 1 3 represents an adiabatic process.
Definition of Spontaneity
Spontaneous (=natural) processes Left to itself a sytem has two possibilities a) it stays
in its initial state (=if it is in equilibrium; = state of rest) or
b) moves towards its equilibrium state, if it is away from equilibrium.
Hence, a process which involves, the movement of a system away from equilibrium towards its equilibrium state, is called a spontaneous process. Since, this process cannot be
reversed without the application of an external agency, it is called an irreversible process,
as it would require an irreversible change in the properties of the external agency.
Examples of two spontaneous processes,
1. Mixing of gases
2. Flow of heat down a temperature/conc. gradient
In both cases, the state of equilibrium is in (a) where the composition is uniform in the
gas mixture, and in (b) the temperature of the system becomes uniform. A knowledge
of the equilibrium allows us to decide, the direction of the spntaneous reaction given the
initial state of the the system. During a spontaneous process, work is performed and as
equilibrium is reached the ability to perform work is reduced and finally at equilibrium,
the system is at rest. As woek is performed, there is degradation of energy to heat and
the ability to do work is lost.
Entropy and the quantitfication of irreversibility
eservoirsystem
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There exist two distinct types of spontaneous processes,

Conversion of work to heat (i.e degradation of mechanical energy to thermal energy)
Flow of heat down a temperature gradient
If it is considered that during an irreversible process, the ability to do work is degraded,then it is possible to quantify the extent of degradation or the extent of irreversibility
of the system. Consider the weight-heat reservoir system as shown in figure
reservoirsystem
1.10. The system consists of a weight-pulley arangement which is coupled to a constanttemperature heat reservoir , and the system is at equilibrium when an upwrd force
acting on the weight exacty balances the downward force, W, of the weight. If the upward force is removed then the equilibrium is upse and the wieght spontaneously falls
thus performing work which is converted by means of a suitable system of paddle wheels
to heat which enters the constant temperature heat reservoir. Equilibrium is reattained
when the upward force acting on the weight is replaced and the net effect of this process
is that mechanical energy has been converted to thermal energy. Now three different
experiments can be considered with this setup.
1. work performed by weight W transformed to heat Q entering reservoir at
T2
2. same amount of heat flows to a different reservoir at temperature T1 where T1 <
T2 which is in thermal contact
3. same as 1. , but now the main reservoir is at T1 and heat flows into heat reservoir.
Figure 1.10: Weight-heat reservoir system
It can be percieved that essence process 3. is the sum of 1. and 2. And hence, process
(3) should be more irreversible. Examining the processes closely, shows, that the amount
1 30.10.10
33
of heat Q and the temperature between which the heat flows, is imporatant in finding a
quantitative measure of irreversiblity. Hence, we derive a term of the form Q
T , defined
by the amount of heat Q and (absol.)temeratures T1 , T2 . With this definitiion we
directly see that process (3) is more irreversible than (1) for T1 < T2 . This degree of
irreversibility we call as the increase of entropy S and define,
Entropy produced: S =
Q
T .
If irrversibility is quantified, how do we visualize a reversible process?

A reversible process, is one where the degree of irreversibility is minimized. The ultimate
minimization would occur when the concept of spontaneity is no longer applicable, which
apparently implies that the system is only infinitesimaly away from equilibrium such that
the extend of degradation is as small as we please. This a reversible process, wherein, a
system is taken from state A to state B, through string of states all at equlibrium. An
illustration of a reversible process can be seen as follows.
Reversibleprocess
Consider a system as shown in 1.11. it consists of water in equilibrium with its vapor
at given saturated pressure PH2 0 (T ), which is function of temperature T. Now the
system is at rest where the Pext exactly balances the saturated vapor pressure. Now
consider, we reduce the external pressure by P , which would then cause the gas to
expand owing to mismatch of pressure, and the water would start to evaporate to restore
equilibrium. Since, evaporation is an endothermic process, heat would be drawin in
from the reservoir to maintain constant temperature T, by providing the required latent
heat for the process. If after one mole of evaporation, the pressure is agian increased
to its original value, then the evaporation stops, and the work done by the system is
(Pext P )V, where V is the molar volume of the gas. Conversely, when the pressure of
the gas is now increased by an amount P , this would cause the piston to fall rapidly, and
the water-vapor would start to condense to restore equilibrium between the water- and
water vapor. This is an exothermic process, which would need a transfer of heat to the
reseervoir to maintain the same temperature T. After one mole of gas has condensed, the
external pressure is again increased to the saturation vapor pressure at the temperature
T. This restores equilibrium and the total work done is (Pext + P ) V. In the total
cyclic process, the total work done by the external agency is 2P V . Now a reversible
process would be such, where this term is minimized. Or in other words, a system where
the change in the external pressure is an infinitesimal P , and the process is carried out
slowly, such that the change in saturation is reduced and the heat flow keeps up wth the
equilibrium.
It is thus seen that reversibility is approached when the evaporation or condensation
processes are carried out in such a manner that the pressure exerted by the vapor is
never more than infinitesimaly different from its value at the saturation temperature T.
It is also seen that as complete reversibility approached, the process becomes infinitely
slow.
ersibleprocess
1 30.10.10
34
The whole process is summarized below:

example
equilibrium: Pext = PH2 O (T) and T=TH2 O = Tvaporn
1. Pressure drop Pext P , work done

W = (Pext P )V (evaporation)
2. Pressure increase Pext + P
3. W = (Pext + P )V (condensation)
4. W12 = 2P V
Figure 1.11: A hypothetical system of water in equilibrium with its vapor at saturated vapor pressure PH2 0 (T ), which is a function of temperature T. The system is kept
in contact with a heat reservoir, and an external system to adjust the external
pressure Pext .
1 30.10.10
35
Entropy and reversible heat Consider just the process of evaporation in the previous
text. For a reversible process, the work done by the system is Pext V . For any irreversible
process, the work done by the system is (Pext P ) V . It is clearly seen that maximaum
work Wmax occurs during a reversible process.
1. Reversible process (P P ):
Wmax = Pext V ;
Qrev = U + Wmax
U indep. of process
W = (Pext P )V ;
Q = U + W
differenceWmax W = Qrev Q
is degraded into heat within the irrev. process
Rev.: entropy change of heat reservoir: Sheat

of H2 O/ vapour: SH2 O+vap. =
res.
= QTrev
Qrev
T
Stotal = 0
Irrev.: Q < Qrev ; Sheat
SH2 O+vap. =
Stotal =
Qrev Q
T
Q
T
res
= Q
T
Qrev Q
T
= Sirrev > 0
for each possible process SH2 O+vap. =
Q
T
+ Sirrev
2. Condensation, reversible:
)
SH2 O+vap. = QTrev
Stotal = 0
Sheat+res. = QTrev
irreversible
Q Q Qrev )
SH2 O+vap. =
+
T
| {zT } |
{z
}
leaving
SH2 O+vap. =
heat created
QTrev
Stotal =
QQrev
T
for each poss.: process SH2 O+vap. = Q

T + Sirrev
Q > Qrev , > 0
1 30.10.10
36
important S = SB SA =
Q
T
+ Sirr =
Qrev
,
T
indep. of the path/process.
S is state function, only measurable for reversible process

Reversible isothermal compression, ideal gas (1 mole)
eq. path (VA ,T) (VB ,T)
isotermal comp U = 0 ; Wmax = Qrev
RV
RV
VB
W = VAB P dV = VAB RT
V dV = RT ln VA < 0
entropy change of gas Sgas =
Sheat
res
Qrev
T
= Rln VVBA < 0
= Sgas = Rln VVBA
Figure 1.12
Reversible adiabatic expansion, ideal gas

eq. path (PA , TA ) (PB , TB ), Q=0 if rev. proc. (quasistatic) and isolated (adiabatic)
S = 0, const. entropy P V = const
Wmax = U
CP
CV
5
2
1 30.10.10
37
Sudden increase of PA PB from (PA , TA ): System leaves the P-V-T surface, entropy
is produced, TB > TB,rev
W = U < Wmax
Summary
1. Entropy S increases for irrev. process
2. Srev = 0 (entropy is transfered from one part to another of the system)
3. S is a state function, S =
Qrev
T
Heat engines
Figure 1.13
efficiency
= work obtained =
heat input
W
Q2
Studied by Sadi Carnot (1824)

1. AB isoth. expansion at T2
2. BC adiab exp. (rev.) T2 T1
3. CD isoth. compression at T1
4. DA adiab. comp. T1 T2
One cycle: W = W1 + W2 W3 W4
Q = Q2 Q1
U = 0 Q = W = Q2 Q1
=
W
Q2
Q2 Q1
Q2
two heat engines 1 and 2, 2 > 1 : reverse direction=heat pump
1 30.10.10
38
Figure 1.14
)
2: W 0 = Q2 Q01
W 0 W = Q1 Q01 heat transferred directly to
1: W 0 = Q2 + Q1
work other changes (Perp. mobile of 2nd kind)
)
2: W = Q02 Q01
Q2 Q02 = Q1 Q01 = Q heat flows from low
1:W 0 = Q2 + Q1
|
{z
}
(Q1 +Q01 )
temp.T1 to high temp.T2 without other changes

2nd Law of Thermodynamics
There is no cyclic process to convert heat from reservoir directly into work without transferring heat to a cold reservoir
- To transfer heat from cold to hot reservoir, some amount of work is necessary.
(discuss.) All rev. Carnot cycles (T2 , T1 ) have the same efficiency (the max.) and depend
1 30.10.10
39
Figure 1.15
Figure 1.16
1 30.10.10
40
only on temperature
Q1
:= 1 f (T1 , T2 )
Q2
Q1
Q2
= f (T1 , T2 )
= f (T2 , T3 )
Q2
Q3
Q1
= f (T1 , T3 )
Q3
Q1 Q3
Q1
f (T1 , T3 )
=
=
= f (T1 , T2 )indep. of
Q3 Q2
Q2
f (T2 , T3 )
T3 f (T1 , T3 ) = F (T1 )/F (T3 )
Q1
F (T1 ) Kelvin T1
=
:=
Q2
F (T2 )
T2
efficiency
Q2 Q1
T2 T1
=
=
Q2
T2
=1
defines an absolute temperature scale (indep. of warley substance)(Kelvin scale)

to ideal gas (eq. of state)
A Bisoth. expansion
B Cadiab exp.
U = 0;
Q = 0;
Q2 = W1 = RT2 ln
W2 = U =
ZT1
VB
VA
CV dT
T2
C Disoth. compression U = 0;
D Aadiab. comp.
Q = 0;
Q1 = W3 = RT1 ln
W4 =
ZT2
CV dT
T1
total work done by gas:

W = W1 + W2 + W3 + W4 = RT2 ln VVBA + RT1 ln VVD
C
total heat absorbed from hot reservoir
Q2 = RT2 ln VVBA
within
VB
VA
VC
VD
(T V 1 = const) W = R(T2 T1 )ln VVBA
VD
VC
1 30.10.10
this =
W
Q2
41
=
T2 T1
T2
The second law of thermodynamics

Carnot process
Q2 Q1
Q2
T2 T1
T2
Q1
T1
Q2
T2
=0
Any
P Qcyclic process can be broken down in a number of Carnot cyces for Zig-Zag path:
T =0
Q > 0 heat entering, Q < 0 heat leaving system

I
Q
can be replaced in the limit by
T
| {z }
total
dif f.
1. the entropy S, defined by dS =

(eg loop ABA
dS = 0 =
RB
of
Qrev
T
dS +
RA
state
=0
f unction
is a function of state
dS = (SB SA ) + (SA SB ) = 0)
2. For an adiabatically enclosed system, the entropy can never decrease

irreversible p. : S > 0
reversible p. : S = 0
Maximum work A B
UB UA = W Q
2nd Law limits the maximum amount of work extractable
Q
+ dSirr , Q = dU + W
T
dU + W
dS =
+ dSirr
T
W = T dS dU T dSirr
dS =
W 6 T dS dU
example: isothermal process, Wmax = T (SB SA ) (UB UA ) if proc. is revers.

S is state function S it the sane if expansion is used to create work or free expanded
Equilibrium= reached. when entropy reaches a maximum value
in an isolated system of constant int. energy U and volume V, eq. is attained at maximum entropy
1 30.10.10
42
example: reaction
A+B
C+D
Figure 1.17
Figure 1.18
for closed system

dU = Q W ; W = P dV
Q
dS =
T
dU = T dS P dV ()
U
U
)V dS + (
)S dV
U = U (S, V )with dU = (
S
V
1 30.10.10
43
compare to ()
U
)V temperature def.
S
U
P = (
)S pressure def.
V
S = S(U, V )
T =(
dS =
S
U
dU +
V
S
V
dU
P dV
+
T
T
S
P
(
)U =
V
T
()
dV =
U
Equilibrium occurs:
- in a system with fixed U and V, if entropy is maximized
- in a system with fixed S and V, if internal energy is minimized
Further development: S and V are inconvenient variables to be controlled in real world.
2 1.11.10
2.1 lecture 3
Entropy from statistical mechanics
Motivation: What is the physical significance of entropy? The second law of thermodynamics is only valid because of the failure of human ingenuity to invent a perpetual
machine. Thus, within the scope of classical thermodynamics, the second law is a Law
only because it has not yet been disproved. Physical interpretation of entropy came from
the development of quantum theory and statistical mechanics. So, in the present class
we search an interpretation of entropy in the framework of statical mechanics.
Definition from Gibbs:
Entropy is the degree of disorder or the degree of mixedness Correlation with macroscopic picture: Melting of a substance absorption of quantity of heat (Latent)
H
= Tmf
q s = Tq
m
m atT
sm
m
s
Only true however for reversible process. For irreversible process the surroundings +
system should be considered
Concept of Microstate:
1. Quantification of the idea of degree of disorder or mixedness In statistical mechanics, equilibrium state of the system in the most probable
of all its possible states.
2. Energy is quantized. Particle in a box, has discrete values of energy. Spacing between
the discrete values of energy decreases and the energy space becomes continuous when
the space available for the particle increases and the restriction placed on the position
of the particle reduces.
3. Description of Microstates:. Example: consider a crystal with 3 non-identical particles
located on different lattice sites. Suppose, for simplicity,
that the quantization is such
EnergyLevels
that the energy levels are equally spaced as below Fig. 2.1.
Total energy U = 3u.Three possibilities exist.
2 1.11.10
EnergyLevels
Configurations
45
Figure 2.1: Energy levels of the different possible lattice sites.
Figure 2.2: The different possibilities for the arrangement of the particles in the different energy
levels with the total energy 3u.
Possibility (a):-1
Probability of (a):-
1
10
Possibility (b):-3
Probability of (b):-
3
10
Possibility (c):-6
Probability of (c):-
6
10
Each of the individual

possibilities is a microstate also called a complexion, which
Configurations
are shown in Fig. 2.2
4. Relation between microstate and macrostate. The number of a arrangements within
a given distribution , that have n particles among energy levels n0 in 0 , n1 in 1 , n2
in 2 and so on can be written as,
n!
n!
= r
.
n0 !n1 !n2 !...nr !
i=0 ni !
ln =n ln n n
i=r
X
(ni ln ni ni ).
i=0
U =n0 0 + n1 1 + n2 2 ....nr r Macrostate property fixed
2 1.11.10
46
i=r
X
ni i (Energy constant)
i=r
X
ni (Particles Constant). Macrostate property fixed
i=0
n =constant = n0 + n1 + n2 ... + nr .
=
i=0
Any interchange of particles, among the energy levels must confirm with the condition
X
X
U =
i ni = 0 and n =
ni = 0.
i
If is maximum
X
ni ni
ni ).
(ni ln ni +
ni
X
=
(ni lnni ) = 0
ln =
1, 2, 3 need to be simultaneously satisfied for the most probable distribution. Method

of undetermined Coefficients
X
X
i ni = 0;
ni = 0.
1,2,3 together gives:i=r
X
(ln ni + + i )ni = 0.
i=0
This needs to be true for all ni ; hence.
2 1.11.10
47
ln ni + + i = 0.
ni = e ei .
Summing over all r energy levels.
n=
i=r
X
ni = e
i=0
Pi=r
i
i=0 e
( i=r
X
i=0
ei
is called the partition function P.
e =
ni =
n
.
p
n i
e
;
p
is the Boltzmann constant =
1
KT
The distribution of the particles in the r energy levels reduces exponentially with the
energy value of the r energy level.
Variation with Temperature The relation the
occupancy of the different energy levels
nivsepsilon
at different temperatures is shown in Fig. 2.3. At higher temperatures the occupancy
shifts towards higher energy levels.
Relation between macroscopic variables and microscopic property .
For large no of particles, the maximum possible distribution max min and max
2 1.11.10
nivsepsilon
48
Figure 2.3: Plot showing the variation of the particles in the various energy levels at different
1
temperatures, through the choice of different values of =
.
KT
total.
ln total = ln max = n ln n
=1/KT.
ln total =n ln n
=n ln n
Xn
p
i /KT
ni ln ni .
ln
n i /KT
e
p
X
i
n
n X
(ln n ln p)
ei /KT +
i e KT .
p
pKT
But
U=
X
n i i =
i ei /KT =
Xn
p
i e KT =
UP
.
n
ln = n ln p +
U
.
KT
Thermal. Equilibrium and Boltzmam Equation.
n X i /KT
i e
.
p
2 1.11.10
49
Consider equilibrium between reservoir and particles.

U = U particles + U neat bath
V = V particles + V heat bath
At Thermodynamic Equilibrium;
ln =
U
KT
At constant n, P(i , T )
at constant volume;
U = Q.
Q
ln =
.
KT
For reversible process; s =
Q
KT
= K ln .
Since S and are state functions, the above expression can be written as a differential equation, integration of S gives, S = K ln . This is also known as configurational
entropy. An exemplary calculation of configurational entropy can be seen in the following:
The distribution of particles at the available sites can be visualized in the following
binary alloy consisting of two types of atoms A and B as shown in the following:
Figure 2.4: Configurations of atoms before mixing.
During the mixing process: A + B (divided) A/B mixed, different possibilities exist.
For example, when there is no mixing, there is just one possible state written as 4 :
0 = 1. With one atom transfer, the number of possibilities of arrangement on each side
of XY plane is 4 and hence, the total number of possibilities of such an arrangement
is 16, given by 3 : 1 = 16. With an exchange of two atoms, we have six possibilities,
which gives a total of 36 possibilities 2 : 2 = 36. Finally with 3 atoms exchanged,
2 1.11.10
50
we have a total of 16 possibilities 1 : 3 = 16. Among the 70 possibilities, the one

with highest probability is 2 : 2 = 36 as this maximizes the entropy and hence is the
equilibrium state of the system. From the above discussion, we derive that the total
number of possibilities for a given configuration of na :A atoms and nb :B atoms can be
(na + nb )!
given by
. The change in the configurational entropy going from a non-mixed
na !nb !
state can be calculated as:
Sconf = Sconf 2 Sconf 1 =K ln conf 2 K ln conf 1

conf 2
=K ln
.
conf 1
(na + nb )!
=K ln
na !nb !
Other potentials:
dU = T dS P dV +
dH = T dS V dP +
dF |T,V,nj
X U
i
ni
dni .
s,v,nj
X H
dni . H = U + P V
ni s,p,nj
X F
dni . F = U T S
dF = SdT P dV +
ni T,V,nj
i
!

F
U
=
.
dni = dU |T,V,nj T dS|T,V,nj =
ni T,V,nj
ni S,V,nj
compare,
with (*)

G
U
= n
i = ni
i
T,P,nj
S,V,nj
Complete set of the potentials:
H
ni
S,P,nj
F
ni
T,V,nj
2 1.11.10
51
dU = T dS P dV +
dH = T dS + V dP +
i dni
i dni
X
dF = SdT P dV +
i dni
X
dG = SdT + V dP +
i dni
fundamental relation
U is characteristic function of the independent variables S, V and nj . First law:
dU = Q W P
with Q = T dS(reversible)
W = P dV i dni
Thermodynamic relations (from (1-4))
T
P
V
S

U
U
=
.
=
S v,nj
S P,nj

U
F
=
=
.
V s,nj
V T,nj

G
H
=
=
.
P s,nj
P T,nj

F
G
=
=
.
T v,nj
T P,nj

Maxwell relations
Z is a state function of independent variables X and Y :Z=Z(X,Y)

Z
Z
dZ =
dX +
dY
X Y
Y X
=L(X, Y )dX + M (X, Y )dY
2 1.11.10
52
order of differentiation doesnt make a change:

Z
2Z
=
=
Y X Y X
X Y X Y
XY

L
M
=
U X
X Y
applied to (1)-(4): Maxwell relations:

T
V S

T
P S

S
V T

S
P T

P
=
.
S V

V
=
.
S P

P
=
.
T V

V
=
.
T P
Example 1 Entropy of ideal gas S = S(T, V )
dS =
S
T
S
V
dT +
dV
T
heat capacity at const.V : T dS = Qv = dU = nCv dT
S
T
nCv
=
;
T
S
V
nR
V
T
v
nCv
nR
dS =
dT +
dV
T
V
T2
V2
S2 S1 = nCv ln
+ nR ln
T1
V1
R
T2
V1 Cv
is-entropic process
=
T1
V2
=
P
T
2 1.11.10
53
Example 2 closed system / fixed comp.

U
V
=T
S
V
dU = T dS P dV

P
P =T
P
T V
equation of state, relation of U to measurable quantities P, V, T

Upstairs - downstairs-inside- out formula
three state variables X,Y,Z with X=X(Y,Z)

X
X
dX =
dY +
dZ
Y Z
Z Y

X
X
dY =
dZ
forX = const :
Y Z
Z Y

Y
X
X
=
Y Z Z X
Z Y

X
Y
Z
= 1
Y Z Z X X Y
Phase Equilibrium in a one component system

two phase in contact: open to was exchange
intensive Thermodynamic properties of a system are temperature pressure and
chemical potential. There properties are measures of potentials, spatial gradients
of which
Temperature Potential of heat decides direction of heat flux
PressurePotential for expansions or contraction
chemical potentialTendency of species i to leave the system. Measure of the chemical
pressure exerted by i in the phase direction of diffusive mass flux
2 1.11.10
54
Variation of Gibbs free energy as Temperature

G
T
= S;
2G
T 2
dG = V dP SdT

S
CP
=
=
T P
T
Figure 2.5
Phase transition dG<0

fixed -S:= Slope of the line G(T).
First order transition: There is a change in the slope of the line as there is a phase
transition S l 6= S s
Second
2order
Transition: Slopes are continuous; but a discontinuity in the second deriva G
tive T 2 . CPl1 6= CPl2 Example:-Glass-Transition
3 1.11.10
3.1 Lecture 4
Gibbs Free energy as a function of temperature and pressure.
Consider equilibrium between solid and liquid. Gs = Gl
For infinitesimal changes:
dGs = dGl
dGs = S(s) dT + V(s) dP
dGl = Sl dT + Vl dP
S(s) dT + V(s) dP = Sl dT + Vl dP
V(s) V(l) dP = (S(s) S(l) )dT

S
Ss Sl
dP
=
=
dT eq. V
Vs Vl
at eq.:
S =
Clausius Clapeyron equation:
Hf
T
P
T
eq.
Hf
T V
This gives the dependence of pressure on temperature (or the relation between the two)
to maintain equilibrium. Alternatively this defines the properities of the equilibrium line
denoting the co-existence between the solid and liquid phase.
Behavior of Gases, solutions, Phase-Diagrams:
P:-Pressure of Gas.
V:-Molar Volume.
R:-Gas constant.
3 1.11.10
56
T:-Absolute temperature

pV
1
RT
Real gases
P 0
Mixture of Ideal Gases - (a model for solubility and mixing)

How do we treat a mixture of gases? For a pure gas:- what is the relation of Gibbs free
energy and pressure in a closed isothermal system given by dT=0, (Isothermal change
from P1 P2 )
dG = V dP.
For 1 mole of ideal gas,
RT
dP = RT dlnP.
P
P2
G(P2 , T ) G(P1 , T ) = RT ln
P1
dG =
G = G0 + RT ln
(I)
P
P0
G0 (Free energy of 1 mole, P0 = 1 atm Standard state)

Mixture of gases:
To describe a mixture of gases we need to derive the concept of mole fraction, partial
pressure and partial molar quantities.
Mole fraction:
XA =
nA
nA +nB +nC
XB =
XA + XB + XC = 1
Partial pressure:
container,
nB
nA +nB +nC ;
XC =
nC
nA +nB +nC
(representing composition)
PA :-Pressure exerted by component A, if it were alone present in a
Total pressure P = pA + pB + pC
3 1.11.10
57
nA RT
V0
nB RT
pB =
V0
pA =
P = pA + pB =
(nA + nB )RT
V0
Daltons law of partial pressures pA = XA P

Partial molar quantities
Partial molar value of on extensive quantity Q, in a mixture i, j, k denoting (components),
Qi =
Q0
ni
= rate of change of Q0
with ni
at
T, P, nj , nk = const.
T,P,nj ,nk
Q0 :- Value of Q for an arbitrary quantity system size of mixture for Q G.
Gi =
G0
ni
= i (chemical potential of the component in mixture)
T,P,nj ,nk
Maxwell relations are also applicable for partial molar quantitiesfrom fundamental
rel.
ni
=
G0
ni
G0
P
!
T,P,nj
Solutions
e(A) :- equilibrium rate of evaporation (A).
G0
P
!
T,comp
T,comp
=V0
T,comp
=V
T,P,nj ,nk
Gi
P
T,
3 1.11.10
58
Figure 3.1: Example of mixture of gas molecules A and B.
In pure A, we have the activation energy as E A the rate of evaporation is proportional

EA
to e( KT
).
(1) e(A) = kp0A := p0A (saturated vap. pressure)
Similarly in pure B we have the rate of evaporation (B) given by - e(B) ,
e (B) = k 0 p0B ,
where k, k 0 are the rate constants related to the process of evaporation.
In a mixture, the rate of evaporation of A is reduced by XA (the mole fraction). (with
the assumption of identical bond energies A-A, A-B, B-B and composition of suface like
in bulk) while,
(2)e(A) XA = kpA
e(B) XB = k 0 pB
giving us the Raoults Law pA = XA p0A
pB = XB p0B .
Gibbs duhem Equation

How are partial molar quantities of components in a system related?
3 1.11.10
59
Let Q be an extensive property

Q0 = Q0 (T, P, ni , nj , nk ...)
at const. T,P
0
dQ =
Q0
ni
dni +
T,nj ,nk
Q0
ni
dnj +
T,nj ,nk
dQ0 = Qi dni + Qj dnj + Qk dnk ...(1)
Q0
nk
T,ni ,nj
also from definition:

Q0 = Qi ni + Qj nj ...
dQ0 = (Q1 dni + Qj dnj + ...) + dQi ni + dQj nj + ...)(2)
(1) and (2) gives.
X
dQi ni = 0 ;
or dividing by no. of moles of system
Binary solution(A,B) if Q0 G0 ;
X
i
T, P =const:
G0 = n A GA + n B GB
(1)G XA GA + XB GB
G0 : Gibbs energy
G = molar Gibbs energy
Gi = Excess enthalpy
Gibbs - Duhem:
XA dGA + XB dGB = 0
dG = GA dXA + GB dXB
dG
= GA G B
dXA
dG
= XB GA XB GB
(2) XB
dXA
dG
dG
(1) + (2) G + XB
= GA ; GB = G + XA
dXA
dXB
Properties of Raoultion Ideal Solutions
dQi xj = 0
dnk ...
3 1.11.10
60
Figure 3.2: Definition of partial molar Gibbs-free energies given the free energy at a given
composition
Some terminology
ai (activity of component i) =
fi
fi0
When the vapor in equilibrium is ideal

ai =
pi
....(II)
p0i
In addition if the component i exhibits Raoultion bahavior ai = Xi .

Change in Gibbs-free energy due to the formation of a solution: (A,B)
Deriving the free energy change in a mixture of gases (I)
Gi = Gisolution Gi(pure) = RT ln
pi
p0i
= RT lna0i
= Gi G0i = RT lnai = RT lnXi
Free energy before mixing:-(na : A, nB : B)

nA G0A + nB G0B
3 1.11.10
61
Free energy after mixing:n A GA + n B GB

Free energy change accompanying mixing:
G0 = nA (GA G0A ) + nB (GB G0B ).
= nA GA + nB GB .
= nA RT lnaA + nB RT lnaB .
= RT (nA lnaA + nB lnaB ).
For Ideal Solution

G0 = RT (nA lnXA + nB lnXB ).
for a mole
G = RT (XA lnXA + XB lnXB ).
Figure 3.3: Concept of the change in free energies
Change in volume of an ideal Solution.
3 1.11.10
62
Using:

G
P T,comp

Gi
P T,C

(Gi G0i )
P
T,C

Gi
P
T,C
=V
= Vi ;
G0i
P
= Vi0
T,C
= Vi Vi0
= Vi Vi0
Gi = RT lnXi
Gi
P
or V i Vi0 = 0
=0
T,C
Vi = 0
From this it follows:change of volume is zero in ideal mixing

V 0 M = nA V A + nB V B
V A = 0 and V B = 0
Heat of formation of an ideal solution.

"
Gi /T
T
0
Gi /T
P,comp
Hi
;
T2
0
P,comp
H
= 2i
T
(H i Hi0 )
H i
= 2 =
2
T
T
(Gi G0i )
T
"
(RlnXi )
Hi
=
=0
T
T2
H 0 = nA H A + nB H B = 0 HA 0
Entropy of formation
G /T
=
T
and HB 0.
3 1.11.10
63
GM
T
G
T
P,comp
= S.
P,comp
= S M = R(XA lnXA + XB lnXB )
III
From the definition of configurational entropy.

(NA + NB )!
NA !NB !
= k[ln(NA + NB )! lnNA ! lnNB !]
S 0 = k
Apply stirlingss approximation
ln
S 0 = k[(NA + NB )ln(NA + NB ) NA NB .
NA lnNA + NA NB lnNB + NB ]

(NA )
NB
= k NA ln
+ NB ln
(NA + NB )
(NA + NB )
NA
nA
=
= XA .
NA + NB
nA + nB
NA
NB
NA :
moles = nA ; NB :
moles = nB .
N0
N0
Avogadro no
S = kN0 (nA lnXA + nB lnXB )
1 mole:-
S = R(XA lnXA + XB lnXB ) IV

III IV
!!!
The thermodynamic activity of a comp in solution

at temperature T: activity is the ratio of fugacity of a substance
ai =
fi
fi0
for solution vapor
fi = Pi
Raoultian behaviour
ai = Xi
at T
ai =
Pi
Pi0
3 1.11.10
64
Henry behaviour
ai = ki Xi
The Gibbs-Duhem equation

(Gi /T )
T
P,comp
Hi
T2
G = H TS

G
=H +T
T P

G
H
G
=
+
T
T
T

G
( T )
H
1 H
2G
= 2 +
+
T
T
T T P
T 2
2G
S
=
T
T
dH
S=
T
1 H
S
=
T
T T
( G
H
T)
= 2
T
T
Gibbs-Helmoltz relation.
Gibbs-Phase Rule.
* N phases, K components
NK degrees of freedom
(N-1)K Equations of equilibrium
NK-(N-1)K=K
N Equations of sum constraint
F=K-N
For Non, constant T,P F=K-N+2
CA GA + (1 CA )GB + RT (CA lnCA + CB lnGB )
G = CA (GA + RT lnCA ) + (1 CA )(GB + RT ln(1 CA )).
3 1.11.10
65
CA GA + (1 CA )GB
GA = GA + RT lnCA
GA
B = GB + RT lnCB
4 1.11.10
4.1 lecture 5
Figure 4.1: A solution is different from a mixture of pure A and pure B. Therefore for a compostion of XA in binary system A, B,
G0A XA + G0B (1 XA ) 6= G0 (XA ).
G0 (XA ) = GA XA + GB XB .
G(XA ) = (GA G0A )XA + (GB G0B )XB .

= GA XA + GB XB .
Where GA is the partial molar Gibbs free energy change of the system for the component A.
For Ideal Solution (Raoultian)
GA = RT lnXA .;
GB RT lnXB .
GM IX (XA ) = XA RT lnXA + XB RT lnXB
4 1.11.10
67
Figure 4.2
Free energy change of entropy of missing S(X)

S M IX = R(XA lnXA + XB lnXB )
Maximum randomners for equal mole fractions of components A, B. This holds also
Figure 4.3
for more than 2 components (A, B, C...) (XA = XB = XC ...)
4 1.11.10
68
To get the free energy of the system,

G = G0A XA + G0B XB + GA XA + GB XB .
Nobody can (calculate)
measure absolute G, but only change. So one would need a reference
state. For the discussion, we fix the reference state as T0 = 298K, P=1 atm. because
most measurements are done at 1 atm.
Then at const P=1 atm.
G = XA
dG0A
+ XB
dG0B + GA XA + GB XB .
T0 =298
T0 =298
G = H T S.
G = H S T S S (Free energy change)

Z T
Z T
Z
S
S
= XA
CpA dT + XB
CpB dT T
T0 =298
l
T0 =298
T0 =298
T HfA
Tf
Z
T0 =298
T HfA
Tf
Z
)XA + (HfB
CpSB dT T
)XA + (HfB
CplA dT + XB
T0 =298
+(HfA
Tm
T0 =298
+(HfA
Z
T0 =298
CpSA
dT
T
G = H T S .
Z Tm
Z
= XA
CpSA dT + XB
Gl = XA
Tm
T0 =298
T HfB
TfB
Z T
CplB dT T XA
T HfB
TfB
T0 =298
CpSA
dT T
T
CpSB
dT.
T
Tm
T0 =298
CpSB
dT.
T
)XB .
T0 =298
CplA
dT TXB
T
T0 =298
CplB
dT
T
)XB
Hf
CVl dT
+ Hf T
.
Tf
Tm
Tm T d
Z T
Z T
Z T
Z T
dT
dT
Gl = XA
CplA dT + XB
CplB dT XA T
CplA
XB T
CplB
T
T
Tm
Tm
Tm
Tm
B
A
T Hf
T Hf
)XA + (HfB
)XB .
+(HfA
Tf
Tf
Z T
Z T
Z T
Z T
dT
dT
CpSA dT + XB
CpSB dT XA T
CpSA
GS = XA
XB T
CpSB
.
T
T
Tm
Tm
Tm
Tm
=X
CVl dT T
Gl GS .
Z l
Z
dT
XA
CpA dt XA T CplA
0
T
Tm
for
Cpls
A =0
for
Cpls
B = 0.
4 1.11.10
69
Z
Gls
dT
CpB dT XB T CpTB
XB
0.
T
Tm

(Tf T )
Tf T
XA + HfB
= HfA
XB .
Tf
Tf
Taking liquid as reference.

(T Tf )
(T Tf )
XA + HfB
XB .
GS : HfA
Tf
Tf
Gl = 0.
GS = XA HfA
(T TfA )
Gl =
TfA
l
GA XA
+ XB HfB
(T TfB )
TfB
+ GA XA + GB XB .
+ GB XB .
Points to note:
HfA : - Latent heat of fusion. for S L transition. In principle, the latent heat of
transformation will then depend on the solid phase and the liquid phase.
We name Hf LA L transformation for pure A.
What is the latent heat of transformation for an alloy of comprosition XA ?
We can analogously derive as for the case of pure components at equilibrium;
GSL = 0.
H SL = T (S S S L ).
GS
.
T
Gl
S l =
.
T
S S =
SL
1
=
T
GS
Gl
T
T
.
XA
How do we geometrically see the equilibrium between tow phases in a binary system?
S
GA = GA
GB = GB
4 1.11.10
70
Figure 4.4
Thus, for a binary system (A,B) phase equilibrium between two phases (, l) implies the
partial molar Gibbs free energy of each component in each phase is equal.
Equivalently, the compositions of the phases and l at which these conditions hold
correspond to the common tangent constructions.
For a system Ni-Cu:
Can we derive the phase-diagram?

G = XA
L
(T TA )
(T TB )
+
X
L
B B
TA
TB
+ RT (XA
lnXA
+ XB
lnXB
)
l
l
l
l
Gl = RT (XA
lnXA
+ XB
lnXB
)
At a Temperature T
GA = GA .
(T TA )
l
LA
+ RT lnXA
= RT lnXA
...(1)
TA
(T TB )
l
LB
+ RT lnXB
= RT lnXB
...(2)
TB
For Ni-Cu:
4 1.11.10
71
LN i = 2310 J/cm3 LCu = 1728 J/cm3 .

R = 8.314 J/Kmol v = 7.42 cm3 .
Figure 4.5
For phase-field purposes we always take free energy density so if we divide the free energy
by the molar volume we get the free energy pure unit volume. The equations for the
free energies per-unit volume become,
(T TA ) RT
RT
l
+
lnXA
=
lnXA
TA
Vm
Vm
(T TB ) RT
RT
l
LB
+
lnXB
=
lnXB
.
TB
Vm
Vm
LA
We can now non-dimensionalize our system by dividing throughout with

ing TA as reference temperature

l
A (T TA ) + TlnXA
L
= TlnXA
T
A
l
B (T TB ) + TlnXB
= TlnXB
L
TB

A (T TA )
lnXA
= lnXn L
TT
A
RTA
Vm
and choos-
4 1.11.10
72

A (T TA ) .
= lnXA
L
TTA
Similarly;
B
ln(1 XA
) = lnXB
L
(T TB )
TTB

l
exp lnXA

) =
(1 XA
l
exp lnXB
XA
A (TT )
L
A
TT
A
B (TT )
L
B
TT
B

l LA (T TA )
exp lnXA
TTA
XA
=

l LB (T TB )
1 + exp lnXB
TT
B
Equivalently the liquidus can be written as:

+ LA (T TA )
exp lnXA
TTA
l
XA
=h

i
+ LB (T TB )
1 + exp lnXB
TT
B
Slopes of solidus and liquidus.

I
l
A (T TA ) + TlnXA
= TlnXA
L
T
II
l
B (T TB ) + TlnXB
L
= TlnXB
TB
XA
+ XB
=1
l
l
XA
+ XB
=1
, X , X l , X l
Variable T, XA
B
A
B
4 1.11.10
73
There are four equations V Degree of freedom 5-4=1.

l
We choose XB
a8 our independent variable.
Differentiate I
LA
T2
III
T
Xal
LA
XA
2
T
l
XB
1 XA
1
= l
l
XA XB
XA
XA
XA
=
l
l
XB
XA
Similarly for II
IV
LB
XB
2
T
l
XB
XB
XB
=
l
l
XB
XB
Adding III and IV;
XA
XB
+
=0
l
l
XB
XB
XB
XA
1 T

(X
L
+
X
L
)
=
A A
B B
l
l
l
T 2 XA
XB
XA
T
=
l
XB
Similarly for solidus
T
=
XB
1
T2
XB
XA
l Xl )
XB
A

L + X L
XA
A
B B
Xl
l
XA
)
X
B
A

1
l L + X l L
X
2
A A
B B
T
( XB
5 1.11.10
5.1 lecture 6
Phase-field Evolutions:
1. Van-der Waals: - 1893 (Density variations as a functions of h
h distance along gas-liquid interface.
Introduction of square gradient energy term).
2. Ginzburg-Landau: - 1920 (Free energy of a non-uniform system).
Cahn-Hilliard: - 1958 (Free energy of a non-uniform system).
3. Allen, Langer: - First phase-field formulations of dynamics
in phase transitions (solidification,Langer).
Free energy of a non-uniform system:
Postulate: - The free energy of a system dependent on an intensive property of the
system depends on the local value and on its variation a cross a system (gradients).
f0 : - Equilibrium energy of a uniform system at c.
f (c, c, 2 c )
Expanding f around f0 as a Taylor series would allow us to write f as a function of
compositions and its gradients. Since f is a scalar, its value should be independent of
the directions of the gradient: - hence only even powers of the gradient can occur in the
expansion.
f (c, c, 2 c) = f0 (c) + k1 2 c + k2 (c)2
Integrating over a volume,
F = NV
f dV = NV
(f0 (c) + k1 2 c + k2 (c)2 )dV.
5 1.11.10
75
NV : - Number of molecules per unit volume.

Z
k1 cdV =
k1
(c)2 dV +
c
k1 (c n
)dS
One can always choose a surface such that the second integral goes to zero.
F = NV
k1
fo (c) + k2
c
F = Nv
(c) dV ;

k1
k2
k
c
(fo (c) + k(c)2 )dV
For convenience, and in cases where partial molar volumes of components are equal, one
can write f0 also as a energy E/vol. such that,
F =
(fo0 (c) + k 0 (c)2 )dV
f00 and k 0 (c)2 are quantities per unit vol. of the system.
What is the interfacial energy with this definition of energies?
Interface energy of the system by definition is the difference per unit area of the actual
free energy of the system with the interface and what the system would have, if it were
continuous.
The continuous term is uniquely defined at equilibrium between the phases and .
can be written as: Z
F = A [fo0 (c) + k 0 (c)2 (cB (e) + (1 c)A (e))]dx.
Z x
= [fo0 (c) + k 0 (c)2 (cB (e) + (1 c)A (e))]dx.
x
fo0 (c) = cA + (1 c)B .

Z
= {B B (e)) + (1 c)(A A (e)) + k 0 (c)2 }dx.
x
f (c) = c(B B (e)) + (1 c)(A A (e)).

f (c) > 0.
5 1.11.10
76
{f (c) + k
c
x
2
}dx.
Figure 5.1
c 2
If one reduces k 0 ( x
) by making the interface broader if will be at the expense of incorporating more material at the interface, such that f (c) (goes up). On the other hand,
reduction of material at the interface increases the gradient. A compromise between two
terms gives an equilibrium interface.
Concept of variational derivative/(Derivation of the Euler -Lagrange equation).

Z
f (c, c)dV

Z
2f
f
c +
c dV
F (c + c) =
f+
c
c

Z
f
f
F =
c +
c dV
c
c
Weak approximation c = c

Z
f
f
F =
c +
c dV
c
c

Z
Z
Z
f
f
f
=
cdV +
n
dSc
cdV
c
c
c
ZV
ZS
f
f
F =
cdV
cdV
c
V c
S
F =
5 1.11.10
77
The above is obtained by choosing a surface over which the surface integral goes to zero,
this is always possible.
c is a delta function around c where we compute the variation. Using the property
of function
Z
f (x)(x x0 )dx = f (x0 )x

(

)
f
f
F =

c.
c c0
c
F
f
f
=
c
c
c

F
=
f
c
c
c
we name this operator : =

c
Using this operator on,
=
c
c
Z "
x
f (c) + k
c
x
2 #
f
2c
= 2k 0 2 .
c
x
Z
Z
f dc
2 c dc
= 2k 0 2
.
c dx
x dx
2
c
0
f = k
+ const.
x
2
c
At x =
= 0 and
x
Therefore:
const = 0
dx.
f = 0.
5 1.11.10
78
f = k
=
c
x
2
: Equipartition of energy
f (c) + k
c
x
2
dx.

c 2
=2 k
dx.
x
Zx
Z p
c
c
0
=2 k
dx 2 k 0 f /k 0 dc.
x
x
x
x
Z
Z p
=2
k 0 f dc.
x

dc 2
Also
dx
p
dc
f /k 0 =
dx
dc
dx = p
f /k 0
Z
Z c
dc k 0
x=
f
c
o
f
=
k0
is the interface width.

We see - is inversely proportional to
Z c
c
k 0 dc
.
f
dc
p
f (c)
6 1.11.10
6.1 lecture 7
In the Cahn-Hilliard approach, the surface energy is fixed by the form of the free
energy. While this is true for certain systems, in general the surface excess is a property
independent of the free energy parameters. Hence one would like to set this property
independent of the bulk system.The way to do this, is to choose two fields. 1) denoting
the volume fraction of a phase and the second 2) the mole fraction of the components.
Let us say the volume fraction corresponding to a phase is . Then in a two-phase
system, the second phase has volume fractions (1-). This system can have minimum of
two components. We denote A,B, with mole fractions cA and cB such that cA + cB = 1
in each phase and we can denote the concentration field in the system as c.
Following the same principles to write the energy of the system as the Cahn-Hilliard
equation, we can write,
F =

f (c, ) + k |O|2 dx.
Points to note:
1) We have chosen the energy functional to be independent of the gradient in the concentration. This is true for small concentration gradients and corresponding small gradient
energy coefficients for the concentration field.
2) k , is the gradient energy coefficient for the gradients in the order parameter . This
can be tuned to set the right surface energies.
3) f(c,) can be broken down into: fb (c, ) + w().
6 1.11.10
80
where w() denotes an equivalent term to f (c) in the Cahn.Hilliard equation.
Figure 6.1
To define our surface energy we would need to define our energy of a uniform homogeneous system; consisting of a mixture of two phases. This can be done similar to what
we have encountered in the case of the Cahn-Hilliard equation.
Figure 6.2
l
(c) + (1 c)feq
) + w().
f (c, ) = f (c, ) (feq
Or alternatively in terms of the Grand Chemical potential or the partial molar Gibbs
free energy of the system, we can write;
eq
f (c, ) = f (c, ) (eq
A c + B (1 c)) + w().
6 1.11.10
81
Then, the surface energy reduces to:

eq
2
[f (c, ) (eq
A c + B (1 c))] + w() + k |O| dx.
Notice, we have not lost the dependence of on the free energy density of the phases.
However, there exists now another tunable function w() to get the surface energies that
is representative of an interface.
The extremizer of the above function would be the Euler-Lagrange equations, we had
for the Cahn-Hilliard equation.
c
f
c
f (, c)
c
f (c, )
d2
+ w0 () 2k 2 = 0 (1)
dx
f
=
(B A ) = 0.
c
=
= (B A ) = eq chemical potential of the system.

= (B A ) (2).
(c,)
To integrate () we need to write ( f
) in terms of the total derivative of .
f
df
df dc
=
d dc d
From (2) the minimizing condition for
f
df
dc
d
=
eq
(f c).
d
d
d
Equation (1) becomes
d2
d
(f c) + w0 () 2k 2 = 0.
d
dx
d
d2
(f c) + w0 () = 2k 2 .
d
dx

d
Multiplying
on both sides.
dx
f
= (B A ) = eq .
c
6 1.11.10
82
d2 d
d
d
d
=
(f c)
+ w0 ()
.
dx2 dx
d
dx
dx
Integrate both sides.
2
d
= (f c) (f (0) c(0)) + w().
k
dx
We denote F (c, ) = (f c).
2
d
= F (c, ) F (c(0), 0) + w().
k
dx

d
1 p
=p
F (c, ) F (c(0), 0) + w().
dx
k
2k
The surface energy
can then be derived using,
F (c, ) F (c(0), 0) = f (c, ) (f (0) + ep c c(0))
eq
= f (c, ) (eq
A c + B (1 c)).
2
Z 1
Z
d
d
dx 2
k
d
=2
k
dx
dx
0
Z 1
1 p
=2
k p
F (c, ) F (c(0), 0) + w() d.
k
0
Z 1
p p
=2
k F (c, ) F (c(0), 0) + w() d (3)
0
The interface width can also be derived as;

d
1 p
=p
F (c, ) F (c(0), 0) + w().
dx
k
p
Z 1
k d
p
= (4)
F (c, ) F (c(0), 0) + w()
0
Notice we can also use (2) to derive the equilibrium concentration profile.
f
(, c) = (B A ). Hence c can be written as a function from.
c
In systems, where the free energy of the (phases) are closely related the term
F (c()) F (c(0), 0)
is generally small, which implies equations (3) and (4) can be simplified to,
6 1.11.10
83
Figure 6.3
=2
1p
p

w() d (5) k w
p
k
k
p
d (6)
w
w()
k (7) k
/w (8) w/
Therefore one can propose to write down F as;
F =
[fb (c, ) + |O|2 +
w()]d.
where w() is dimensionless term.

We will use this formulation of the model throughout in our discussion.
Points to discuss:
1)what is the form of w()?
If we see (5) and (6) and use (7) and (8) we get;
=2
Z
we want 2
1p
w()d.
0
1p
w()d = 1.
6 1.11.10
84
Posible constructions are;

w() =
16
(1 )
2
(Obstacle)
and
92 (1 )2
(Double-well)
Integrate and verify the ansatz

Dynamics
We have two fields; c, in our system, while c is a conserved quantity, is nonconserved as we have transition from one phase to another.
The field c evolves through gradient dynamics. This implies the driving force for flux
is the gradient of a potential.
Conservation law for c can be writing down as
c
= O Je
t
From irreversible thermodynamics one can write down.
Je ; as a result of a linear combination of driving forces in the system. the driving fores
are the gradients of the intensive properties of the system.
Je L0 O(T )L1 O
Je L0 O(T ).
f
c
f
chemical potential
c

f
f
c
= O L0 O(T ) + L1 O
= O L0 OT + L1 O
t
c
c
L0 represents the coupling between the temperature and concentration field. L0 , L1
are mobility coefficients which denote velocity/(unit driviforce).
The system is uniform and stationary when there are no gradients in the system:
O(T ) = 0;

f
O
= 0.
c
6 1.11.10
85
In general for a multi-component system;

X
ci
= O (L00 O(T )) +
Lij O
t
j
f
cj
The field has a dynamics based on a phenomenological minimization of energy,
F
= M
.
t
6 1.11.10
86
6.2 Tasks to perform

1. Make an infile, with the free energies of the form:
f (c, T ) = cN i LN i
T TN i
RT
T TCu
(c log cN i + cCu log cCu ) ,
+
c
L
+
Cu Cu
TN i
TCu
vm N i
where stands for both the solid and the liquid phases. The parameters for each
of the phases are listed below:
=Solid
=Liquid
LN i
235e7
0.0
LCu
172.8e7
0.0
=Solid
=Liquid
TN i
1728K
1.0
TCu
1358K
1.0
Table 6.1: Table containing the values for the latent heats and the temperatures for the Ni-Cu
alloy.
2. Plot the phase diagram, get the concentrations of the liquidus and the solidus at
the temperature 1500K. You can input the temperature in the program as 1500K
and plot the full phase diagram. Use the tool binphasediag .
3. Using the concentrations at the solidus and the liquidus at the temperature 1500K
calculate the slope of the liquidus using the formula:
csolidus
Ni
mLiquidus
Ni
cliquidus
Ni
1 csolidus
Ni

liquidus
1 cN i
RT

=

vm 1
solidus
solidus
solidus
solidus
(1 cN i
)LCu
+ cN i
LN i
T
4. Compute the Latent heat of transformation at 1500K. Use the equation:

L = T S liquidus S solidus ,
where, S liquidus and the solidus S solidus denote the entropy and can be written as
f
, standing for both solid and the liquid.

T
5. Compute the parameter in the following fashion from the Sharp Interface limit.
Propose that the Grand Chemical Potential as the difference as the following:
(f c) |10 = L
(T )
|mliquidus
cN i |
Ni
6 1.11.10
87
where, (T ) is the equivalent undercooling that would give rise to the same driving
force than that given by the grand chemical potential difference of the phases. Then
use the following relation:
V
T
= L
=
(T )
|mliquidus
cN i |
Ni
V liquidus
|mN i
cN i | = V,
L
where is the kinetic coefficient of the phases. and cN i is the difference in

the concentrations of the solidus and the liquidus at the given temperature. This
denotes the freezing range of the alloy. The above expression gives an expression
for the paramete ,
L
cN i |
T |mliquidus
Ni
where is given as (0.33e-2 m/K/s) for the present system. We derive this from
the fact that for the pure materials Ni the measured is (0.29e-2m/K/s) and for
Cu it is (0.37e-2m/K/s), and so for the present case we approximate an alloy of the
following to be an average of the two. YOU CAN THINK OF BETTER ONES.
6. Next we input the surface energies and the diffusivities at the particular temperature given as below. Note, here too we use an average value for the case of the
surface energy = 0.335 J/m2 . In the solver we input surface entropy densities
instead of the surface energy. Hence to retrieve the same surface energy, one would
need to divide the surface energy by the temperature at which one is simulating,
which would help retrieve the same surface energy one needs to input in the simulation = /T .
In a binary alloy there is only one independent inter-diffusivity in a given phase.
We use the following values for the diffusivities.
DN i = DCu
Solid
1e-13 m2 /s
Liquid
1e-9 m2 /s
7. Start a simulation with this infile, for the case of a one dimensional simulation with
the solid and the liquid phases at the equilibrium concentrations, and verfiy that
6 1.11.10
88
indeed the calculations of the phase diagram and the equilibrium concentrations
are correct.
8. Next change the concentration of the liquid towards that of the liquid and redo
the simulation. One should observe that now the interface profile moves. Note
down the profile of the concentration that you see. This is called giving a supersaturation to the liquid, that is the liquid has more Cu, than the solid can dissolve
at equilibrium which gives a driving force for the system. Compare the solute
profiles with those that you observe for the case of equilbrium.
9. Change the simulation domain to a two dimensional one and perform the simulation
by placing the nuclei at the center. In a two dimensional case, the driving force for
the transformation needs to exceed a critical driving force required to overcome
the capillary tension. This gives the size of the critical radius at a given super
saturation. For the given setting of the grid-sizes the nucleus is far beyond the
critical size, and hence you see it growing. Note, it is growing circular.
10. Change Function A in the infile to 1, and put the strength of the anisotropy in the
infile to 0.04 and put the nucleus at the corner of the domain. What shape do you
see? The change in shape is due to surface energy anisotropy in the system. This
will eventually give rise to a dendrite if run long enough.

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Microstructure Simulations

B. Nestler, F. Wendler, A. Choudhury

B. Nestler, A. Choudhury, F. Wendler

B. Nestler, A. Choudhury, F. Wendler

General problem definition

B. Nestler, A. Choudhury, F. Wendler

Effect of microstructure - example

J.M. Garcia-Infanta et al., Scripta Mater. 58 (2008) 138.

Technical importance of solidification

Technical solidification processes (incomplete)

B. Nestler, A. Choudhury, F. Wendler

Some general terms used in the course

Equilibrium: State of minimal free energy (G or F ). Phases in contact do

B. Nestler, A. Choudhury, F. Wendler

Solidification basics - casting

B. Nestler, A. Choudhury, F. Wendler

Kurz, Fisher, Fig. 0

Solidified ingots - morphology

B. Nestler, A. Choudhury, F. Wendler

Solidified ingots - morphology II

Aluminum ingot (5 cm)

H. K. D. H. Bhadeshia, University of Cambridge

Kurz and Fisher, Fig. 1.6

B. Nestler, A. Choudhury, F. Wendler

The role of heat extraction

After casting the liquid metal, heat of different physical

B. Nestler, A. Choudhury, F. Wendler

Figure: Quasi 1-D experiment,

1. Cooling from pouring temperature,

B. Nestler, A. Choudhury, F. Wendler

Directional solidification - experiments

Figure: Eutectic growth in SCN - DC,

[Akamatsu et al., Journal of Crystal Growth 299 (2007) 418]

B. Nestler, A. Choudhury, F. Wendler

Directional solidification - principles

B. Nestler, A. Choudhury, F. Wendler

Directional solidification - technical applications

Al alloy - polycrystal [Tom Quested,

Solar grade silicon, directionally

B. Nestler, A. Choudhury, F. Wendler

Special solidification methods - metal matrix composites

Figure: Steps of gas pressure infiltration: a)

B. Nestler, A. Choudhury, F. Wendler

Figure: Pure Al matrix reinforced

Special solidification methods - Thixocasting

Sample in solid state as

material with rheology like

B. Nestler, A. Choudhury, F. Wendler

What is the aim of computational materials science?

B. Nestler, A. Choudhury, F. Wendler

Why is study of solidification important to physicists and

B. Nestler, A. Choudhury, F. Wendler

[W. Losert et al., Phys. Rev. E 58(6) (1998) 7492.]

B. Nestler, A. Choudhury, F. Wendler

Dendritic Solidification - phase-field simulations

with P. Galenko, D. Herlach, (DLR Koln),

B. Nestler, A. Choudhury, F. Wendler

Eutectic Solidifications - Types and Instabilities

Below the eutectic

B. Nestler, A. Choudhury, F. Wendler

Eutectic Solidification - Length Scales

B. Nestler, A. Choudhury, F. Wendler

Eutectic Solidification - Instabilities

B. Nestler, A. Choudhury, F. Wendler