vz
D
L
_
where z is the distance from the solidliquid interface and D
L
is the diusion coe
cient of solute in the liquid. The solute concentration prole in the liquid causes the
liquidus temperature T
L
to increase away from the solidliquid interface (curved lines
in Figure 2.2 show how solute concentration C changes T
L
). The resulting liquidus
temperature prole is shown in the lower left, along with the the temperature prole
required for heat ow, T
q
. Without the eect of solute rejection, as in the case of a
pure material, any perturbation to the solidliquid interface would result in the solid
protruding further and the temperature gradient becoming sharper, which would cause
26
the perturbation to remelt and preserve the stability of the planar interface. However,
due to the variation of T
L
with z, under some conditions T
q
can be less than T
L
. Under
steadystate conditions the temperature is T
q
< T
L
, so solidication can occur. Any
perturbation increases the composition gradient, so the perturbation will tend to grow.
Because the constitution of the alloy determines the dierence between T
L
and T
q
, this
eect is known as constitutional undercooling.
Figure 2.2. The conditions which give rise to constitutional undercool
ing. Top, the solute concentration prole in the liquid during steadystate
directional solidication at velocity v. Assuming thermodynamic equi
librium at the interface, the temperature in the liquid T
L
is governed by
the phase diagram, bottom right. T
L
is shown as a function of z in the
lower left. Constitutional undercooling occurs if the temperature prole
required for heat balance T
q
is less than T
L
ahead of the interface. Figure
from [2].
A more rigorous approach to the criteria for growth of a perturbation to a solid
liquid interface moving at velocity v, as in directional solidication, was developed by
Mullins and Sekerka [3]. Unlike the constitutional undercooling criteria, they took
27
capillarity into account. Assuming isotropic bulk and surface parameters and local
equilibrium at the interface, and no convection in the liquid, they calculated the time
rate of change
of the amplitude of a sinusoidal perturbation of innitesimal initial
amplitude superimposed on a planar solidliquid interface as a function of perturba
tion wavelength and solidication conditions. When the rate of change is positive, the
perturbation grows, leading to instability in the interface. In this model, the interface
is stable if there are no perturbation wavelengths which have positive growth rates
(Figure 2.3).
Figure 2.3.
/ as a function of wavelength for two cases: curve 1 unsta
ble, curve 2 stable [3].
The shape of a dendrites during steadystate growth has also been closely studied.
Ivantsov [4] showed that a dendrite with a parabolic tip (or a paraboloid in 3D) grows
with a constant shape under the constraint of constant interface temperature and
composition. The relationship between interface composition and velocity is:
(2.2) C
t
= C
0
/ [1 (1 k)Iv(P)]
28
where C
t
is the composition at the tip of the dendrite, C
0
and k are as dened before,
and P is the solute Peclet number P = V R/2D
L
where V is the steadystate velocity,
R the tip radius, and D
L
the solute diusion coecient in the liquid. The Ivantsov
function is dened as Iv(P) = P exp
P
E
1
(P) and E
1
(P) is the rst exponential integral.
Ivantsovs solution, however, does not include the eect of capillarity, which can be
an important eect at highcurvature regions such as the tip of a dendrite. The more
recent development of solvability theory [5, 6] showed that anisotropy in the surface
energy perturbs the shape of the growing tip and selects the velocity of the tip. Four
fold anisotropy in the surface energy is assumed for crystals with cubic symmetry. The
eects of this anisotropy lead to a perturbation to the paraboloid shape by a term of
the form [7]
(2.3) z =
r
2
+ A
4
r
4
cos 4
where A
4
= 1/88 and (r, ) are polar coordinates in the plane normal to z, the growth
direction.
2.2. Coarsening
The process of coarsening also has an important eect on the properties of dendritic
microstructures. During casting or other processes where dendritic microstructures are
formed, coarsening occurs while the dendrites grow. Coarsening can be most easily un
derstood as a consequence of thermodynamics, where the system seeks to reduce its
total energy by reducing its interfacial area and therefore its total interfacial energy.
29
Coarsening can be especially important at the center of a cast part, where the rela
tively slow removal of heat can lead to a region of solidliquid coexistence (called the
mushy zone) which can last long enough for coarsening to cause signicant changes to
the microstructure. Coarsening in the mushy zone causes secondary arms to dissolve
away, leading to less ne dendritic microstructures and generally degrading mechanical
properties.
Kinetically, the process of coarsening is driven by dierences in concentration at
the solidliquid interface caused by the GibbsThomson eect, in which the equilibrium
composition of an twocomponent system is modied by variations in curvature at
the solidliquid interface. This composition dierence is due to equilibrium pressure
changes caused by interfacial tension. The GibbsThomson equation states
(2.4) P
L
P
S
=
where is the interfacial energy between the solid and liquid phases, and is the mean
curvature of the solidliquid interface (to be explained in greater detail in Section 2.3).
Starting from the GibbsThomson equation, it can be shown [8] that the equilibrium
composition of the liquid at the solidliquid interface in a twocomponent system is
given by
(2.5) C
L
= C
0
L
+ H
C
L
is the composition of the liquid at a curved interface, C
0
L
is the equilibrium composi
tion of the liquid at a at interface, and is the capillary length determined by material
30
parameters including interfacial energy, molar volume of the solid, and curvature of the
free energy function.
The dierences in composition caused by the GibbsThomson eect lead to solute
concentration gradients in the liquid. These gradients cause solute diusion in the
liquid, leading to transport of solid from highcurvature regions to lowcurvature re
gions and therefore coarsening. The same process occurs in the solid, but since solute
diusion through the solid is usually much slower than through the liquid, coarsening
in the liquid phase usually causes much greater changes to the microstructure.
2.2.1. Coarsening of Spherical Particles
Lifshitz and Slyozov [9] and Wagner [10] independently developed a theory of the
coarsening of spherical particles, generally referred to as the LSW theory. The model
assumes a system composed of A and B atoms containing a distribution of spherical
particles of the phase composed entirely of B atoms in a matrix of the Arich
phase. Because of the GibbsThomson eect, B atoms ow from the smaller particles
to the larger particles through the phase, which causes the smaller particles to shrink
and the larger particles to grow. The mean particle size of the distribution grows as
(2.6)
R
3
(t)
R
3
(0) = K
LSW
t
where
R(t) is the mean particle radius at time t, and K
LSW
is a rate constant de
pending on material parameters and temperature. The LSW theory also predicts a
distribution of particle radii about the mean radius that is timeindependent when
scaled by
R
3
(t). Because of this property, the particle size distribution is said to be
31
selfsimilar. Important limitations of this model are that it assumes that the spherical
particles are innitely far apart and have a negligibly small volume fraction relative to
the matrix phase. Nonetheless, this model has proved useful in describing coarsening
in many binary alloys, and has also served as the basis for more advanced coarsening
models for spherical particles.
2.2.2. Coarsening of Dendritic Microstructures
Because dendritic microstructures are so much more complicated than a spherical par
ticle distribution, developing a comprehensive theory of the coarsening of dendrites is
a much more dicult problem than a spherical particle distribution. However, due to
the important eects of dendritic microstructure on castings, directional solidication,
and other technologically important processes, coarsening in dendritic microstructures
has been studied extensively.
The change in spacing between the secondary arms
2
has frequently been used
to quantify the timedependence of the coarsening process. By measuring the time
evolution of the spacing between secondary arms during coarsening of dendritic AlCu,
Bower et. al. [11] showed that
(2.7)
2
t
1/3
f
Thus
2
evolves with time analogously to average particle radius in the LSW model.
Several dierent theoretical models have been used to describe the mechanism of
coarsening in dendrite secondary arms. Most have treated the arms of the dendrites as
either cylinders or teardropshaped protrusions. Kattamis et. al. [12] treated the arms
32
as cylinders, but assumed that one cylinder had a smaller radius than the others and
therefore dissolved with a shrinking radius, called radial remelting. Kahlweit et. al. [13]
treated the dendrite arms as cylinders with spherical tips. Since the tips have a smaller
radius of curvature, dissolution primarily occurs at the tip in this model and the arms
shrink from their tips down to the roots while the radii remain practically unchanged.
This process is known as axial remelting. The rst attempt to model dendrite arms
as teardropshaped objects considered individual dendrites which would detach from
the primary arm as the thin neck at the arm shrank due to solute diusion from the
neck to the wider portion of the teardrop. [14, 15] The next such model considered
two adjacent teardropshaped secondary arms which eventually coalesce into a single
arm. [16] These models are summarized in Figure 2.4.
2
is a useful metric to describe a dendritic microstructure because it has been
correlated with physical properties, and because it is easy to measure given a physical
specimen that has been properly prepared. However, the use of
2
has disadvantages.
It is highly dependent on which 2D plane is visible after sample preparation, and
because it is based on a 2D section, cannot fully describe the complexity of a 3D
microstructure. Also, it has been observed that after extremely long coarsening times,
an initially dendritic microstructure can break up into spherical particles [17], in which
case
2
loses its meaning.
In order to adequately characterize a dendritic microstructure in 3D, the inverse
of surface area per unit volume, S
1
v
, has proven useful. It also scales with t
1/3
[17],
is independent of the morphology of the system, and does not depend on stereological
assumptions necessary for 2D images. The relationship S
1
v
t
1/3
has been shown to
33
Figure 2.4. Four dierent models for isothermal coarsening: (1) radial
remelting, (2) axial remelting, (3) arm detachment, (4) arm coales
cence [12].
hold during the coarsening of directionally solidied dendritic SnBi [17], AlCu [18],
and PbSn [19] and equiaxially solidied dendritic AlCu [20].
2.3. Interfacial Curvature
Because curvature drives coarsening as shown by Equation 2.5, it is important to
have a rigorous mathematical description to characterize the curvature at every point
of an interface. For any given patch of surface area on an interface, two orthogonal
planes can be chosen whose intersections c
1
and c
2
with the interface are curves with
radius of curvature R
1
and R
2
. Both these planes also contain the normal vector to the
interface n. The principal curvatures
1
and
2
are the inverse of the radii of curvature
of the two curves c
1
and c
2
, as in Figure 2.5. The mean curvature H is the average of
34
Figure 2.5. A interfacial patch with corresponding radii of curvature, R
1
and R
2
. n represents the unit normal vector, while p is the point of
interest.
the curvatures
(2.8) H =
1
2
(
1
+
2
)
Through linear algebra, it can be shown that the mean curvature H is independent
of the choice of curves c
1
and c
2
. Another invariant of the choice of curves is the
Gaussian curvature K:
(2.9) K =
1
2
=
1
R
1
R
2
Although the principal curvatures are easier to understand physically, H and K are
easier to calculate for digital representations of 3D microstructures. This can be done
35
using either a surfacemesh based description of the interface, or using a diuse inter
face representation. For a diuse interface representation, the mean curvature can be
calculated using
(2.10) H =
1
2
( n)
where n is the normal vector to the interface calculated from gradients of the order
parameter
(2.11) n =
[[
The Gaussian curvature can be calculated using
(2.12) K = n adj(He()) n
where He() is the 3 3 Hessian matrix of second partial derivatives of the order
parameter, and adj(He()) is the adjoint of the Hessian matrix [21]. More detail on
the numerical implementation of these methods will be provided in Chapter 3. The
principal curvatures can then be calculated from H and K using
1
= H
H
2
K (2.13)
2
= H +
H
2
K (2.14)
36
2.3.1. Interface Shape Distributions
In order to summarize the distribution of the principal curvatures found throughout the
interface of a multiphase microstructure, the Interface Shape Distribution, or ISD, has
been developed [22, 23]. An ISD is a twodimensional contour plot of the probability
P(
1
,
2
) of nding a patch with curvatures
1
and
2
between
1
+d
1
and
2
+d
2
.
(
2
is always dened to be greater than or equal to
1
.)
Figure 2.6. Interface Shape Distribution (ISD).
The ISD can be broken down into four regions (Figure 2.6):
37
Region 1: solid on the concave side of the interface.
Region 2: saddleshaped with H > 0, K < 0.
Region 3: saddleshaped with H < 0, K < 0.
Region 4: liquid on the concave side of the interface.
Other features of interest occur along the axes and the line
1
=
2
:
The interface is planar along the line
1
=
2
= 0.
No patches appear below the line
1
=
2
since
2
1
by denition.
Interfacial patches on the
1
=
2
> 0 line correspond to solid spherical shapes,
and patches along
1
=
2
< 0 are liquid spherical shapes.
For
1
= 0, the interface is cylindrical with solid inside, and for
2
= 0, the
interface is cylindrical with liquid on the inside.
2.3.2. Rate of Change of Curvatures
Because coarsening changes the morphology of interfaces, we are concerned with not
just a static description, but also in how curvatures change as the interface itself
changes. Mendoza et. al. calculated the change in curvatures of a complex microstruc
ture by computing the time rate of change of H and K using an order parameter
description as in Equation 2.10 and 2.12 [24]. However, this approach did not consider
the eect of the motion of the interface itself on curvatures. To account for this eect,
another term must be added which has the form of a convective derivative. Following
is a more detailed exposition of this eect.
Let o(t) be a surface evolving in time with v(x, t) dened to be the velocity eld of
o(t), which gives the velocities for evolving particles constrained to o. Given a scalar
38
eld (x, t), smooth in a 3dimensional neighborhood of o(t) for all t, then by the
chain rule [25],
(2.15)
=
t
+v
Therefore the time derivative of mean curvature for a point on the interface moving
through space with velocity v can be found in the same way:
(2.16)
H =
H
t
+v H
Similarly, the time derivative of Gaussian curvature for a point on the interface moving
through space with velocity v is
(2.17)
K =
K
t
+v K
Using a diuse interface model,
H and
H = (2H
2
K)v
1
2
(v
11
+ v
22
)
(2.19)
K = 2HKv H(v
11
+ v
22
) +
H
2
K(v
11
+ v
22
)
39
(where we have used the notation
H and
K rather than
H
t
and
K
t
as in [26] to be
clear that we are considering a point moving with the interface).
2.4. Topology
Topology is the study of solid bodies which are not changed by elastic deformations
such as stretching and bending. In materials science, methods from topology are used
to characterize the connectivity of multiphase microstructures. The use of topological
measurements as a means of characterizing microstructures was pioneered by DeHo
et. al. [27]
One of the most convenient measures of the topology of a microstructure is the
genus, which is dened as the maximum number of cuts along closed simple curves
that can be made in a body without breaking it up into smaller bodies. Genus is a
topological invariant of a surface, meaning that it does not change if the surface is
elastically deformed. Genus can also be related to the number of loops or handles in
the structure minus the number of independent bodies or voids:
(2.20) g = h v + 1
To illustrate genus, consider a few simple examples. For a simple sphere, g = 0,
since there is no cut that can be made along a simple curve that will render the body
still connected. Using Equation 2.20, a sphere has no handles and is itself a single void,
giving g = 0. A sphere, cube, pyramid, and cylinder are all topologically equivalent
and therefore all have g = 0. For two isolated spheres, g = 1 because you would need
to join the two surfaces (a negative cut) in order to produce a connected body. A
40
torus or doughnutshape will remain connected after a single cut, so it has a genus of
1.
Genus can also be related to other geometric properties of a microstructure. Us
ing the GaussBonnet theorem, genus can be related to the integral of the Gaussian
curvature K of the interface [28]:
(2.21) g = 1
1
4
_
S
KdS
where the integral is over the surface area of the interface.
Genus can also be related to the Euler characteristic, another topological invariant.
For a surface of polyhedra, the Euler characteristic is calculated from the number of
vertices V , edges E, and faces F:
(2.22) = V E + F
The genus can be calculated from the Euler characteristic using
(2.23) g = 1
2
2.5. SelfSimilarity
In the context of a system evolving in time, a microstructure that is selfsimilar is
timeindependent when scaled by the appropriate timedependent characteristic length.
For example, in the LSW theory [9,10], the particle size distribution is selfsimilar when
scaled by the average particle radius
R(t), which is proportional to t
1/3
(Figure 2.7).
41
Figure 2.7. Particle radius distribution predicted by the LSW the
ory [29]. The horizontal axis is the radius of a particle divided by the
average particle radius for the entire collection of particles at time t. The
vertical axis is the probability of nding a particle with that radius. Be
cause the distribution is constant with time, the particle size distribution
is said to be selfsimilar.
Since this rst use of the concept of selfsimilarity in materials science, other mate
rials systems have been investigated to determine if they exhibit selfsimilar evolution
in the late stages of coarsening. Mendoza [18] and Kammer [19] investigated the
evolution of directionally solidied dendritic AlCu and PbSn, respectively, coarsened
just above the eutectic to form a solidliquid mixture. They found that S
1
v
t
1/3
,
and thus that S
1
v
is an appropriate characteristic length scale for coarsening in this
system, analogous to
R(t) for a spherical particle distribution. Since in each case the
morphology is a complicated interconnected structure, ISDs were used to characterize
the morphologies, and were scaled by S
1
v
. They found that for these directionally
solidied systems, the scaled ISDs were not selfsimilar, even for extremely long coars
ening times. Instead, the nal morphology was liquid cylinders whose axis was aligned
with the solidication direction.
Fife conducted a similar study of dendritic AlCu during coarsening [20], but in
this case the dendrites were produced by equiaxial solidication. She found that again,
42
S
1
v
t
1/3
, but that in this case, the ISDs were selfsimilar for suciently long coarsen
ing times. When compared with [18] and [19], this shows how the initial morphology
of the dendritic structure can have a signicant impact on its morphological evolution.
Selfsimilarity has also been found in the shape of the interface between phases
before and after pincho by Rayleigh instability. As the pincho is approached, a
nitetime singularity occurs as the curvature at the point of pincho becomes innite.
The length and time scales near the singularity become much smaller than the scale of
the initial conditions that caused the singularity to form.
The following example is presented to clarify this concept. Consider a rod of one
phase embedded in another, with surface energy at the interface between the two
phases. To reduce its surface energy, the rod will pinch o if a perturbations to the
interface to the interface position forms with a wavelength of 2R or greater, where
R is the radius of the perturbation. This is the wellknown Rayleigh instability, which
causes a stream of liquid owing from a faucet to break up into drops.
In Figure 2.8, the time evolution of the rod is shown. As the cylinder approaches
the time of pincho, its shape approaches that of two opposing cones with angle 2.
Depending on the physical laws that govern the system as it approaches pinching, the
radial and axial positions of the interface may be made timeindependent by scaling by
the appropriate timedependent characteristic length. Scaling by this timedependent
factor is referred to as a similarity transformation, and is of the form:
(2.24) =
rB
(t
s
t)
, =
zB
(t
s
t)
43
5
4
3
2
1
0
1
2
3
4
5
5 4 3 2 1 0 1 2 3 4 5
5
4
3
2
1
0
1
2
3
4
5
5 4 3 2 1 0 1 2 3 4 5
5
4
3
2
1
0
1
2
3
4
5
5 4 3 2 1 0 1 2 3 4 5
5
4
3
2
1
0
1
2
3
4
5
5 4 3 2 1 0 1 2 3 4 5
Solid
Liquid
Figure 2.8. The pincho of a cylinder by Rayleigh instability as a func
tion of time. For some systems, when the coordinates of the interface
position are scaled by B/(t
s
t)
.
Although this example has focused on the time prior to pincho, selfsimilarity can
also occur after pinching in the shapes of the cones as they draw away from each other.
44
Selfsimilarity was rst found in the shape of a tapered liquid sheet after breaking
and a liquid wedge just after contact with a at solid surface [30]. An axisymmetric
lm bridge of inviscid liquid was found to exhibit selfsimilar behavior near breakup
into two droplets with an even smaller satellite droplet in between [31]. An important
result of this work was that a unique cone angle for the liquid droplets shape was
found prior to lm breakup, regardless of initial conditions. A similar result was found
for the splitting of an inviscid liquid droplet in air when a thin bridge between the two
larger drops forms [32]. Wong et. al. investigated the pincho of rods via capillarity
driven surface diusion [33]. They found that selfsimilar solutions to the shape existed
both before and after pincho, but the solutions before and after were of a dierent
nature. After pincho, a solution was found for any cone angle 2. However, prior
to pinching, a solution was found only for a unique angle = 46.04. This implies
that the pinching event introduces a universality in the morphology, which persists
after pinching, even though solutions are found at any angle after pinching. Zhang
et. al. investigated a similar geometry as [32] for a uid of viscosity (where is a
constant) surrounded by another uid of viscosity [34]. They found the selfsimilar
shapes and asymptotic angles of the liquid bridges, which were in good agreement with
the experimental results of Cohen et. al. [35]. In summary, selfsimilarity is found in
a variety of systems undergoing topological singularities driven by interfacial energy
reduction, and the singularities cause universality in the interface shapes. Although
some experiments have veried these theoretical predictions, selfsimilarity has not yet
been observed experimentally in a system of interest to materials scientists.
45
2.6. PhaseField Models
In the past few decades, great progress has been made in simulating various solidi
cation processes through the use of phaseeld models. Phaseeld models use an order
parameter to represent the phase of a system at each point. For instance, in models
of solidication, the order parameter may be assigned a value of = 0 for the solid
phase and = 1 for a liquid. The interface between the two phases is represented by
a continuous variation of the order parameter between the equilibrium values, with a
width that is typically much larger than the actual width of an interface between two
phases in a real system. Because of the continuous variation of the order parameter,
this type of model is referred to as a diuseinterface model, as opposed to a sharp
interface model, in which the boundaries between dierent phases must be explicitly
tracked.
To model the dynamics of the system, it is assumed that a freeenergy functional
(function of a function) exists that depends on the order parameter , its gradient ,
and other variables such as temperature and composition. For instance, in the case of
an isothermal, constant volume process such as coarsening, the Helmholtz free energy
is the appropriate thermodynamic quantity to be represented by a functional:
(2.25) T =
_
V
_
f(, c, T, . . . ) +
2
[[
2
+
2
c
2
[c[
2
_
dV
This functional is minimized with respect to changes of the appropriate variables
using the calculus of variations. In order to ensure that the free energy decreases
46
monotonically with time, it is assumed that
(2.26)
t
= M
= M
_
f
_
This is known as the AllenCahn equation [36]. The free energy density f(, c, T, . . . )
is typically a doublewell potential function of the order parameter with local minima
at the equilibrium values of solid and liquid. The width of the interface is a balance
between the local free energy and the gradient energy; the system wants to minimize
the interface width to minimize its free energy, but then order parameter cannot change
too quickly or the gradient energy term will become excessively large.
In a singlecomponent system, evolution is also determined by temperature varia
tion and the net rate of latent heat production at the solidliquid interface, which is
proportional to
t
:
(2.27) C
P
T
t
+ L
t
= (kT)
where T is the local temperature, C
P
is the constant pressure heat capacity, L is the
latent heat of solidication, and k is the thermal conductivity.
The model can easily be extended to a binary alloy by modifying the free energy
density using ideal or regular solution models. For regular solution model of compo
nents A and B,
f(, c, T) =(1 c)f
A
(, T) + cf
B
(, T)
+ RT [c ln c + (1 c) ln(1 c)] + c(1 c) [
S
(1 p()) +
L
p()]
(2.28)
47
where f
A
and f
B
are the (doublewell) free energy density functions for component A
and B alone, c is the mole fraction of component B,
S
and
L
are the regular solution
parameters of the solid and liquid, and p() is an interpolating function with values
p(0) = 0, p(1) = 1. In the case of a multicomponent system, it is usually assumed
that heat diusion through the system occurs much more quickly than solute diusion,
so that system can be considered isothermal or having a xed temperature gradient
with conditions set by external constraints. Using this assumption, the evolution of
the system is determined by the AllenCahn equation coupled with the CahnHilliard
equation [37]
(2.29)
c
t
=
_
M
c
c(1 c)
_
T
c
__
=
_
M
c
c(1 c)
_
f
c
2
c
2
c
__
For a more general, thermodynamically rigorous formulation, an entropy functional
S is postulated [38, 39]
(2.30) S =
_
V
_
s(e, c, )
2
e
2
[e[
2
2
c
2
[c[
2
2
[[
2
_
dV
where s is the entropy density and e is the internal energy density. Using this
functional, the system is evolved such that entropy is monotonically increasing as a
function of time. By making the appropriate substitutions and simplications, the
equations for heat diusion, solute diusion, and phase eld evolution can be derived,
and all the previously discussed models can be recovered.
To prove that their models are consistent with physical laws, most authors perform
an asymptotic or thininterface analysis. In this procedure, it is shown that when
48
the interface between phases is made suciently thin, the equations which dene the
analytical solution to the problem are recovered from the equations that dene the
phaseeld model. For example, when an asymptotic analysis is applied to a phase
eld model of alloy solidication, the equations for solute conservation, solute diusion,
and the GibbsThomson equation are recovered.
2.6.1. PhaseField Modeling of Pure Material Solidication
Phaseeld models have been especially popular for modeling solidication problems.
For pure materials, many authors have modeled dendrite growth in an undercooled
liquid. [4048] To simulate dendrite growth, some form of anisotropy in the system is
required, either in the gradient energy coecient
. The
concentration of the liquid is set to be supersaturated for the given temperature, and
a seed of solid or thermal noise is introduced to provide a nucleation site.
McFadden et. al. [42] helped validate some of the original models of 2D dendritic
growth in a pure material [40, 41] by using an asymptotic analysis to show that their
model for anisotropy of the gradient energy term reduced to the anisotropic form of
the GibbsThomson equation in the sharpinterface limit. Karma and Rappel [43]
introduced a new method for performing a sharpinterface analysis which allowed the
use of much wider interface thicknesses (on the same size scale as the capillary length)
and therefore facilitated modeling much larger physical systems. It also allowed the
selection of model parameters such that modications to the interface kinetic coecient
M
could be made much smaller than modications to the gradient energy coecient,
which could be useful for modeling systems under a variety of undercoolings. They then
49
applied the model to 3D dendritic growth and showed that their results for dendrite
tip velocity and radius were comparable to the analytical solutions of solvability theory
and to experimental results in succinonitrile [44]. Karma and Rappel also used a phase
eld model with intentionally introduced thermal noise to allow the system to grow
secondary arms [45]. Bragard et. al. modeled dendritic solidication in undercooled
nickel, using the results of molecular dynamics simulations to obtain realistic values
for the kinetic and gradient energy coecients [48].
Although most models have been numerically simulated on a uniform rectangular
grid using standard nitedierencing techniques, some models have been implemented
with more ecient computational techniques. Provatas et. al. modeled dendrite growth
using an adaptive grid whose spacing was set progressively larger farther away from
the solidliquid interface. [49] That way, the resolution was ne near the interface
where and c were large, and resolution was much coarser far from the interface
where and c were not spatially varying. Plapp and Karma introduced a model which
used an ensemble of random walkers to solve the diusion equation for heat far from
the interface, which took progressively larger steps with increasing distance from the
growing interface [46].
2.6.2. PhaseField Modeling of Binary Alloy Solidication
By modifying the free energy density to include corrections for alloy composition,
phaseeld solidication models can be extended to binary alloys [41,5057]. However,
to avoid the additional computation necessary to solve for coupled heat and solute
diusion, it is usually assumed that heat diuses much more quickly than solute, so
50
the system is either isothermal or held at a xed temperature gradient by external
constraints.
Wheeler et. al. introduced a model for isothermal binary alloys in which the compo
sition gradient energy coecient
c
= 0 [50]. They used an asymptotic analysis to show
that the solute diusion equation and solute conservation at interfaces were recovered
in the sharpinterface limit. Wheeler et. al. then expanded this model to include a
nonzero
c
in order to reproduce the experimentally observed eect of solute trapping,
in which the composition of solid growing rapidly into a liquid region is higher than
the equilibrium solid composition [41]. Elder et. al. created a model of an isother
mal eutectic system and included a stochastic noise term in both the AllenCahn and
CahnHilliard equations to stimulate nucleation [52]. Depending on initial conditions,
they reproduced in 2D diusionlimited growth, lamellar growth, and spinodal decom
position (or Ostwald ripening for oeutectic compositions). Warren and Boettinger
created a model for an ideal binary alloy in 2D based on an entropy functional with
anisotropic interfacial energy (
) [54].
Diepers et. al. added the capability to model convective ow in the melt of an
isothermal binary system [55]. They simulated coarsening of an array of particles
without and with convective ow and found that particle radii evolved with t
1/3
without
ow, in agreement with the LSW theory, and changed to t
1/2
with ow, in agreement
with theoretical predictions.
A major advance in phaseeld modeling of binary alloys came with the realiza
tion by Karma that unequal diusivities in the solid and liquid phases would lead
to three important nonequilibrium eects at the solidliquid interface, (i) a chemical
51
potential jump across the interface leading to solute trapping, (ii) an interface stretch
ing correction to solute conservation, and (iii) a surface diusion correction to solute
conservation [56]. These eects scale with the thickness of the interface, meaning that
models with relatively large values of interface thickness (for computational eciency in
modeling physically large systems) would see solute trapping and other nonequilibrium
eects appear at a much lower interface velocity than would be expected physically.
Karma then employed several clever tricks in order to eliminate these eects. He intro
duced an antitrapping current into the CahnHilliard equation which would eliminate
the eects of solute trapping:
(2.31)
c
t
=
_
M
c
T
c
j
at
_
He then used an asymptotic analysis to show how to choose the parameters of
the phaseeld model correctly in order to eliminate all three nonequilibrium eects.
Although this approach is less appealing from a thermodynamic standpoint since the
systems evolution is no longer determined from an energy functional alone, the as
ymptotic analysis shows that it accurately reproduces the sharpinterface equations
and therefore should accurately model the evolution of the system. It even has the
additional benet of allowing corrections to the kinetic coecient to the interface to
be made arbitrarily small, as in [43].
52
CHAPTER 3
Methods
3.1. ThreeDimensional Microstructure Characterization
In a diuseinterface or order parameterbased representation of a microstructure,
the phase of the system at each point is represented by the value of the order parameter
in a 3D array. This array is made up of voxels, or volume elements, the 3D equivalent of
the 2D pixels that make up a digital image. Much useful information can be obtained
from analysis of the microstructure using this 3D array as a starting point. The volume
fraction V
f
of each phase can be calculated by counting voxels of each phase.
In many cases we are interested in the interface between the two phases. A digital
representation of the interface is needed to calculate surface area, interfacial curvatures,
and topological characteristics. This digital representation is created starting from the
3D order parameterbased array. A threshold value of the order parameter is chosen,
usually halfway between the equilibrium values of the order parameter in each phase.
The surface dividing the phases at the threshold value is then calculated from the 3D
voxel array using a marching cubes algorithm [58]. This surface is represented digitally
as a set of small polygons in space connected at their vertices. The positions of the
vertices are specied by their (x, y, z) coordinates. This surface mesh calculation is
performed in the IDL software package using the SHADE VOLUME command.
53
3.2. Interfacial Curvature
Once the digital representation of the interface is calculated, the curvatures at each
vertex of the interface can be computed. This has also been accomplished in the IDL
software packages programming language, using the algorithm described in [59]. The
mean and Gaussian curvatures H and K are calculated rst since they are invariants
of the curvature tensor for each vertex. Then, principal curvatures
1
and
2
are
calculated using Equation 2.13 and 2.14. The surface area and surface area per unit
volume S
v
can also be calculated from the surface areas of the polygons that make
up the interface. Interface Shape Distributions are made by summing the area around
each vertex (the Voronoi area) in a bin for the appropriate combination of
1
and
2
and plotting the bins as a contour plot.
The curvatures of the interface can also be calculated using a dierent algorithm.
Using a diuseinterface representation of the microstructure, the mean and Gauss
ian curvatures are calculated at each grid point of the 3D volume based array using
Equation 2.10 and 2.12:
H =
1
2
( n)
K = n adj(He()) n
Rewriting these equations in terms of the order parameter ,
(3.1)
H =
xx
_
2
y
+
2
z
_
+
yy
(
2
x
+
2
z
) +
zz
_
2
x
+
2
y
_
2 (
x
xy
+
y
yz
+
x
xz
)
2
_
2
x
+
2
y
+
2
z
_
3/2
54
K =
2
x
_
yy
zz
2
yz
_
+
2
y
(
xx
zz
2
xz
) +
2
z
_
xx
yy
2
xy
_
_
2
x
+
2
y
+
2
z
_
2
2 [
x
y
(
xy
yz
xy
zz
) +
y
z
(
xy
xz
yz
xx
) +
x
z
(
xy
yz
xz
yy
)]
_
2
x
+
2
y
+
2
z
_
2
(3.2)
where subscripts denote derivatives in the x, y, z directions. First and second deriva
tives of the order parameter are calculated using central dierences:
x
=
i+1,j,k
i1,j,k
2x
(3.3)
xx
=
i+1,j,k
2
i,j,k
+
i1,j,k
(x)
2
(3.4)
where
i,j,k
represents the value of the order parameter at grid coordinates i, j, k, and
similar for derivatives in the y, z directions. These stencils are accurate to second
order, meaning they have an error of order (x)
2
. A fourpoint stencil is used for
mixed partial derivatives:
(3.5)
xy
=
i+1,j+1,k
i+1,j1,k
+
i1,j1,k
i1,j+1,k
xy
which is also of secondorder accuracy. Once H and K are determined at all grid
locations i, j, k, their values on the interface can then be determined by interpolating
the values at the xed gridpoints onto the interface using the IDL INTERPOLATE
function.
55
3.3. Topological Characterization
The topological characteristics of the microstructure are quantied using the genus.
The genus can be calculated using the GaussBonnet theorem:
(3.6) g = 1
1
4
_
S
KdS
In this case, the Gaussian curvatures K are calculated using the order parameter
representation of the microstructure using Equation 3.2. The values of K at the xed
3D grid points are then interpolated onto the vertices of the digital representation of the
interface described in Section 3.1. This is performed in IDL using the INTERPOLATE
function. Equation 3.6 is then numerically integrated using the areas of the polygons
making up the interface.
3.4. Calculation of Interfacial Velocities
Using an orderparameter based representation of a 3D microstructure, the veloci
ties of the interface can be calculated using:
(3.7) v =
t
[[
where
t
is the time derivative of the order parameter, which is calculated using a nite
dierence approximation between times t and t + t:
(3.8)
t
=
i,j,k
(t + t)
i,j,k
(t)
t
56
The components of [[ are calculated using central dierences as in Equation 3.3. The
magnitudes of velocities on the xed 3D grid are then interpolated onto the polygonized
interface using the IDL INTERPOLATE function. When the components of velocity
v
x
, v
y
, and v
z
are needed, they can be calculated from the magnitude of velocity and
derivatives of the order parameter:
(3.9) v
x
=
_
t
__
1
/x
[
1
[
2
_
(3.10) v
y
=
_
t
__
1
/y
[
1
[
2
_
(3.11) v
z
=
_
t
__
1
/z
[
1
[
2
_
When calculating velocities from an experimentally measured 3D microstructure,
the order parameter data is initially binary. Before the velocity calculation, the order
parameter data is smoothed to obtain a smoother velocity prole when interpolated
onto the interface. The binary data at each point is averaged with surrounding data
points using the IDL SMOOTH function with a width of 5 voxels. This means that
each point is averaged with the nearest two points in the +x direction and the nearest
two points in the x direction for a total of ve points being averaged, and similarly
for the y, z directions.
57
3.5. Phase Field Models
3.5.1. Isothermal Solidication of CuNi
The isothermal solidication of a CuNi alloy (58 at.% Ni) was simulated using the
phaseeld method as described in [60]. The solidication temperature is 1574 K. At
this temperature and for this alloy composition, the equilibrium solid volume fraction
is 75%. The free energy is given by the functional
(3.12) T =
_
V
_
T
2
[[
2
+ f(, c, T) + f
ori
_
dV
where is an order parameter representing the state of the system at each point
( = 0 for solid, and = 1 for liquid), T is the temperature,
2
[[
2
_
dV
where f(, T
m
) is the double well potential for the order parameter
(3.15) f(, T
m
) = H(
2
/2 +
4
/4)
59
with a solid represented by = 1 and liquid by = 1. f
AB
interpolates between the
two bulk free energies
(3.16) f
AB
(, c, T) = f
A
(T
m
) (T T
m
)s() +
RT
m
v
0
(c ln c c) + ()c
where s() and () interpolate independently between entropy and internal energy
between the phases, and the expression for the mixing entropy has been simplied by
assuming that c is small so that (1 c) 1 and ln(1 c) c. The dynamics of
the system are controlled by the AllenCahn equation, derived as before from the rst
variation of the order parameter, and the CahnHilliard equation modied to include a
phenomenological antitrapping current as in Equation 2.31. This approach allows the
use of unequal diusivities in the liquid and solid phases while simultaneously canceling
spurious eects at the interface caused by these unequal diusivities, including, as
mentioned before, (i) a chemical potential jump across the interface leading to solute
trapping, (ii) an interface stretching correction to solute conservation, and (iii) a surface
diusion correction to solute conservation.
The model is implemented on a uniform rectangular grid in three dimensions us
ing FORTRAN 90, with explicit time steps and central dierences used to evaluate
derivatives. The time step
(3.17) t = 0.6
(x)
2
4D
(where x is the grid spacing in units of interfacial width W, and D is the nondimen
sional diusion coecient as described in [61]) is chosen to ensure numerical stability
in 3D. The model is run on parallel computing systems using MPICHMX message
60
passing to pass data at interfaces between nodes. Since the model is intended for use
with experimental data represented as a 3D binary array, where the interfaces between
phases are initially sharp in the raw data, it is necessary to have a procedure to allow
the interfaces to reach their equilibrium shape (a hyperbolic tangent prole in 1D)
without allowing the interface positions to move signicantly while equilibrating. The
procedure is to rst allow both the order parameter and composition to simultaneously
evolve for only a short time to allow the order parameter to equilibrate. The order pa
rameter is then held xed and composition is allowed to equilibrate. Once composition
has equilibrated, both variables are then allowed to evolve simultaneously again.
61
CHAPTER 4
PhaseField Simulation of Equiaxed Dendritic Solidication in
a Binary Alloy
4.1. Microstructure, Volume Fraction, and Surface Area
The isothermal solidication of a CuNi alloy (58 at.% Ni) was simulated using
the phaseeld method as described in Section 3.5.1. As shown in Figure 4.1, isolated
dendrites grow from the supercritical seeds with random orientations relative to one
another. As time progresses, the dendrites continue to grow and begin to impinge on
one another, and the solid phase gradually becomes interconnected. Following 78.6
s, (Fig. 4.1(d)) the system has essentially reached the equilibrium volume fraction
solid of 75%. Afterwards, coarsening begins to dominate the changes to the systems
microstructure. Figure 4.2 shows the microstructure after the system enters the coars
ening regime. Due to the high V
f
, it is helpful to also visualize the system with the
liquid phase capped at the boundary.
The systems volume fraction solid V
f
initially grows very rapidly, then slows as
the system approaches its equilibrium V
f
, as determined by the systems position on
the phase diagram (Figure 4.3). S
v
also grows rapidly in the beginning as V
f
grows.
However, as the system approaches its equilibrium V
f
, S
v
begins to decrease due to the
eect of coarsening.
62
(a) (b)
(c) (d)
Figure 4.1. Microstructures of CuNi system undergoing dendritic solid
ication at (a) 26.2 s, (b) 41.9 s, (c) 57.6 s, and (d) 78.6 s. Visual
izations are a 640 390 128 subset of the 640 640 640 simulation
volume. The solid phase is capped at the boundary of the visualization
region.
As previously discussed, S
1
v
has been recognized as a useful quantity to describe the
length scale of the system during coarsening. However, its behavior during solidication
has not been previously explored. As S
v
is rapidly increasing during solidication,
S
1
v
rapidly decreases, then begins to grow again as the system begins coarsening
(Figure 4.4(a)). Soon after the system begins coarsening, it is found that for the
limited amount of time simulated, S
1
v
increases linearly with t
1/3
(Figure 4.4(b)).
63
(a) (b)
(c) (d)
(e) (f)
Figure 4.2. Microstructures of CuNi system entering the coarsening
regime at (a),(b) 105 s, (c),(d) 131 s, and (e),(f) 157 s. The
solid phase is capped at the boundary of the visualization region in
(a),(c),(e) and the liquid phase is capped in (b),(d),(f). Visualizations
are a 640 390 128 subset of the 640 640 640 simulation volume.
64
!
!#$
!#%
!#&
!#'
!#(
!#)
!#*
!#+
!
$
%
&
'
(
)
! %! '! )! +! $!! $%! $'! $)! $+!
V
o
l
u
m
e
F
r
a
c
t
i
o
n
S
o
l
i
d
S
v
(
m

1
)
Time (s)
,
./
Figure 4.3. V
f
and S
v
versus time.
!
!#$
!#%
!#&
!#'
(
(#$
(#%
(#&
(#'
$
$ ) % * &
S
v

1
(
m
)
t
1/3
(s
1/3
)
(a)
! # $%$&'() * $%$+,
./ # $%
$
$%$0
$%+
$%+0
$%1
$%10
$%2
& &%0 0 0%0 ,
S
v

1
(
m
)
t
1/3
(s
1/3
)
(b)
Figure 4.4. S
1
v
vs. t
1/3
during (a) solidication and coarsening, (b)
coarsening regime only (last 3 data points of (a)). The straight linet to
the data is consistent with other observations of S
1
v
during coarsening,
but much longer simulation times would be required to prove this scaling
conclusively.
This is consistent with other observations of coarsening behavior, but data over several
decades of time is necessary conrm this scaling behavior conclusively, which was not
practical given the time required to perform these simulations.
65
During solidication, S
1
v
is not a useful length scale because surface area increases
rapidly as dendrites nucleate and grow. However, as shown in Figure 4.5, for this
system, V
f
/S
v
remains constant to within 7% during solidication, and thus this
quantity is a useful length scale to characterize this microstructure. As the system
approaches the equilibrium solid volume fraction and coarsening begins to determine
the changes in the microstructure, S
1
v
begins to increase with the characteristic t
1/3
dependence of coarsening, while V
f
remains constant, making V
f
/S
v
a characteristic
length useful throughout the solidication and coarsening process.
!
!#$
!#%
!#&
!#'
!#(
!#)
!#*
!#+
!#,
$
!
!#!(
!#$
!#$(
!#%
!#%(
!#&
!#&(
!#'
! %! '! )! +! $!! $%! $'! $)! $+!
V
o
l
u
m
e
F
r
a
c
t
i
o
n
S
o
l
i
d
(
V
f
)
V
f
/
S
v
(
m
)
Time (s)
./01
.
Figure 4.5. Volume fraction solid approaches the equilibrium value of
0.75. V
f
/S
v
remains constant (7%) during solidication, then begins
to increase as the system enters the coarsening regime.
Several authors have suggested possible relationships between V
f
and S
v
during
solidication. Cahn [62] suggested that S
v
V
2/3
f
or(1 V
f
)
2/3
as V
f
approaches 0 or
1, respectively. Rath [63] suggested that S
v
V
m
f
(1 V
f
)
n
, where m, n are param
eters t to the experimental data. Limodin et.al. [64] found that experimental data
from solidication of Al10 wt.% Cu during continuous cooling at 3
C/min was t
well by Raths equation. However, the present simulations dier from the conditions
employed in Limodins experiments since we are considering isothermal solidication
66
and thus a volume fraction of solid of 1 can never be reached. Li and Beckermann [65]
analyzed data from an isothermal dendritic growth experiment performed in micro
gravity and found scaling relationships between dendrite tip radii, surface area, and
volume fraction, but the results are only applicable to a single dendrite without making
assumptions about the density of nuclei.
4.2. Interface Shape Distributions
Interface shape distributions were created for the microstructures at each time step
as described in Section 3.1. It was necessary to smooth the microstructures in order to
eliminate noise from the ISDs. Volume smoothing with a width of 3 and 5 voxels was
tested as described in Section 3.4. Figure 4.6 shows that resulting ISDs were consistent
at both the early and late stages of simulation. 5 voxel smoothing was chosen for the
remaining ISDs for consistency with the smoothing necessary in Section 4.3.
Figure 4.8 shows how the ISDs of the simulation change during the initial stages
of the transformation when solidication dominates. At 26.2 s, where the structure
consists mostly of freegrowing dendrites, approximately 50% of interfacial area has
both principal curvatures positive. These patches are primarily located at the tips of the
stillforming primary and secondary dendrite arms. 45% of interfacial area has K < 0
or
1
< 0,
2
> 0 (saddleshaped patches), and is mostly found between adjacent tips
of the growing secondary arms. The 5% remaining area has both curvatures negative
and is found in the regions between adjacent primary and secondary arms. These
regions are shown highlighted in color for a single isolated dendrite in Figure 4.7.
67
15 10 5 0 5 10
10
5
0
5
10
15
0.000E+00 6.106E03 1.221E02 1.832E02 2.442E02 3.053E02
!
!
[1/"m]
!
#
[
1
/
"
m
]
(a)
15 10 5 0 5 10
10
5
0
5
10
15
0.000E+00 6.351E03 1.270E02 1.905E02 2.540E02 3.175E02
!
!
[1/"m]
!
#
[
1
/
"
m
]
(b)
15 10 5 0 5 10
10
5
0
5
10
15
0.000E+00 6.350E03 1.270E02 1.905E02 2.540E02 3.175E02
!
!
[1/"m]
!
#
[
1
/
"
m
]
(c)
15 10 5 0 5 10
10
5
0
5
10
15
0.000E+00 6.350E03 1.270E02 1.905E02 2.540E02 3.175E02
!
!
[1/"m]
!
#
[
1
/
"
m
]
(d)
Figure 4.6. ISDs for (a), (b) 26.2 s, (c),(d) 157 s. (a) and (c) were
volume smoothed with a width of 3, (b) and (d) with a width of 5.
Comparison shows no signicant dierences due to smoothing.
68
Figure 4.7. An isolated dendrite at t = 26.2 s. Patches in Region 1
of the ISD (
1
,
2
both positive) are colored red. Patches in Regions 2
and 3 of the ISD (
2
positive,
1
, negative) are colored grey. Patches in
Region 4 of the ISD (
1
,
2
both negative) are colored blue.
As volume fraction increases, there is a general shift of the distribution to saddle
shaped interface patches and a decrease in the intensity of the peak for solid cylindrical
patches (
1
= 0). After 78.6 s, where the system has essentially reached its equilibrium
volume fraction, only 35% of patches have both principal curvatures positive, while 59%
are saddleshaped, and the peak of the distribution is almost completely contained in
the saddleshaped region. This shift is due to the dendrites impinging on one another
and therefore a slower increase in concave interfacial area relative to saddleshaped
interfacial area. However, during the process, there is actually an increase in the region
where
2
> 10 m
1
between 41.9 s and 57.6 s, which starts to shrink back down
by 78.6 s. Figure 4.9 shows that this region is dominated by the tips of secondary
69
arms which form as the systems volume fraction increases. As the equilibrium volume
fraction is approached, these highcurvature regions are the rst to be eliminated by
coarsening, which is evident in the ISDs from later times (see Figure 4.10). Despite
the signicant change in the volume fraction from 26.2 to 78.2 s, there is no major
change in the breadth or peak location of the ISDs. This implies that there is no major
change in the scale of the curvatures in the structures during solidication, which is
consistent with the constant length scale, V
f
/S
v
, noted above.
Figure 4.10 shows the evolution of the ISDs at later times. Saddleshaped regions
with relatively low curvature are the dominant feature of the microstructure. The
peak is mostly comprised of patches that are located on the gently curved solidliquid
interfaces. These gently curved interfaces are frequently separated by a thin liquid
layer between adjacent solid dendrites which approach each other, but the remaining
liquid is too enriched in solute to freeze. The high
2
regions corresponding to dendrite
tips are gone. However, regions with
1
< 8 m
1
,
2
0, also relatively high in
the magnitude of the curvature, persist longer. Many of these liquid cylindrical shapes
are caused by liquid tubes pinching o then retracting, as shown in Figure 4.11. Many
liquid cylindrical shapes are also found at the edges of the interdendritic liquid. This
tail remains relatively constant throughout the ISDs shown in Figure 4.10, indicating
that the interdendritic liquid remains and that pinching events continue to occur.
As discussed in Section 2.5, during coarsening, microstructures may become self
similar, in which case the ISD becomes timeindependent when scaled by S
v
. For the
early stages of coarsening simulated in this system, the ISDs are not selfsimilar after
scaling (Figure 4.12). Therefore, the system has not yet begun to exhibit selfsimilar
70
15 10 5 0 5 10
10
5
0
5
10
15
0.000E+00 6.351E03 1.270E02 1.905E02 2.540E02 3.175E02
!
!
[1/"m]
!
#
[
1
/
"
m
]
(a)
15 10 5 0 5 10
10
5
0
5
10
15
0.000E+00 6.350E03 1.270E02 1.905E02 2.540E02 3.175E02
!
!
[1/"m]
!
#
[
1
/
"
m
]
(b)
15 10 5 0 5 10
10
5
0
5
10
15
0.000E+00 6.350E03 1.270E02 1.905E02 2.540E02 3.175E02
!
!
[1/"m]
!
#
[
1
/
"
m
]
(c)
15 10 5 0 5 10
10
5
0
5
10
15
0.000E+00 6.350E03 1.270E02 1.905E02 2.540E02 3.175E02
!
!
[1/"m]
!
#
[
1
/
"
m
]
(d)
Figure 4.8. ISDs of CuNi system undergoing dendritic solidication at
(a) 26.2 s, (b) 41.9 s (c) 57.6 s, (d) 78.6 s. Color bar set to the
same scale for all plots.
71
Figure 4.9. A (1.31 1.83 1.44 m) subset of the microstructure at
41.9 s. Patches with
1
> 0,
2
> 10 m
1
are colored red.
coarsening. However, the system may eventually exhibit selfsimilar coarsening after
suciently long coarsening time, as in [66].
4.3. Interfacial Topology
The topological characteristics of the simulated CuNi alloy were also investigated.
The genus, g, was the primary metric used to quantify the systems topology. Since g =
hv+1, the number of voids v contributes to genus. To quantify this contribution, the
number of voids of each phase was counted using the IDL LABEL REGION function.
Since the simulations use periodic boundary conditions, single voids which extend over
the boundaries cause an overcount of the number of voids by one. To correct for this,
an IDL program was written to scan along the x = 0, y = 0, and z = 0 planes and
subtract one from the void count for every void which extended across the periodic
boundary.
Table 4.1 shows that periodic boundary conditions have an important eect on
the count of bodies. By visualizing the edges of the simulation region, it was found
that the majority of the excess voids removed were small tips which barely extended
72
15 10 5 0 5 10
10
5
0
5
10
15
0.000E+00 6.350E03 1.270E02 1.905E02 2.540E02 3.175E02
!
!
[1/"m]
!
#
[
1
/
"
m
]
(a)
15 10 5 0 5 10
10
5
0
5
10
15
0.000E+00 6.350E03 1.270E02 1.905E02 2.540E02 3.175E02
!
!
[1/"m]
!
#
[
1
/
"
m
]
(b)
15 10 5 0 5 10
10
5
0
5
10
15
0.000E+00 6.350E03 1.270E02 1.905E02 2.540E02 3.175E02
!
!
[1/"m]
!
#
[
1
/
"
m
]
(c)
Figure 4.10. ISDs of CuNi system undergoing coarsening at (a) 105 s,
(b) 131 s, and (c) 157 s.
73
Figure 4.11. A (1.31 1.83 1.44 m) subset of the microstructure at
105 s. (The liquid phase is capped at the boundary.) Patches with
1
< 8 m
1
, 4 m
1
<
2
< 12 m
1
(liquid cylindrical regions)
are colored red. These patches show the origin of the extended tail
found mostly in Region 3 of in the ISDs of Figure 4.10. These regions
are associated with liquid tubes that are pinching o and with the edges
of interdendritic liquid regions that separate solid dendrites.
Time (s) V
f
(%
solid)
Solid voids Solid voids
(PBC)
Liquid
voids
Liquid
voids
(PBC)
26.2 7.69 82 58 1 1
41.9 26.0 84 11 2 1
57.6 49.6 93 1 11 1
78.6 69.2 57 1 18 2
105 72.7 28 1 25 8
131 73.1 15 1 35 15
157 73.3 12 1 35 20
Table 4.1. Number of solid and liquid voids for each time. PBC= cor
rected for eect of periodic boundary conditions.
over the periodic boundary. The solid phase becomes continuous at 41.9 s, when
V
f
= 50%. The system is bicontinuous at that time as well. Following 41.9 s, the
solid phase remains continuous, while the liquid phase begins to develop isolated voids.
74
5 4 3 2 1 0 1 2
2
1
0
1
2
3
4
5
0.000E+00 8.446E02 1.689E01 2.534E01 3.378E01 4.223E01
!
!
/S
v
!
"
/
S
v
(a)
5 4 3 2 1 0 1 2
2
1
0
1
2
3
4
5
0.000E+00 8.446E02 1.689E01 2.534E01 3.378E01 4.223E01
!
!
/S
v
!
"
/
S
v
(b)
5 4 3 2 1 0 1 2
2
1
0
1
2
3
4
5
0.000E+00 8.446E02 1.689E01 2.534E01 3.378E01 4.223E01
!
!
/S
v
!
"
/
S
v
(c)
Figure 4.12. ISDs of CuNi system undergoing coarsening at (a) 105 s,
(b) 131 s, and (c) 157 s. ISDs scaled by S
v
and plotted with same color
bar. The changes in the ISDs with time mean that the microstructure is
not selfsimilar.
75
(a) (b)
(c)
Figure 4.13. Portion of the simulation microstructure at (a) 105 s, (b)
131 s, and (c) 157 s. Liquid phase is capped at the boundary. Red
arrow highlights a long liquid cylinder that pinches o by Rayleigh in
stability at two points simultaneously, leaving an isolated liquid void in
between after pinching.
These isolated liquid voids form when a long liquid tunnel pinches o by a Rayleigh
instability at two points simultaneously, leaving a liquid void in between (Figure 4.13).
The calculated number of voids v was also used to test the accuracy of the genus
calculation. Genus was calculated as described in Section 3.3. The original phaseeld
data at time 26.2 s was compared to data volumesmoothed with widths of 3, 5, 7,
and 9 (Table 4.2).
76
Smoothing Interface width (points) Genus
None 5 1370
3 6 92.9
5 8 54.4
7 9 44.5
9 11 32.9
Table 4.2. Computed genus versus volume smoothing width for isolated
dendrites at t = 26.2 s. The interface width is dened as the number
of interface points where the order parameter is between 10%  90% of
the equilibrium liquid value.
Since there are 58 solid voids at t = 26.2 s, each of which has 0 handles, the
expected genus is 57. The computed value with a smoothing width of 5 gives the best
agreement with the computed value (within 4.6%). Smoothing with a width of 3 does
not produce wide enough interfaces for an accurate Gaussian curvature calculation,
while smoothing with a width of 7 or more begins to weld adjacent solid dendrites
together.
Genus was calculated for each time step after the order parameter was volume
smoothed with width 5. Results are shown in Table 4.3 and plotted on a per unit
volume basis in Figure 4.14. Genus is initially negative as isolated solid dendrites
without handles nucleate throughout the simulation volume. Handles in the solid
structure (or equivalently, tunnels of liquid) form as adjacent dendrite arms coalesce,
as shown in Figure 4.15. From 26.2 to 105 s, handles form much more quickly than
new solid particles nucleate, causing genus to increase.
As the system approaches its equilibrium solid volume fraction and coarsening
begins to dominate (105 s to 157 s), genus decreases due to the breakup of liquid
tubes that result from a capillarydriven instability, as shown in Figure 4.16. Each
77
!"
$
"
%
&
'
(
)
$ %$ '$ )$ *$ "$$ "%$ "'$ ")$ "*$
G
e
n
u
s
/
V
o
l
[
!
1
0
9
/
m
m
3
]
Time (s)
Figure 4.14. Genus per unit volume versus time.
Figure 4.15. A handle (liquid tunnel) is formed as adjacent secondary
arms join, in red circle (t = 41.9 s). The solid phase is capped at the
boundary.
78
Time (s) Genus
26.2 54.40
41.9 213.8
57.6 1022
78.6 2292
105 2836
131 2666
157 2492
Table 4.3. Computed genus versus time.
pinching event will cause genus to decrease by one. At the same time, although the
solid phase remains continuous, isolated liquid droplets begin to form (Figure 4.13),
which also causes genus to decrease. However, it can be seen by comparing Figure 4.14
and 4.17 that g
v
decreases by 5.8 10
8
/mm
3
while the number of liquid bodies per
unit volume increases by only 3.2 10
7
/mm
3
from 105 s to 157 s, meaning that the
pincho of handles is a much more important contributor to the change in topology
than the formation of liquid voids at this early stage of coarsening.
(a) (b)
Figure 4.16. The breakup of liquid tubes due to capillaritydriven insta
bility. The liquid phase is capped at the boundary. (a) 78.6 s, (b) 157
s.
79
!
!#!$
!#!%
!#!&
!#!'
!#(
!#($
! $! %! &! '! (!! ($! (%! (&! ('!
B
o
d
i
e
s
/
V
o
l
[
!
1
0
9
/
m
m
3
]
Time (s)
Solid Bodies/Vol
Liquid Bodies/Vol
Figure 4.17. Number of independent bodies per unit volume for solid and
liquid phases. The formation of either a liquid or solid body decreases the
genus by 1. The minimum value plotted for each series, 1.7 10
6
/mm
3
,
represents a single continuous body divided by the simulation volume.
During coarsening, quantitative comparison between systems is facilitated by con
verting the genus to a scaled genus, g
v
S
3
v
. This is a dimensionless number that can
most easily be understood as the genus per characteristic volume, and is expected
to be a constant for systems undergoing selfsimilar coarsening. From 105 s to 157
s, g
v
S
3
v
increased from 0.068 to 0.087, meaning that the system is not topologically
selfsimilar during the early stages of coarsening.
4.4. Comparison with Other Systems
The morphology and topology of other dendritic microstructures produced under
dierent conditions have also been characterized [18, 19, 66]. In this section, we will
compare these experiments to the results of Section 4.2 and 4.3. The use of simulations
allows direct characterization of the solidication process that was not available in
these experiments, and shows that the morphology and topology of the system during
solidication were not selfsimilar.
80
In [66], the morphology and topology of dendritic microstructures produced by
equiaxial solidication in AlCu were characterized using ISDs and genus per unit vol
ume. In these experiments, the initial morphology of the dendrites is controlled by the
interfacial energy anisotropy, not the kinetic coecient anisotropy as in these simula
tions. In both cases, the morphology and topology of the initial microstructures evolve
nonselfsimilarly during the early stages of coarsening. In [66], after long coarsening
times (18 hours and longer), the morphology and topology did become selfsimilar for
both solid volume fractions investigated (46% and 72%). Such long coarsening times
were not accessible for these simulations due to the extremely long computation times
that would be required. The scaled genus g
v
S
3
v
of the 74% solid sample was 0.02
for the liquid phase genus and 0.06 for the solid phase genus, both of which are in the
same order of magnitude as the CuNi simulations, but the several orders of magnitude
dierence in time scales makes any conclusions about the universality of scaled genus
dicult.
The morphology of dendritic microstructures after directional solidication in Al
Cu [18] and PbSn [19] were also characterized using ISDs. In these systems, a strong
directionality was observed as coarsening proceeded due to the directional solidication
process, and selfsimilarity was not observed in the morphology. Like the present
simulations, the initial morphology introduced by the solidication process lacks self
similarity, and in the case of the experiments, this nonselfsimilar evolution persists
long into the coarsening regime.
The topology of the AlCu system after directional solidication was also investi
gated [67]. The systems solid volume fraction was 74%, very close to the 75% of the
81
simulated CuNi system being studied. In spite of the very dierent time scales (the
earliest coarsening time investigated in [67] was 10 min), the scaled genus g
v
S
3
v
= 0.11
at 10 min was quite close to the value found at t = 157 s of 0.087 for the simulations.
The topology of the AlCu system continued to evolve nonselfsimilarly into the late
stages of coarsening, as g
v
S
3
v
decreased to 0.45 after 964 min of coarsening. In both
systems, in the early stages of coarsening there were many more handles than voids,
so handles contributed much more to genus. In the later stages of [67], the number of
voids becomes comparable to the number of handles, causing the scaled genus g
v
S
3
v
to
decrease. The large number of liquid droplets formed in [67] result from the pinching
of liquid cylinders, similar to the process described in Section 4. Again, since very long
coarsening times were not accessible for these simulations, it is not known whether
the g
v
S
3
v
for these simulated dendrites will achieve a steadystate value or begin to
decrease due to the formation of liquid voids.
4.5. Conclusions
A rapidly solidifying CuNi alloy was simulated using a phaseeld model, and
the morphology and topology of the dendritic microstructure were characterized. V
f
increased rapidly until it reached the equilibrium value of 75%. S
v
rapidly increased
during solidication, then began to decrease as the microstructure began to coarsen.
V
f
/S
v
remained relatively constant during solidication and then began to increase
during coarsening, suggesting its possible use as a characteristic length throughout the
solidication and coarsening process.
82
The morphology of the microstructure was characterized using ISDs. Initially the
majority of interfacial area had both principal curvatures positive, then shifted to a
majority of saddleshaped patches as the equilibrium V
f
was reached. During the
coarsening regime, the peak of the ISD remained in the saddleshaped region. There
was also an extended tail in the liquidcylindrical region caused by liquid cylinders
pinching o and by the edges of interdendritic liquid regions. The systems morphology
evolved in a nonselfsimilar manner early in the coarsening regime.
The microstructures topology was characterized using the genus. g was initially
negative as isolated dendrites without handles nucleated, then increased rapidly as
handles formed by adjacent dendrite arms grew together. Genus then decreased as
the system entered the coarsening regime, due to the pincho of liquid tubes and the
formation of liquid voids by simultaneous Rayleigh instabilities in long tubes. Pinching
of liquid tubes has a much larger eect on the changes in topology than formation of
liquid voids. The systems topology also evolved in a nonselfsimilar manner early in
the coarsening regime.
83
CHAPTER 5
Rate of Change of Curvatures
5.1. Details of Algorithm
As discussed in Section 2.3.2, the time evolution of mean and Gaussian curvatures
can be found using Equation 2.16 and 2.17:
H =
H
t
+v H
K =
K
t
+v K
An algorithm to calculate
H and
H and
H =
H
t
+v H (5.6)
H = 0 +
_
x
_
x
2
+ y
2
v,
y
_
x
2
+ y
2
v, 0
_
_
H
x
,
H
y
, 0
_
(5.7)
H =
v
2 (x
2
+ y
2
)
(5.8)
which shows that
H is nonzero, as expected.
5.2.2. Translating Cylinder
Another example which will demonstrate this method is a translating cylinder with
constant radius moving at constant velocity v
x
in the x direction. In this case, we
intuitively expect that since the cylinders radius is not changing,
H = 0. The cylinder
can be represented mathematically by the function
(5.9) = tanh
__
_
(x v
x
t)
2
+ y
2
k
_
/W
_
87
The normal is given by
(5.10) n =
[[
=
_
x v
x
t
_
(x v
x
t)
2
+ y
2
,
y
_
(x v
x
t)
2
+ y
2
, 0
_
and mean curvature is
(5.11) H =
1
2
( n) =
1
2
_
(x v
x
t)
2
+ y
2
In this case since there is explicit time dependence in the mean curvature,
H
t
=
t
_
1
2
_
(x v
x
t)
2
+ y
2
_
(5.12)
=
v
x
(x v
x
t)
2 [(x v
x
t)
2
+ y
2
]
3/2
(5.13)
which is nonzero as expected. To nd the time derivative of curvature at a point
moving with the interface, since v = v
x
x,
H =
H
t
+ v
x
H
x
=
v
x
(x v
x
t)
2 [(x v
x
t)
2
+ y
2
]
3/2
v
x
(x v
x
t)
2 [(x v
x
t)
2
+ y
2
]
3/2
= 0
as expected.
5.3. Testing of Algorithm
The algorithm was then tested on the examples of Section 5.2. The algorithm to
calculate H and K was tested rst using a cylinder as represented using a hyperbolic
88
tangent function as in Equation 5.2 (as shown in Figure 5.1) with vt = 25, and varying
interface width W (units of length are dimensionless gridpoints). At the interface, the
curvature calculation should give H = (1/25 +0)/2 = 0.02. After calculating H at the
xed gridpoints and interpolating H to the interface, a minimum of H = 0.0199 and a
maximum of H = 0.0203 were found for the W = 5 case, in good agreement with the
expected value.
Figure 5.2. Plot of mean curvature H for =
tanh
__
_
x
2
+ y
2
vt
_
/W
_
along x for y = 0, z = 0. vt = 25,
W = 2.5 (white), W = 5 (red).
For an accurate calculation of the term H, H should vary smoothly through the
interface. Figure 5.2 shows the eect of varying the number of points through the
interface (controlled by W) on the prole of H. As W is increased and the number
of points through the interface increases, H varies more smoothly. To quantify the
89
number of points through the interface, we dene the interface as the region where
0.9 < < 0.9. Using this denition, W = 2.5 gives 5 points through the interface,
and W = 5 gives 15 points. As Figure 5.2 shows, the magnitude of H is close to 0.02 at
the interface (plotted as x = 25, 75) for either value of W, but the derivative is much
smoother for W = 5, which will be required for later calculation of H.
The example case of the expanding cylinder was also used to test the calculation
of interfacial velocities and v H. Equation 5.2 for an expanding cylinder was again
used, with vt = 25 for the array at time t and vt = 25.01 used for time t + t, and
W = 5. In the case of the expanding cylinder, the expected value of
H on the interface
is given by Equation 5.8 as
(5.14)
H =
v
2 (x
2
+ y
2
)
=
x
2t (x
2
+ y
2
)
= 1.38 10
4
/(gridpoints
0
)
where v = x/t = 0.173 gridpoints/
0
(which is determined by is the arbitrary
dimensionless time step t = 0.0577
0
).
Initial testing showed the calculation of
xx
=
1
x
2
_
1
12
(
i+1,j+1,k
2
i,j+1,k
+
i1,j+1,k
)
+
10
12
(
i+1,j,k
2
i,j,k
+
i1,j,k
) +
1
12
(
i+1,j1,k
2
i,j1,k
+
i1,j1,k
)
_
(5.17)
and the stencil for mixed partial derivatives remains as in Equation 3.5. Using isotropic
derivative stencils resulted in the maximum value of [H[ decreasing to 1.27 10
3
,
meaning error decreased from 89% to 59%. Since this error is still unacceptably high,
the code for calculating H and K was modied to use fourthorder accurate stencils
for rst, second, and mixed partial derivatives. The rst derivative stencil remains as
in Equation 5.16. The second derivative stencil is
(5.18)
xx
=
1
12x
2
(
i2,j,k
+ 16
i1,j,k
30
i,j,k
+ 16
i+1,j,k
i+2,j,k
) + O(x
4
)
and the mixed partial derivative stencil is
xy
=
1
144xy
[
i2,j2,k
8
i2,j1,k
+ 8
i2,j+1,k
i2,j+2,k
8
i1,j2,k
+ 64
i1,j1,k
64
i1,j+1,k
+ 8
i1,j+2,k
+ 8
i+1,j2,k
64
i+1,j1,k
+ 64
i+1,j+1,k
8
i+1,j+2,k
i+2,j2,k
+ 8
i+2,j1,k
8
i+2,j+1,k
+
i+2,j+2,k
]
(5.19)
93
W vt at (t + t) N. points 0.9 < < 0.9 Max. Error in
H
5 25.01 15 1.50%
5 25.1 15 1.62%
5 25.5 15 2.10%
4 25.01 11 3.27%
3 25.01 9 33.0%
Table 5.1. Summary of testing for expanding cylinder test scenario.
Using fourthorder accurate stencils, the accuracy of the calculation of [H[ improved
considerably, with variation on the interface only from 8.02 10
4
to 8.5 10
4
.
With condence in the calculation of its components,
H
Min.
H
5 25.01 15 6.59 10
5
6.01 10
5
5 25.1 15 9.37 10
5
8.56 10
5
4 25.01 11 6.66 10
5
6.17 10
5
3 25.01 9 1.08 10
4
8.57 10
5
Table 5.2. Summary of testing for translating cylinder test scenario.
5.5. Conclusions
An algorithm to numerically calculate
H and
l
k
2
+ D
l
k
2
D
l
D
s
s
k
2
+ D
s
k
2
D
s
where D
l
, D
s
are the equilibrium liquid and solid diusivities,
l
,
s
are the capillary
lengths in liquid and solid,
p
is the wavelength of the perturbation, and k = 2/
p
.
98
Figure 6.1. Sample input array: White is solid, black is liquid.
p
= 120
gridpoints, perturbation amplitude A = 10, D
s
= 0. The gray border is
for visual clarity only and is not part of the simulation region.
(See Appendix A for details of the linear stability analysis.) This equation can be
solved numerically for .
To simulate the perturbation decay, a 2D array with a sinusoidal perturbation at
the solidliquid interface was used as input to the phaseeld model. Wavelength was
set to a xed number of gridpoints, and grid spacing x = y = z = 0.8W where
W is the dimensionless interface width. Noux boundary conditions were used. Other
parameters used were for the AlCu system, where C
0
S
= 5.65%, C
0
L
= 33.0%, and
each timestep t = 0.6(x)
2
/4D
L
where D
L
is the dimensionless diusion coecient
in the liquid. The diusion coecient in the solid D
S
is assumed to be zero. Figure
6.1 shows the input array with solid ( = 1) represented by white and liquid ( = 1)
represented by black.
The size of the liquid region is much larger than the solid region in this example to
allow the diusion eld to reach its equilibrium value at the boundary of the simulation
99
Figure 6.2. Decay of a perturbation from simulation results (red) com
pared with analytical solution calculated from Equation 6.2 (blue).
(at the top of the ydirection in this plot). Since D
s
was set to 0 this was not necessary
on the solid side.
Once initial conditions were established as described in Section 3.5.2, each simula
tion was allowed to evolve so the perturbation could decay, and the composition and
order parameter elds were periodically output to disk. For the initial (equilibrated)
array and for each output, the position of the interface was determined along the x = 0
edge of the boundary by linearly interpolating to nd the point where = 0. A plot of
the perturbation amplitude as a function of time is shown in Figure 6.2 along with the
expected perturbation amplitude from the linear stability analysis. The decay constant
was calculated using leastsquares tting to an exponential decay function.
100
45%
40%
35%
30%
25%
20%
15%
10%
5%
0%
5%
0 20 40 60 80 100 120 140 160 180 200
D
e
c
a
y
C
o
n
s
t
a
n
t
E
r
r
o
r
Perturbation Wavelength (gridpoints)
% Error
(a)
0%
5%
10%
15%
20%
25%
0 20 40 60 80 100 120
D
e
c
a
y
C
o
n
s
t
a
n
t
E
r
r
o
r
Epsilon
% Error
(b)
Figure 6.3. (a) Decay constant error for perturbation with A = 10 with
various perturbation wavelengths, (b) decay constant error for constant
system size, varying .
Simulation results were rst compared to theory by varying the wavelength of the
perturbation
p
and comparing the decay constant predicted by the linear stability
analysis to the simulated decay constant. In the simulations, the perturbation ampli
tude A = 10 gridpoints and the parameter = W/d
0
(which sets the capillary length
d
0
and therefore the strength of capillary forces) was set to 30. Agreement between
the linear stability analysis and simulation (Figure 6.3(a)) was good except for smaller
wavelengths where the assumption
p
A is no longer valid.
The parameter = W/d
0
is expected to have an impact on the accuracy of the
phaseeld model. In [61], the model was tested against the predictions of a linear
stability analysis for the amplication of a perturbation to a solidliquid interface during
directional solidication. Agreement between simulations and experiment was worse as
was increased to a value of 100. The eect of was also tested in our implementation
of the model. The systems physical size was kept constant by maintaining the product
of (in grid points) and constant, so that only the eect of changing was tested.
101
The systems physical size is set by the product of the perturbation wavelength in
grid points and the grid spacing x which converts from grid spacing to physical
dimensions:
(6.3) =
grid
x
and since x = y = z = 0.8W (as set in the simulation parameters) and W = d
0
,
(6.4) = 0.8
grid
W = 0.8
grid
d
0
Since d
0
is a physical parameter of the system, Equation 6.4 shows that the systems
physical size is maintained constant by keeping
grid
constant. The same scaling was
applied to the perturbations initial amplitude. Similar to [61], agreement became
worse as increased toward 100 (Figure 6.3(b)).
The eect of the antitrapping correction (as described in Section 3.5.2) on the decay
of the perturbation was investigated by repeating the calculation for a perturbation
of = 120, A = 10, = 30 with the antitrapping current set to zero. The decay
constant found from this simulation was 1.46 10
4
, meaning that deviation from the
analytical prediction increased from 1.00% to 6.12% when the antitrapping current was
not included. This shows that the antitrapping current does minimize errors caused by
unequal diusivities between the two phases, although agreement between simulation
and theory is still relatively good without antitrapping current. This is likely due to the
low velocity of the interface in this coarsening simulation relative to the much larger
velocity in directional solidication, which the model of [61] was created to simulate.
102
6.4. Calculating Interfacial Velocities from Experimental Data
Interfacial velocities in the normal direction were calculated from the experimental
microstructure as described in Section 3.4. The order parameter arrays were from two
subsequent tomographic scans, the rst after 2.6 hours of isothermal coarsening, the
second 5 min 46 s later. Because the 3D arrays created by tomographic scans were large
(451 451 349 voxels), the full arrays are too large to simulate using phaseeld
modeling in a reasonable amount of time. For this reason, a 100 80 150 voxel
subset of the array was selected for the velocity calculation and input into the phase
eld model. The arrays were smoothed using a 5voxel volume smooth. To determine
the velocities on the solidliquid interface, the velocities calculated at each point of the
order parameter array were linearly interpolated onto the level set representation of
the interface calculated from the rst tomographic scan.
Figure 6.4 shows the subset of the microstructure used for the velocity calcula
tion at the initial time step, and the velocities calculated using two dierent methods
of smoothing the order parameter array. In Figure 6.4(b), the order parameter was
smoothed only using the 5voxel volume smoothing. Although the velocity prole is
fairly smooth across the surface, there are subtle variations caused by variations in
surface curvature in the experimental microstructure after only one smoothing oper
ation. To determine whether these variations cause signicant error in the calculated
velocities, the volumesmoothed order parameter arrays were input into the phaseeld
model. The phaseeld model quickly reduces smallscale surface curvature variations
in order to reduce the total interfacial energy of the system. The phaseeld model
evolved both order parameter arrays for 60,000 iterations, with a interface width of
103
x = 0.4W and = 1000. Figure 6.4(c) shows that the interfacial velocities calcu
lated using phaseeld smoothing of the experimental microstructures does not dier
signicantly from those calculated using only volumesmoothing. Therefore, the ex
perimental velocities of Figure 6.4(b) will be used as the basis of comparison with
simulation results.
Interfacial velocities were also calculated from experimental time steps near those
shown in Figure 6.4. The purpose of these tests was to verify that there were no
anomalies in the experimental microstructures which could lead to errors in the velocity
calculation, and that the microstructure was not changing too fast to allow accurate
velocity calculation using a 5 min 46 sec interval. Velocities were calculated from the
2.6 hour microstructure and the microstructure two time steps (11 min 32 seconds)
before, and also one four time steps (23 min 4 sec) after. Velocities calculated were
consistent with the initial calculation.
6.4.1. Choosing Simulation Parameters
Many factors were considered in selecting parameters for the phaseeld simulations
used to predict interface evolution. Previous testing showed that at least 10 points
through the interface (0.9 < < 0.9) were needed for accurate calculation of
H
and
K from phaseeld simulations (not covered in this work but an eventual goal of
the sponsoring project). Therefore, x = 0.4W was selected, which gave an interface
width of 10 points, as opposed to x = 0.8W, which gave an interface 6 points wide.
Initial testing of the velocity calculation with x = 0.4W showed that the liquid
particle in the upper portion of the simulation volume (at z = 200 m, Figure 6.4(a))
104
(a)
(b) (c)
Figure 6.4. (a) 100 80 150 voxel portion of microstructure used for
calculation of interfacial velocities (liquid phase is capped at boundaries),
(b)(c) solidliquid interface colored by normal interfacial velocities cal
culated from experimental data (negative velocities point into the liquid),
experimental time steps 5 min 46 sec apart. In (b) the order parameter
array was smoothed using only a 5voxel volume smooth, in (c), the order
parameter array was also smoothed by the phaseeld model.
105
had a signicant negative velocity over the entire surface, in contrast with experimental
data and the simulations assumption of D
S
= 0. It was found that due to the wide
interface in comparison with the particles size, the order parameter never reached the
equilibrium value for liquid in the particle; the minimum value of the order parameter
in the liquid particle was = 0.74 instead of 1. Therefore, the particle was shrinking
in an eort to reach the equilibrium value to minimize the systems energy. Because
there are many features in the system with similar sizes as this particle, it was necessary
to increase the grid point density of the simulation volume to allow the interfaces to
be adequately resolved. This was accomplished by using the REBIN command in IDL
to produce a simulation volume of 200 160 300 and changing the parameter ,
which sets the physical size scale of the system as follows. Since by the denition of ,
W = d
0
,
(6.5) x = 0.4W = 0.4d
0
(6.6) =
x
0.4d
0
Since the grid spacing x is given by the resolution of the Xray experiment, prior
to the rebin command, x = 1.4 m. After rebinning, x = 0.7 m. d
0
and other
physical parameters used are shown in Table 6.1.
(6.7) =
0.7 m
0.4 2.27 10
3
m
= 771
106
Parameter Value Reference
D
L
(liquid diusion coecient) 2.4 10
9
m
2
/s [74]
m
L
(liquidus slope) 7.25 K/at. % [75]
k (partition coecient) 0.145 [75]
(GibbsThomson coecient) 2.41 10
7
mK [76]
d
0
(Capillary length) 2.27 nm
m
L
(c
0
L
c
0
S
)
[61]
Table 6.1. Physical parameters used in phaseeld simulations.
The parameters of Table 6.1 are used to convert simulation time to real time. To
convert the dimensionless time step per iteration to physical time, the dimensionless
time step per iteration (Equation 3.17) is multiplied by the characteristic time as
described in [61]:
(6.8) =
a
1
a
2
3
d
2
0
D
L
where a
1
, a
2
are dimensionless constants and D
L
is the diusion coecient of solute in
the liquid.
As discussed in Section 3.5.2, before the velocity simulations were begun, the or
der parameter and composition elds were allowed to equilibrate in a 2step process.
The rst step is to allow the order parameter and composition elds to simultaneously
evolve. The number of iterations must be long enough to fully equilibrate the order
parameter, but short enough that the microstructure does not begin to change signi
cantly. Testing was performed on a at interface to estimate the number of iterations
required to equilibrate the order parameter at the solidliquid interface. A 10 10
30 array was created with a sharp solidliquid interface at z = 15. This array was
smoothed with a 5voxel volume smooth and resized to 20 20 60 to match the
107
interface shapes of the experimental microstructure as closely as possible. The phase
eld code was modied so that every 10
4
iterations it subtracted the value of the order
parameter at each point from its value 10
4
iterations ago, and continued to run until
the maximum change in the order parameter at any point was less than 10
8
. This
provided an estimate of the number of iterations required for the interfaces to equi
librate. The simulation was run with simulation parameters x = 0.4W, k = 0.145,
D
S
= 0, and = 700 (based on a rough estimate of the capillary length). 8.5 10
5
iterations were required for the interface to reach its equilibrium shape.
The resized subset of the experimental data was then input in to the phaseeld
model. To further test the number of iterations required for the rst step in the in
terface equilibration process, the number of iterations in the rst step was varied, and
the composition eld was then equilibrated holding the order parameter xed. The
resulting , c elds were evolved together for another 100,000 iterations, and interfa
cial velocities were calculated between the beginning and end order parameter arrays
(Figure 6.5). The simulation parameters were x = 0.4W, k = 0.145, D
S
= 0, and
= 700, and noux boundary conditions. The large positive and negative velocities
near the boundaries of the simulation volume are due to the noux boundary condi
tions imposed. The velocities on the isolated liquid droplets and the bulbshaped liquid
region in the center of the simulation volume were chosen as the basis for comparison
with the experimental data, as they were best isolated from anomalous eects at the
boundaries due to the assumption D
S
= 0.
Figure 6.5 shows that after 800,000 initial iterations, the large anisotropy in ve
locity seen in the bulb and liquid droplets (most clearly visible in Figure 6.5(a)) has
108
(a) (b)
(c) (d)
Figure 6.5. Interfacial velocities simulated using (a) 500,000, (b) 800,000,
(c) 1,000,000, (d) 1,500,000 initial iterations of the phaseeld model,
followed by composition eld equilibration and 100,000 further iterations
for the velocity calculation. The liquid phase is capped at the boundaries
and surfaces are colored by interfacial velocity.
109
(a) (b)
Figure 6.6. (a), (b) Two dierent views of the larger simulation volume
selected for velocity calculations.
decreased signicantly. Because of this result and the results obtained on the at
interface described previously, 800,000 iterations was chosen as the number of initial
iterations to equilibrate the order parameter, followed by composition eld equilibra
tion as described previously. Again, this was chosen to equilibrate the order parameter
while maintaining the system microstructure as close to the original as possible.
Figure 6.5 shows the strong eect the noux boundary conditions imposed on the
simulation have on the calculated velocities at the boundaries. To further investigate
the eects of boundary conditions, a larger system volume was selected for input into
the phaseeld model (Figure 6.6). The principles used in choosing this simulation
volume were:
110
The liquid bulb at the center of the simulation volume will be the basis for
quantitative comparison of theory and experiment.
The simulation volume is larger to provide a buer for the bulb shape from the
eects of the noux boundary conditions. Additionally, the volume is chosen
so that the solidliquid interfaces intersect the simulation boundaries as close
to perpendicular as possible, to minimize solute ux created by articially
large curvatures due to noux boundary conditions.
The height in the zdirection is large enough that the order parameter eld
surrounding the liquid bulb reaches its equilibrium value before intersecting
the boundary.
A large liquid volume remains connected to the liquid bulb to act as a reservoir
for solute in the simulation volume.
This 150 120 115 voxel simulation volume was rebinned in IDL as before to
a size of 300 240 230 voxels and loaded in to the phaseeld model. Simulation
parameters were x = 0.4W, = 771, k = 0.145, and noux boundary conditions
were used. The initial microstructure was equilibrated 800,000 iterations, followed by
holding the order parameter xed and equilibrating the composition eld. After the
order parameter and composition elds were equilibrated, the system was allowed to
evolve for 0.5, 1, and 5 seconds of real time and interfacial velocities were calculated.
The interfacial velocities were approximately the same for all three simulation times.
111
(a) Interfacial velocities calculated from experi
mental data. 5 minutes 46 seconds between Xray
scans.
(b) Interfacial velocities calculated from phaseeld
simulations. 5 seconds simulated time elapsed for
velocity calculation.
Figure 6.7. Comparison of experimental and simulated velocities. The
solidliquid interface is shown colored by normal velocities, with negative
velocities pointing into the liquid. Liquid is inside the bulb shape, and
the solid phase is transparent. Note color bars between left and right
images dier by a factor of 3.
6.5. Comparing Experiment to Theory
Experimental results are compared with simulation data in Figure 6.7. Interfacial
velocities are shown for a 150160180 voxel (105112126 m) subset of the mi
crostructure. The qualitative features of the velocity distribution on the liquid bulb
are similar, but it is important to note that the color bars of Figure 6.7(a) and 6.7(b)
dier by a factor of 3.
Figure 6.7 shows that qualitative agreement between experimental and simulated
velocities is good, with the model accurately reproducing most of the ner details of
the velocity distribution and their relative magnitudes correctly. However, as shown
112
Figure 6.8. Normalized histograms of experimentally measured and
scaled simulated interfacial velocites. The simulated velocities are scaled
by 1/2.9, the scale factor that produced the best leastsquares t between
the two normalized histograms.
by the color bars, the overall magnitude of the velocities estimated by the phaseeld
simulations is higher by approximately a factor of three.
To better quantify how much the simulations overestimate the interfacial velocities,
the distributions of velocities from experiment and simulation (Figure 6.7) were plotted
as normalized histograms. A leastsquares t was used to determine the scale factor
between the normalized histograms (Figure 6.8). The simulated interfacial velocities
were a factor of 2.9 0.1 greater than experimentally measured velocities.
6.6. Analysis of Contributions to Error
To understand the causes of the dierences between experimentally measured and
simulated velocities, the following potential causes were considered: accuracy of the
phaseeld model at high , use of a dilute solution approximation in the model, the
113
assumption D
S
= 0, and the physical parameters used to convert from dimensionless
simulation results to physical units.
6.6.1. PhaseField Model at Large
To quantify the contribution of error from the phaseeld model, it is necessary to
understand the limits of the models validity. Echebarria et. al. achieved wellconverged
results using in the range of 10 to 100, even though their sharpinterface analysis
assumes that is of order unity. They showed that in the limit of vanishing interface
kinetics, results would still be wellconverged for larger as long as W/R 1, where
W is the interface width and R is the local radius of curvature of the solidliquid
interface, or equivalently, WH 1, where H is the local interfacial mean curvature.
For future work, it was desired to maintain the ratio of grid spacing to interface width
at x/W = 0.4 in order to maintain approximately 10 points through the interface for
accurate calculations of mean and Gaussian curvatures and their rates of change. This
means wellconverged results could be obtained as long as 2.5xH 1. This clearly
illustrates the tradeo between accuracy, which requires x small, and computation
time, memory and storage requirements, which increase as (1/x)
3
.
The mean curvature of the solidliquid interface was calculated for the experimental
data using H =
1
2
( n). The highest mean curvature was found at the tip of the
bulbshaped region where H = 0.07 m
1
. To test the accuracy of the model at
this curvature and for an interface width of W = 0.4x, the decay of a sinusoidal
perturbation at a stationary solidliquid interface with the same curvature and interface
width was simulated in two dimensions and compared with the results of the linear
114
stability analysis. The maximum curvature of the perturbation is found at its point of
maximum amplitude and is given by
(6.9) H =
4
2
A
2
where A is the perturbation amplitude and is the wavelength. Assuming no diu
sivity in the solid, the linear stability analysis predicts that the perturbation decays
exponentially with decay constant :
(6.10) =
D
L
d
2
0
k
4
2
_
1
1 +
4
d
2
0
k
4
_
where k is the magnitude of the wave vector of the perturbation.
To evaluate the eect of and grid spacing x, perturbation decay simulations were
run maintaining a constant physical system size by simultaneously varying and grid
spacing as in Section 6.3. The decay constants of the perturbations were determined at
the time when the maximum curvature of the perturbation was equal to the curvature
at the tip of the bulb, and compared with the predictions of decay constants from the
linear stability analysis. The dierence between the linear stability analysis predictions
and simulation results is shown in Figure 6.9.
The error for = 1400 and grid spacing of x = 1.4 m (the native resolution of
the experimental data) was 26%. At this grid spacing, WH = 0.23, which compares
reasonably with the results of [61], which reported signicant error when WH 0.2.
Since = 771 was used in the simulations for velocity calculations, the phaseeld
model is not a major contributor to error in the velocity predictions. Additionally,
115
0%
5%
10%
15%
20%
25%
30%
0 200 400 600 800 1000 1200 1400 1600
D
e
c
a
y
c
o
n
s
t
a
n
t
E
r
r
o
r
Epsilon
Error
Figure 6.9. Dierence between theoretical prediction and simulation re
sults for perturbation decay for high values of .
using this much larger value of than previously tested allows this model to be used
to simulate much larger physical systems for studies of isothermal coarsening.
6.6.2. Eect of Assumption D
S
= 0
The phaseeld model used for these calculations assumes zero solute diusivity in
the solid phase. Using D
S
= 1.5 10
13
m
2
/s [77], D
S
is more than four orders of
magnitude less than D
L
. Solute ux balance at the interface requires that
(6.11) (C
0
L
C
0
S
)v
n
= D
L
C
L
n
D
S
C
S
n
where v
n
is the velocity of the interface in the normal direction, derivatives with respect
to n are spatial derivatives taken in the normal direction, C
0
L
and C
0
S
are the equilibrium
liquid and solid compositions, and we assume that (C
L
C
S
) (C
0
L
C
0
S
). By
estimating the magnitude of
C
S
n
, we will show that the contribution from the term
D
S
C
S
n
is three orders of magnitude smaller than (C
L
C
S
)v
n
. This will show that
the assumption D
S
= 0 used in the phaseeld model is valid for calculating interfacial
116
velocities, and that this assumption is not a signicant contribution to the disagreement
between simulations and experiment.
To estimate the amount of diusion through the solid, we focus on the spherical tip
of the bulbshaped liquid region. First we show that solute gradients remaining from
solidication should be eliminated by the time of this scan. The distance through the
solid from this spherical tip to the nearest interfacial regions (not shown) is 40 m.
The system had been isothermally coarsened for approximately 2.6 hours at the time of
this scan. The characteristic length for diusion through the solid at this time is given
by
D
s
t = 37 m, meaning that solute concentration gradients in the solid remaining
from the solidication process should be relatively smooth on the scale of the distance
between the spherical cap and nearest interfaces. Therefore, the solute ux through
the solid is driven primarily by the GibbsThomson eect.
To estimate solute ux through the solid, it is assumed that since the spherical tip is
moving with velocity v
n
= 0.005 m/s, v
n
/D
S
= 3.4 10
4
m
1
, and the diusion eld
surrounding the spherical tip is approximately Laplacian. The solute concentration
eld surrounding the spherical cap can be approximated by the concentration eld
surrounding a spherical particle of radius R [78, 79]:
(6.12) C
S
(r) = C
0
S
+
R
r
_
C
S
(r = R) C
0
S
where C
S
(r = R) is found from the GibbsThomson equation. Using this assumption,
the ux of solute through the solid is given by
(6.13) D
s
C
S
r
= D
S
[C
S
(r = R) C
0
S
]
R
117
By the GibbsThomson equation,
(6.14)
_
C
S
(r = R) C
0
S
= (C
0
L
C
0
S
)d
0
H
and using R = 1/H = 1/0.07 m
1
at the tip of the spherical cap, the ux of so
lute through the solid is [1.7 10
6
m/s (C
0
L
C
0
S
)]. This is more than three
orders of magnitude less than the lefthand side of Equation 6.11, (C
0
L
C
0
S
)v
n
=
[5 10
3
m/s (C
0
L
C
0
S
)]. This shows that the ux through the solid is a much
smaller contribution to interface motion than ux through the liquid, and that D
S
= 0
is a valid assumption for these simulations.
6.6.3. Physical Parameters
Another possible source of disagreement between theory and experiment is the physical
parameters used in converting the dimensionless model results to dimensional units,
shown in Table 6.1. The phaseeld model uses a dilute solution approximation which
assumes straight liquidus and solidus lines. Since the values of k and m
L
used were
taken from the AlCu phase diagram [75] at the coarsening temperature, the dilute
solution approximation should not cause error since the systems position on the phase
diagram does not change.
The capillary length d
0
is calculated from the GibbsThomson coecient and phase
diagram parameters as in [61]. The GibbsThomson coecient was measured by
G und uz and Hunt in their grain boundary cusp experiments [76]. This measurement
was taken at very nearly eutectic temperature and liquid composition, and so should
118
be accurate for this experiment. The estimated error in the measured GibbsThomson
coecient is 5% [76]).
Of the necessary parameters, the most dicult to measure is the diusion coecient
of solute in the liquid. By Equation 6.8, D
L
aects the units of dimensionless time
used in the phaseeld equations:
=
a
1
a
2
3
d
2
0
D
L
The eect of a lower D
L
is to reduce the simulated interfacial velocity. The value of
D
L
= 2.4 10
9
m
2
/s (at the eutectic point) used was determined by Lee et. al. [74].
Their measurement was lower than any previously measured values because they care
fully controlled experimental conditions to try to eliminate the eect of convection in
the liquid, and showed how the presence of convection increased the eective diu
sion coecient. D
L
is believed to be the largest possible contribution to disagreement
between the present experiments and simulation results, and the trend in D
L
with in
creasingly accurate experimental measurements points toward better agreement. The
leastsquares t of simulated to experimental velocities can even be used to obtain a
better estimate of D
L
, due to the inverse proportionality of the time step to D
L
:
(6.15) D
L
=
2.4 10
9
m
2
/s
2.9
= 8.3 10
10
m
2
/s
The use of this estimate of D
L
will be further discussed in Chapter 7.
119
Figure 6.10. Interfacial velocity prediction using phaseeld model with
out antitrapping current.
6.7. Eect of Antitrapping Current
To evaluate the eect of the antitrapping current in the phaseeld model on
interfacial velocity prediction and computation time, the simulation was repeated with
the antitrapping term removed from the phaseeld model.
As Figure 6.10 shows, there is very little dierence between the model predictions
with and without the antitrapping current. This is due to the relatively low interfacial
velocities found under conditions of isothermal coarsening relative to directional solid
ication. By removing this term from the model, the computation time per iteration
was reduced by a factor of 1.6 without penalty in accuracy.
120
6.8. Conclusions
The interfacial velocities of a portion of a dendritic AlCu alloy undergoing coars
ening were determined experimentally using Xray tomography and simulated using
phaseeld modeling. The features of the experimental and simulated velocity distri
butions agreed well qualitatively, while the magnitudes of the velocity distributions
diered by a factor of 2.9. The diusion coecient of solute in the liquid is believed to
be the largest contribution to the discrepancy. These results suggest that the phase
eld method could be used to validate or even measure experimental parameters such
as D
L
. In validating the phaseeld model, it was shown that much larger values of
the length scale parameter than previously tested were valid, allowing much larger
physical systems to be simulated for isothermal coarsening. Finally, it was shown that
for the present isothermal coarsening simulation, the antitrapping current could be
neglecting, increasing computational eciency by a factor of 1.6.
121
CHAPTER 7
SelfSimilar Pincho of Rods
As discussed in Section 2.5, selfsimilar pincho has been observed experimentally
in uid dynamics systems. Although it has been shown theoretically that selfsimilar
pincho should occur in pinching by surface diusion, the possibility of selfsimilarity
during pinching by bulk diusion has not been explored theoretically or experimentally.
In the experiments described in Section 6.2, during the coarsening of the solidliquid
mixture in the AlCu alloy, many liquid tubes were observed undergoing the pinching
process following Rayleigh instabilities. The mechanism of pinching is bulk diusion
inside the liquid tube, with negligible contribution from diusion through the solid.
Hundreds of tubes pinching were observed throughout the experiment. Because the
evolution of the tubes was monitored as a function of time, the shape of the tubes could
be observed for several time steps before the time of pinching. In most of the pinching
events, a cone shape with a similar angle was asymptotically approached suciently
close in space and time to the point of pinching. Figure 7.1 shows numerous liquid
tubes at various stages of the pinching process.
Motivated by experimental data as shown in Figure 7.1, we began to investigate
the possibility of a selfsimilar solution for the interface shape of a rod pinching by
bulk diusion.
122
Figure 7.1. The microstructure of the AlCu alloy experimentally ob
served during coarsening, with the liquid region capped at the boundary.
The region boxed in red shows several liquid tubes at various stages in
the approach to pinching and one immediately after pinching.
7.1. Theoretical Formulation
The pinching process is caused by the diusional motion of Cu solute atoms through
the liquid driven by the interfacial energy between the solid and liquid phases. The
diusion eld in the liquid is given by
(7.1)
C
L
t
= D
L
2
C
L
where C
L
is the concentration of solute and D
L
is the diusion coecient of solute in
the liquid. We assume that D
S
= 0 in the surrounding solid. We seek a solution to
123
Equation 7.1 consistent with the boundary conditions. The rst is the GibbsThomson
equation
(7.2) C
L
= C
0
L
+
_
C
0
L
C
0
S
_
d
0
H
where C
L
is the solute concentration on the liquid side of the interface, C
0
L
and C
0
S
are
the equilibrium solute concentrations at a at interface, d
0
is the capillary length, and
H is the mean interfacial curvature. The other boundary condition is the interfacial
mass balance,
(7.3)
_
C
0
L
C
0
S
_
v = D
L
C
L
n
where v is the interfacial velocity in the direction normal to the interface, and C
L
/n
is the derivative of the concentration eld in the normal direction.
7.1.1. Similarity Variables
In cylindrical coordinates, the position of the solidliquid interface as a function of
time is given by r = f(z, t). If a valid similarity coordinate system can be found,
the shape of the interface can be written in a timeindependent form as = f(), or
dened parametrically F = f() = 0. Prior to pinching, the similarity variables
are expected to be of the form
(7.4) =
rB
(t
s
t)
, =
zB
(t
s
t)
124
where r is the radial coordinate of the interface position, z is the axial coordinate,
and are the radial and axial coordinates in the timeindependent similarity variables,
and B is a dimensional constant. (The dependent and independent variables will be
reversed when solving for the postpinching shape, see Section 7.3.)
To determine whether a valid similarity coordinate system exists, we dene the
dierence between the solute concentration in the liquid and the equilibrium concen
tration in terms of a scaled concentration in similarity variables, K(, ):
(7.5) C
L
(r, z, t) C
0
L
= t
AK (, )
Substituting (7.5) into (7.2) and (7.3) and using (7.4), we nd that = = 1/3
is required for a selfsimilar solution that is consistent with the boundary conditions
(see Appendix B for details.) The diusion equation allows a similarity solution only
for = 1/2. However, suciently far from the time of pinching, when the interfacial
velocity is moving slowly in comparison to the time required for the diusion eld to
relax, the quasistationary approximation C
L
/t 0 can be used. In this regime,
the diusion eld is governed by Laplaces equation,
2
C
L
= 0, and = 1/3 is a
valid temporal exponent. From (7.2) and (7.3), a similarity solution also requires that
B = (D
L
d
0
)
1/3
and A = (C
0
L
C
0
S
) (d
2
0
/D
L
)
1/3
.
7.2. PhaseField Simulations
Before determining the shape of the interfaces in the selfsimilar coordinate system,
a pinching event was simulated to determine whether the quasisteady approximation
held long enough for selfsimilar behavior to be observed, and whether the cone angles
125
(a) (b)
Figure 7.2. Phaseeld simulations of liquid cylinder pinching o by bulk
diusion. Black represents liquid, white represents surrounding solid. (a)
Initial conditions, (b) shape just prior to pinching.
observed in modeling were similar to the angles measured in the experimental data.
A liquid cylinder with a sinusoidal perturbation in interface position along its axis,
surrounded by solid, was created as a 3D array in IDL and loaded into the binary
alloy phase eld model described in Section 3.5.2. The diameter of the cylinder was 50
gridpoints, the wavelength of the perturbation was 176 gridpoints, and perturbation
amplitude was 3 gridpoints. The size of the simulation volume was 176 100 100,
= 2, and the interface width was x = 0.8W resulting in an interface width of 5
points. Periodic boundary conditions were used. Figure 7.3 shows the initial conditions
of the system and the shape just prior to the time of pinching.
A plot of r
3
(where r is the minimum radius of the cylinder) versus t should be
linear if t
1/3
is a valid choice of the similarity variable. Early in the pinching process,
r
3
versus t does not follow a linear slope (Figure 7.3(a)), because initial conditions still
exert a strong eect on the dynamics of the pinching process. However, as the time of
pinching is approached, r
3
versus t begins to follow a linear slope as the eects of initial
conditions become less important and the shape becomes locally determined. The slope
126
y = 0.0123x + 24603
R! = 0.99913
0
1000
2000
3000
4000
5000
6000
7000
1.0E+06 1.2E+06 1.4E+06 1.6E+06 1.8E+06 2.0E+06
R
3
(
g
r
i
d
p
o
i
n
t
s
3
)
Time (iterations)
080721a
080804a
(a)
0
5000
10000
15000
20000
25000
30000
35000
40000
45000
50000
1.85E+06 1.90E+06 1.95E+06 2.00E+06 2.05E+06 2.10E+06 2.15E+06 2.20E+06 2.25E+06
(
D
i
s
t
a
n
c
e
f
r
o
m
x
=
0
t
o
c
u
s
p
)
3
(
g
r
i
d
p
o
i
n
t
s
3
)
Time (iterations)
080804a
(b)
Figure 7.3. From phaseeld simulations, (a) minimum radius of a pinch
ing cylinder cubed, (b) distance between tips of cones after pinching
cubed versus time. The linear slope close to the point of pinching sup
ports t
1/3
dependence of the similarity variables close to the point of
pinching.
becomes linear when r 10. Since the original radius of the cylinder is 25, the slope is
actually linear for a considerable fraction of the pinching process. Since the similarity
variables should also be valid after pinching is complete, the distance between the tips
of the cones formed after pinching should also follow the same scaling, and d
3
versus
t should also be linear. Although this behavior is dicult to observe experimentally
because of the much faster speed of the receding tips, the simulation time step can be
made adequately small to observe this behavior. Figure 7.3(b) shows that d
3
versus t
is also linear suciently close to the point of pinching.
These results suggest that the use of similarity variables with t
1/3
dependence is
justied. In some past work, the universal shape of the interface was determined from
timedependent simulations [32]. However, those simulations used an adaptive grid
spacing and time stepping algorithm that allowed the interface shape to be determined
127
arbitrarily close to the point of pinching. As Figure 7.3(a) shows, the time step of
these phaseeld simulations was changed as the time of pinching was approached, but
the lack of adaptive grid spacing in our phaseeld model means that as the point of
pinching is approached, the interface width becomes the same order of magnitude as
the size scale of the pinching tips, so there is insucient resolution to determine the
shape. Additionally, due to the use of the quasisteady approximation, the scaling is
expected to break down suciently close to the point of pinching. For these reasons,
the problem was transformed to similarity variables and shape of the interface was
solved in this coordinate system.
The shapes of the cones from phaseeld simulations and experimental data were
also compared to see if the possibility of a universal shape is suggested (Figure 7.4).
To measure the cone angles, lines were drawn approximating the shape of the cone on
a 2D crosssection of the pinching cylinders as close as possible to the time of pinching.
The cone angles were measured using the Measurement tool in Adobe Photoshop.
The angle measured from the phaseeld simulations was 68
to 71
_
0
_
K[, f()]
[f() + f(
0
) + f
()(
0
)]
(
0
)
2
+ [f() f(
0
)]
2
1
3
[f() f
()] ln
_
(
0
)
2
+ [f() f(
0
)]
2
_
d
+
1
_
0
_
K[, f()]
[f() + f(
0
) + f
()( +
0
)]
( +
0
)
2
+ [f() f(
0
)]
2
1
3
[f() f
()] ln
_
( +
0
)
2
+ [f() f(
0
)]
2
_
d
(7.11)
where primes denote derivatives in the direction.
131
In the similarity coordinate system, K(, ) = n. This can be written in terms
of the interface shape f() as
(7.12) K[, f()] =
f
()
[1 + f
()]
3/2
Equation 7.12 is substituted into Equation 7.11 and a set of integrodierential
equations for f() is obtained. Boundary conditions are that f() approaches a straight
line with angle from the axis (where 2 is the cone angle, see Figure 7.5) as
and f
when =
0
. LH opitals rule is used on the term in the
rst line of 7.11 to show that
(7.13) lim
0
[f() + f(
0
) + f
()(
0
)]
(
0
)
2
+ [f() f(
0
)]
2
=
f
()
2[1 + f
()
2
]
which is used to numerically evaluate this term when =
0
. Newtons method is then
used to iteratively solve for f(), starting with a straight line with angle as an initial
guess for the shape.
The interface shapes found are shown in Figure 7.6, and correspond to the red line
in Figure 7.5(c). As expected from comparing to the results of the surface diusion
case, after pinching, a solution was found for any angle except for very sharp angles
< 20
, when the straightline initial guess is a poor approximation for the nal shape.
132
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5
!
f(!)
30
40
50
60
70
80
Figure 7.6. Shape of the 2D solidliquid interface after pinching by
interfacialenergy driven bulk diusion. For each curve, the solid lies
to the upper left, and the liquid to the lower right of the curve.
The solution for the shape should converge to the exact solution as the grid point
spacing along the axis goes to zero, and the truncation length in the direction goes
to innity. Convergence is therefore tested by varying the grid spacing and by varying
truncation length in the direction. Varying the grid spacing produced no visible
change in a plot of the interface shape. Varying truncation length with xed spacing,
the shape did change slightly as was increased from 5 to 10, but much less as was
increased further (Figure 7.7(a) shows results for = 80
).
Let f(
i
) be the exact solution at
i
, and f
(
i
) be the estimate from numerical
approximation with a grid spacing . Since Newtons Method is a secondorder
convergent approximation scheme, once the grid spacing becomes suciently small,
133
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
!
f(!)
Length=5
Length=10
Length=20
Length=40
(a)
0
1
2
3
4
5
6
7
8
9
0 1 2 3 4 5 6 7 8 9 10
f
(
!
)
!
Error ratio 1
Error Ratio 2
(b)
0
1
2
3
4
5
6
7
0.0 1.0 2.0 3.0 4.0 5.0
R
a
t
i
o
o
f
E
r
r
o
r
s
!
Error ratio 1
Error ratio 2
(c)
Figure 7.7. (a) Variation of 2D solidliquid interface shape (after pinch
ing, = 80
T
= 5 (Error ratio 1), and
T
= 10 (Error ratio 2).
the error ratio
(7.14) Error ratio =
(
i
) f
/2
(
i
)
f
/2
(
i
) f
/4
(
i
)
134
should approach 4.0 at all points
i
. Figure 7.7(b) shows that for the solution with
= 80
, as the initial grid spacing is decreased from 0.5 to 0.25, the expected
quadratic convergence with grid spacing is observed.
Similar testing for truncation length is shown in Figure 7.7(c). In this case, the
error ratio is dened as
(7.15) Error ratio =
[f
T
(
i
) f
2
T
(
i
)[
[f
2
T
(
i
) f
4
T
(
i
)[
where
T
is the truncation length in the direction, and the number of grid points is
simultaneously varied to keep the grid spacing constant. Quadratic convergence is also
observed for variation of truncation length when grid spacing is 0.25.
7.3.2. Interface Shape After Pinching in 3D
After verifying correct operation and convergence of the code in 2D, the code was
modied to solve for the shape of the interface after pinching in 3D. Since by analogy
with the surface diusion case, a solution is expected for any cone angle after the time
of pinching [33], the 3D version of the code could be debugged without simultaneously
needing to search for the correct cone angle. The coordinate system is again given in
Equation 7.7, and the integrodierential equation is given by Equation 7.6. The system
is assumed to be axially symmetric about the axis. In 3D, the freespace Greens
function for Laplaces equation is
g =
1
4 [r
i
(, ) r(
0
,
0
)[
(7.16)
135
=
1
4 [( cos
0
cos
0
)
2
+ ( sin
0
sin
0
)
2
+ (
0
)
2
]
1/2
(7.17)
where is the angular coordinate in the radial coordinate system. The integration is
performed along the axis, and the angular integral is rewritten as a complete elliptic
integral of the rst kind and approximated using the polynomial approximation of [80].
Substituting for the Greens function and using the solute conservation boundary con
dition to substitute for
K
n
the following integrodierential equation for K[, f()] is
obtained (see Appendix D for details):
2K[
0
, f(
0
)] =
_
0
d
_
K[, f()]
_ _
f
()4( +
0
)
(l
2
+ k
2
)
3/2
4[f() f(
0
)]
(l
2
+ k
2
)
3/2
_
_
4
n=0
_
a
n
b
n
ln
_
1
k
2
l
2
+ k
2
__ _
1
k
2
l
2
+ k
2
_
n
_
+
_
16
0
f
() [
2
2
0
[f() f(
0
)]
2
]
(l
2
+ k
2
)
5/2
+
32
0
[f() f(
0
)]
(l
2
+ k
2
)
5/2
_
_
4
n=1
n
_
a
n
b
n
ln
_
1
k
2
l
2
+ k
2
__ _
1
k
2
l
2
+ k
2
_
n1
n=0
b
n
_
1
k
2
l
2
+ k
2
_
n1
__
4[f
() f()]
3(l
2
+ k
2
)
1/2
4
n=0
_
a
n
b
n
ln
_
1
k
2
l
2
+ k
2
__ _
1
k
2
l
2
+ k
2
_
n
_
(7.18)
where a
n
, b
n
are numerical constants dened in [80], l
(
0
)
2
+ [f() f(
0
)]
2
,
and k
2
4
0
. In this coordinate system, the curvature can be written in terms of the
136
interface shape f() as
(7.19) K[, f()] =
f
()
[1 + f
()
2
]
3/2
+
f
()
[1 + f
()
2
]
3/2
Equation 7.19 is substituted into Equation 7.18 and a set of integrodierential
equations for f() is obtained. Having reduced the 3D problem to a 1D integral, the
system of equations is solved numerically using the boundary conditions and numerical
methods as described in Section 7.3.1. LH opitals rule and Taylor expansions were used
as necessary for terms where =
0
.
The interface shapes found are shown in Figure 7.8. As in the 2D case, after
pinching, a solution was found for any angle except for very sharp angles < 20
,
when the straightline initial guess is a poor approximation for the nal shape.
Convergence was again tested by varying the grid spacing and by varying truncation
length in the direction. Varying the grid spacing produced no visible change in a plot
of the interface shape. The interface shape changed much less with changing truncation
length than the 2D case (Figure 7.9(a) shows results for = 80
).
The error ratios for varying grid spacing and truncation length are shown in Fig
ure 7.9(b) and 7.9(c). The error ratios to begin to approach 4 but not as closely as the
results of the 2D solution. This may be due to the use of a numerical approximation
for the angular integral.
137
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
5
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5
!
f(!)
30
40
50
60
70
80
Figure 7.8. Shape of the 3D solidliquid interface after pinching by
interfacialenergy driven bulk diusion. For each curve, the solid lies
to the upper left, and the liquid to the lower right of the curve.
7.3.3. Interface Shape Before Pinching in 3D
To solve for the shape prior to pinching, the dependent and independent variables are
reversed, and the coordinate system is
(7.20) =
rB
(t
s
t)
1/3
, =
zB
(t
s
t)
1/3
The system is assumed to be axially symmetric about the axis in this case. The ge
ometry and portion of the interface shape being determined are shown in Figure 7.5(a).
In 3D, the freespace Greens function for Laplaces equation is again
(7.21) g =
1
4 [( cos
0
cos
0
)
2
+ ( sin
0
sin
0
)
2
+ (
0
)
2
]
1/2
138
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
5
0 0.2 0.4 0.6 0.8 1
!
f(!)
Length=5
Length=10
Length=20
(a)
0
1
2
3
4
5
6
7
8
9
0 1 2 3 4 5
R
a
t
i
o
o
f
E
r
r
o
r
s
!
Error ratio 1
Error ratio 2
(b)
0
1
2
3
4
5
6
7
8
9
0 1 2 3 4 5
R
a
t
i
o
o
f
E
r
r
o
r
s
!
Error ratio 1
Error ratio 2
(c)
Figure 7.9. (a) Variation of 3D solidliquid interface shape (after pinch
ing, = 80
_ _
4f
()(
0
)
(l
2
+ k
2
)
3/2
+
4( +
0
)
(l
2
+ k
2
)
3/2
_
M
_
k
2
l
2
+ k
2
_
+
_
32
0
(
0
)f
()
(l
2
+ k
2
)
5/2
16
0
[
2
2
0
(
0
)
2
]
(l
2
+ k
2
)
5/2
_
M
d
_
k
2
l
2
+ k
2
__
4
3
[f
() f()]
_
l
2
+ k
2
M
_
k
2
l
2
+ k
2
_
+ K[, f()]
_ _
4f
()( +
0
)
(l
2
+
+ k
2
)
3/2
+
4( +
0
)
(l
2
+
+ k
2
)
3/2
_
M
_
k
2
l
2
+
+ k
2
_
+
_
32
0
( +
0
)f
()
(l
2
+
+ k
2
)
5/2
16
0
[
2
2
0
( +
0
)
2
]
(l
2
+
+ k
2
)
5/2
_
M
d
_
k
2
l
2
+
+ k
2
__
4
3
[f
() f()]
_
l
2
+
+ k
2
M
_
k
2
l
2
+
+ k
2
__
(7.22)
where M is the polynomial approximation for a complete elliptical integral of the rst
kind dened in [80], M
(
0
)
2
+[f() f(
0
)]
2
, l
+
(
0
)
2
+[f() +f(
0
)]
2
, and k
2
4
0
. In this
coordinate system, the curvature can be written in terms of the interface shape f()
as
(7.23) K[, f()] =
1
_
1 + f
()
2
()
[1 + f
()
2
]
3/2
140
Equation 7.23 is substituted into Equation 7.22 and a set of integrodierential
equations for f() is obtained. Having reduced the 3D problem to a 1D integral, the
system of equations is solved numerically using the boundary conditions and numer
ical methods as described in Section 7.3.1. LH opitals rule and Taylor expansion to
approximate integrable singularities were used as necessary for terms where =
0
.
Since by analogy with the surface diusion case, solutions are not expected at
arbitrary cone angles [33], an iterative process was used to search for the solutions.
A coarse grid spacing along was used to search for solutions as was varied using
the boundary condition f
() = 0. The angle and f(0) were iteratively rened until a smooth solution with
f
= 52
. The interface
shape found is shown in Figure 7.10.
As shown in [81], in the similarity coordinate system a countably innite number
of solutions is expected at various angles prior to pinching, but only the solution
with the largest cone halfangle is expected to stable in timedependent variables.
The presence of at least one additional solution prior to pinching was veried in the
similarity variables (see Figure 7.10).
141
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
5
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5
f
(
!
)
!
52
75
Figure 7.10. Shape of the 3D solidliquid interface before pinching by
interfacialenergy driven bulk diusion. The solution at = 52
is ex
pected to be stable, while the solution at = 75
is expected to be
unstable ( = 90
).
Varying the grid spacing produced no visible change in a plot of the interface shape.
The interface shape changed much less with changing truncation length than the 2D
case (Figure 7.11(a) shows results for = 52
).
Convergence was again tested by varying the grid spacing and by varying truncation
length in the direction. Changing truncation length produced a smoother f() when
was increased above 5. The error ratios for varying grid spacing and truncation length
are shown in Figure 7.11(b) and 7.11(c). In this case the solution does converge, but not
quadratically. This is likely due to the use of a numerical approximation for the angular
integral, a dierent boundary condition at = 0, and the diculty of identifying the
exact angle of the solution. However at this angle the solution could be resolved to an
142
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5
f
(
!
)
!
Length=5
Length=10
Length=20
(a)
0
1
2
3
4
5
6
7
8
9
0 1 2 3 4 5 6 7 8 9 10
R
a
t
i
o
o
f
e
r
r
o
r
s
!
Error ratio 1
Error ratio 2
(b)
0
2
4
6
8
10
12
14
16
18
20
0.0 1.0 2.0 3.0 4.0 5.0
R
a
t
i
o
o
f
E
r
r
o
r
s
!
Error ratio 1
Error ratio 2
(c)
Figure 7.11. (a) Variation of 3D solidliquid interface shape before pinch
ing ( = 52
( = 40
).
7.3.4. Interface Shape Before Pinching in 3D for Solid Cylinders in a Liquid
Matrix
To broaden the applicability of these techniques, the problem of solid cylinders pinching
o in a liquid matrix was also considered. The formulation of Section 7.3.3 is again
used, the only dierences being that the sign of K and the direction of the normal
vector change. A solution was found using the solution search method as described in
Section 7.3.3 at = 40
.
144
7.4. Comparison with Experimental Data
The results of Section 7.3.3 were compared with experimental data for pinching
liquid cylinders. Quantitative analysis of the experimental microstructures was per
formed by A.E. Johnson of Northwestern University. Since the data is obtained in
three dimensions, it is possible to view the tube along its axis to measure accurately
its smallest cross section or diameter. If the pinching process proceeds in a selfsimilar
fashion, then the diameter of the tube should decrease linearly as (tt
s
)
1/3
. Figure 7.13
shows that the diameter does decrease linearly as (t t
s
)
1/3
. This behavior was also
observed in each of the 19 other pinching events investigated.
To test the validity of the quasistationary approximation, we compare the kinetics
predicted by the similarity solution to the experimental data of Figure 7.13. The error
bars give the minimum and maximum diameter of the liquid tube at a given time. They
are nonzero because the diameter is not circular at all times. Figure 7.13 shows that as
the singularity is approached, the cross section becomes increasingly circular, consistent
with the theoretical prediction. The excellent t to a straight line indicates that the
temporal exponent of 1/3 holds, showing that the quasistationary approximation is
valid over nearly the entire time interval of the experiment.
The prefactor of the temporal power law of the theoretical prediction for time
dependence of diameter can be determined from theory and compared to experimental
data. Using Equation 7.20, the radius at the center ( = 0) of a pinching liquid tube,
R(t), evolves as
(7.24) R(t) = f(0) (D
L
d
0
)
1/3
(t
s
t)
1/3
145
0
5
10
15
20
25
25 20 15 10 5 0
P
i
n
c
h

o
f
f
D
i
a
m
e
t
e
r
(
m
)
(tt
s
)
1/3
(s
1/3
)
Figure 7.13. Tube diameter follows a power law prior to singularity. The
diameter of a pinching tube as a function of (t t
s
)
1/3
along with the
experimentally measured and theoretically predicted interface shapes at
various times and line showing leastsquares t to experimental data.
(Error bars show the maximum and minimum measured diameter of
tubes, which are not circular at all times.) It is clear that even when the
interfacial morphology is far from the selfsimilar shape, the kinetics of
the pinching process are still well described by (tt
s
)
1/3
. Figure courtesy
of A.E. Johnson.
where f(0) = 0.60 and 0.37 for the solutions with cone angles (2) of 76
, and 30
,
respectively, see Figure 7.10. Thus, suciently close to the singularity, the time
dependence of the pincho process is independent of initial conditions and is a function
of only f(0) and materials parameters.
146
From Equation 7.24, the slope of the line shown in Figure 7.13 is related to the
materials parameters and f(0), the interface location in similarity variables at = 0.
Linear slopes were determined for 19 separate pinching events based on diameters
measured for at least 3 time steps prior to t
s
. The average slope from these was
1.28 m/s
1/3
with a standard deviation of 0.178 m/s
1/3
. From Equation 7.24, the
predicted slope, or prefactor of the power law, is given by 2f(0)(D
L
d
0
)
1/3
(the factor
of 2 converts radius to diameter). Using D
L
= 8.310
10
m
2
/s (Chapter 6), d
0
= 2.27
nm [76], and f(0) = 0.60 , the theoretically predicted rate constant is 1.47 m/s
1/3
.
The 16% dierence between the theoretically predicted and experimentally measured
rate constants indicates an excellent agreement between theory and experiment, given
the uncertainties in the materials parameters. If we had used, instead, f(0) for the
solution with a cone angle of 30
, and
linearly scaled the predicted shape such that the diameter at the center of the pinching
147
tube was the same as that measured experimentally. This process was repeated for a
series of times leading to the singularity. The distance from the theoretically predicted
shape to the closest point on the experimentally measured shape was calculated, see
Figure 7.14. As expected, the agreement between theory and experiment improved as
the singularity is approached, since initial conditions have less inuence and the shape
becomes locally determined. Just before pincho, the mean deviation between shapes
is less than the 1.4 m resolution of the Xray tomography scan, indicating excellent
agreement between theory and experiment. Very similar diagrams result if we plot
the distance between the experimentally measured and theoretically predicted shapes
in similarity variables, conrming that the improved agreement as t
s
is approached
is not just a result of the changing length scale. In some cases, the initial shapes of
the rods were asymmetric about the pinching axis and thus the singularity did not
achieve high degrees of selfsimilarity under the time and space resolution constraints
of the experiment. However, in all 19 cases examined the agreement between theory
and experiment improved as the singularity was approached. Thus to the resolution of
the tomography, the experiments conrm that some distance from the pinching point,
the shape approaches a cone with the predicted cone angle 2 = 76
.
7.4.1. Conclusions
The pinching of liquid cylinders caused by interfacialenergy driven bulk diusion was
shown to be a selfsimilar process within the quasisteady approximation. Suciently
close to the point of pinching, the interface approaches a universal shape. The shape is
selfsimilar and follows a t
1/3
power law. The problem was transformed into similarity
148
25 um 25 um 25 um
10 um
25 um 25 um 25 um
10 um
0 8!m+
(a) (b) (c) (d)
Figure 7.14. Quantifying agreement between theoretically predicted and
experimentally measured interface shape. The experimentally deter
mined microstructure is superimposed on the theoretically predicted
shape for the solution with a cone angle of 76
2
C
s
(A.1)
C
l
t
= D
s
2
C
l
(A.2)
and the value of concentration at the interface will be given by the GibbsThomson
equation:
C
s
= C
s
e
+
s
H (A.3)
C
l
= C
l
e
+
l
H (A.4)
The solute conservation boundary condition at the interface is
(A.5)
_
C
l
e
C
s
e
_
V = D
l
C
l
n + D
s
C
s
n
161
Where the interfacial velocity V is in the normal direction; and the ux in the solid
has opposite sign because the normal into the solid is equal and opposite to the normal
into the liquid. Assuming concentration is of the form
C
l
= B
l
0
+ B
l
1
(z) exp (i
k r + t) (A.6)
C
s
= B
s
0
+ B
s
1
(z) exp (i
k r + t) (A.7)
Substituting into the diusion equation:
B
l
1
(z) exp (i
k r + t) = D
l
B
l
1
(z)k
2
exp (i
k r + t) + D
l
2
B
l
1
z
2
exp (i
k r + t)
and cancelling factors of exp (i
k r + t) and :
B
l
1
(z) = D
l
B
l
1
(z)k
2
+ D
l
2
B
l
1
z
2
Assume the solution is of the form B
l
1
(z) = E exp (z) for z > 0
E exp (z)( + D
l
k
2
) = D
l
2
E exp (z)
so
=
_
+ D
l
k
2
D
l
162
Choose the exp +z solution for the solid so concentration does not go to innity
for z . So the solutions are:
B
l
1
(z) = E exp
_
_
+ D
l
k
2
D
l
z
_
B
s
1
(z) = F exp
_
_
+ D
s
k
2
D
s
z
_
To solve for B
l,s
0
, use the fact that far from the interface, the concentration will be
at its equilibrium value as determined from the phase diagram.
C
l
e
= B
l
0
+ E exp (
_
+ D
l
k
2
D
l
z) exp (i
k r + t)
C
s
e
= B
s
0
+ F exp
_
_
+ D
s
k
2
D
s
z
_
exp (i
k r + t)
So as z , the exponential terms go to zero, and C
l
e
= B
l
0
, C
s
e
= B
s
0
. And we
nd
(A.8) C
l
= C
l
e
+ E exp
_
_
+ D
l
k
2
D
l
z
_
exp (i
k r + t)
(A.9) C
s
= C
s
e
+ F exp
_
_
+ D
s
k
2
D
s
z
_
exp (i
k r + t)
Equating to the linearized GibbsThompson equation:
(A.10) C
l
e
+ E exp
_
_
+ D
l
k
2
D
l
z
_
exp (i
k r + t) = C
l
e
+
l
_
2
h
x
2
+
2
h
y
2
_
163
The C
l
e
terms drop out, and
2
h
x
2
+
2
h
y
2
= k
2
exp (i
k r + t)
So canceling factors of exp (i
_
+ D
l
k
2
D
l
z
_
=
l
k
2
This must be evaluated at the interface, where z = exp (i
k r + t)
_
=
l
k
2
The term with exp (i
l
k
2
exp
_
_
+ D
l
k
2
D
l
z
_
exp (i
k r + t)
(A.12) C
s
= C
s
e
s
k
2
exp
_
_
+ D
s
k
2
D
s
z
_
exp (i
k r + t)
Using the linearized form of the ux condition (for small perturbations, V = h
t
)
_
C
l
e
C
s
e
_
exp (i
k r + t) = D
l
l
k
2
_
+ D
l
k
2
D
l
exp
_
_
+ D
l
k
2
D
l
z
_
exp (i
k r + t)
164
D
s
s
k
2
_
+ D
s
k
2
D
s
exp
_
_
+ D
s
k
2
D
s
z
_
exp (i
k r + t) (A.13)
Cancelling exp (i
l
k
2
_
+ D
l
k
2
D
l
D
s
s
k
2
_
+ D
s
k
2
D
s
which can be solved numerically for .
165
APPENDIX B
Determining Time Exponent of Similarity Solution for Rod
Pinching
To determine the time exponents and required for a similarity solution, the
assumed similarity solution for the solute concentration
(B.1) C
L
(r, z, t) C
0
L
= (t
s
t)
AK (, )
is substituted into the boundary conditions for the rod pinching problem. First is the
GibbsThomson equation:
(B.2) C
L
= C
0
L
+
_
C
0
L
C
0
S
_
d
0
H
Substituting we obtain
(B.3) (t
s
t)
AK (, ) =
_
C
0
L
C
0
S
_
d
0
H
H = n in realspace coordinates. To transform this derivative into similarity
variables, we use the chain rule to show
(B.4)
F
z
=
F
z
= F
z
_
zB
(t
s
t)
_
=
B
(t
s
t)
166
(F = f() = 0 is the function that parametrically denes the interface, and F
,
n
where the subscripts , to denote that the divergence operator is applied in the
similarity coordinate system. Substituting back into Equation B.3
(B.6) (t
s
t)
AK (, ) =
_
C
0
L
C
0
S
_
d
0
B
(t
s
t)
(
,
n)
In order for a valid similarity solution for the concentration and interface shape to
exist, the timedependence on the left and right hand sides of the equation must cancel,
meaning that = is required for a similarity solution.
The solute conservation boundary condition is next used so that and can be
determined.
(B.7)
_
C
0
L
C
0
S
_
v n = D
L
C
L
n
This boundary condition must also be transformed into similarity coordinates.
(B.8)
C
L
n
= n C
L
= n
_
C
0
L
+ (t
s
t)
AK (, )
167
Again using the fact that realspace derivatives give
B
(tst)
( n
,
K)
The material derivative at the interface can be used to nd the normal velocity of the
interface in similarity variables.
(B.10)
DF
Dt
=
F
t
+v F = 0
Dividing the above equation by [F[ and using the fact that n =
F
F
,
(B.11) v n =
F
t
[F[
Using the chain rule,
(B.12)
F
t
=
F
t
+
F
t
=
(t
s
t)
(F
+ F
)
and that realspace derivatives give
B
(tst)
[
,
F[
gives
(B.14) v n =
t
1
B
(F
+ F
)
_
F
2
+ F
2
168
Substituting Equation B.9 and B.14 into B.7 yields
(B.15) (C
0
L
C
0
S
)
(t
s
t)
1
B
F
+ F
_
F
2
+ F
2
= D
L
(t
s
t)
(t
s
t)
AB( n
,
K)
For a valid similarity solution to exist, the time dependence on the left and right hand
sides must cancel, yielding 1 = . Substituting = from Equation B.6, the
required exponents for a similarity solution consistent with the boundary conditions
are
(B.16) =
1
3
, =
1
3
However, these exponents must be substituted in to the diusion equation in selfsimilar
coordinates to determine in a selfsimilar solution exists. Substituting the assumed self
similar solution for solute concentration (Equation B.1) in to the diusion equation and
applying the chain rule
(B.17) (t
s
t)
1
[AK A(K
+ K
)] =
(t
s
t)
(t
s
t)
2
AB
2
2
,
K
Therefore, for the time dependence to cancel on the left and right sides, 1 =
2 or = 1/2 must hold, meaning that = 1/3 is not a valid solution for the
diusion equation in similarity coordinates. However, in the quasisteady approximation
where
C
L
t
0,
(B.18)
2
C
L
= (t
s
t)
2
AB
2
2
,
K = 0
169
and the time dependence will always disappear, leaving = 1/3 a valid exponent, and
reducing the problem of solving for the shape to solving Laplaces equation in similarity
variables on the boundary.
170
APPENDIX C
Details of BoundaryIntegral Equation After Pinching in Two
Dimensions
The integrodierential equation is
(C.1)
1
2
K(
0
,
0
) =
_
S
_
K(, )
g
n
g
K
n
_
dS
which applies on the boundary dened by = f(). The freespace Greens function
for two dimensions is
(C.2) g =
1
2
ln
_
(
0
)
2
+ [f() f(
0
)]
2
The surface integral of Equation C.1 must also include the arbitrarily shaped cap
enclosing the area inside the curve = f(). However, as , , C
L
C
0
L
so
K 0 and therefore
K
n
0. Therefore this boundary makes no contribution to the
integral.
The integral along the surface can be performed along the axis. The surface area
element is
d s =
_
d
2
+ d
2
(C.3)
= d
_
1 + f
()
2
(C.4)
171
The normal vector to the interface is given by
n =
F
[F[
=
F
+ F
_
F
2
+ F
2
(C.5)
=
f
()
_
1 + f
()
2
(C.6)
where F = f() = 0 denes the interface, and we have chosen the normal to the
interface pointing outward from the liquid region. To nd
g
n
,
g
n
= n g =
_
f
()
_
1 + f
()
2
_
_
g
+
g
_
(C.7)
=
1
2
_
1 + f
()
2
_
f
()(
0
) (
0
)
(
0
)
2
+ (
0
)
2
_
(C.8)
Using = f(),
(C.9)
g
n
=
1
2
_
1 + f
()
2
_
[f() f(
0
)] + f
()(
0
)
(
0
)
2
+ [f() f(
0
)]
2
_
From the solute conservation boundary condition in similarity coordinates, Equa
tion B.15, once the materials constants and time dependence are cancelled,
K
n
= n K =
(F
+ F
)
_
F
2
+ F
2
(C.10)
=
f() f
()
3
_
1 + f
()
2
(C.11)
172
Substituting g,
g
n
, and
K
n
in to Equation C.1,
K[
0
, f(
0
)] =
1
_
K[, f()]
[f() + f(
0
) + f
()(
0
)]
(
0
)
2
+ [f() f(
0
)]
2
1
3
[f() f
()] ln
_
(
0
)
2
+ [f() f(
0
)]
2
_
d
(C.12)
So that the integration can be performed over + values only, the integral can be split
into positive and negative regions. The integral over negative can be rewritten using
a change of variable and the properties that with respect to , f() is even, f
() is
odd, and K[, f()] is even. This change of variable results in Equation 7.11,
K[
0
, f(
0
)] =
1
_
0
_
K[, f()]
[f() + f(
0
) + f
()(
0
)]
(
0
)
2
+ [f() f(
0
)]
2
1
3
[f() f
()] ln
_
(
0
)
2
+ [f() f(
0
)]
2
_
d
+
1
_
0
_
K[, f()]
[f() + f(
0
) + f
()( +
0
)]
( +
0
)
2
+ [f() f(
0
)]
2
1
3
[f() f
()] ln
_
( +
0
)
2
+ [f() f(
0
)]
2
_
d
(C.13)
173
APPENDIX D
Details of BoundaryIntegral Equation After Pinching in
Three Dimensions
The integrodierential equation is
(D.1)
1
2
K(
0
,
0
) =
_
S
_
K(, )
g
n
g
K
n
_
dS
which applies on the boundary dened by = f(). The freespace Greens function
for three dimensions is
(D.2) g =
1
4 [( cos
0
cos
0
)
2
+ ( sin
0
sin
0
)
2
+ (
0
)
2
]
1/2
The surface integral of Equation D.1 must also include the arbitrarily shaped cap
enclosing the area inside the curve = f(). However, as , , C
L
C
0
L
so
K 0 and therefore
K
n
0. Therefore this boundary makes no contribution to the
integral.
The integral along the surface is performed in radial coordinates. The surface area
element is
d s = d
_
d
2
+ d
2
(D.3)
= d d
_
1 + f
()
2
(D.4)
174
So the integrodierential equation is
(D.5)
1
2
K(
0
,
0
) =
_
2
0
_
0
d d
_
1 + f
()
2
_
K(, )
g
n
g
K
n
_
The solute conservation boundary condition can again be used to write
K
n
in terms of
and f() as
(D.6)
K
n
=
f() f
()
3
_
1 + f
()
2
The normal vector to the interface is given by
n =
F
[F[
=
F
+ F
_
F
2
+ F
2
(D.7)
=
f
()
_
1 + f
()
2
(D.8)
where F = f() = 0 denes the interface, and we have chosen the normal to the
interface pointing outward from the liquid region. To nd
g
n
,
g
n
= n g =
_
f
()
_
1 + f
()
2
_
_
g
+
g
_
(D.9)
=
1
_
1 + f
()
2
_
f
()
g
_
(D.10)
Since we are trying to nd the surface = f(), let
0
= 0 and
0
= f(
0
).
g =
1
4
_
( cos
0
)
2
+ ( sin )
2
+ (f() f(
0
))
2
1/2
(D.11)
=
1
4
_
2
+
2
0
2
0
cos + (f() f(
0
))
2
1/2
(D.12)
175
Let
(D.13) g
_
2
0
d
1
_
2
+
2
0
2
0
cos + (f() f(
0
))
2
1/2
Using the trigonometric identity 1 cos = 2 sin
2
2
and performing a change of
variables = 2,
(D.14) g
=
_
0
2d
_
2
+
2
0
2
0
+ 4
0
sin
2
+ (f() f(
0
))
2
1/2
Let
(D.15) l
(
0
)
2
+ [f() f(
0
)]
2
(D.16) k
2
4
0
Therefore
g
=
4
l
_
/2
0
d
_
1 +
k
2
l
2
sin
2
(D.17)
g
=
4
l
M
_
k
2
l
2
_
(D.18)
where M is a complete elliptic integral of the rst kind. Using the identity
(D.19) M(m) =
1
1 + m
M
_
m
1 + m
_
176
(D.20) g
=
4
_
l
2
+ k
2
M
_
k
2
l
2
+ k
2
_
Using the polynomial approximation for M(m) of [80],
(D.21) M(m) =
4
i=0
[a
i
b
i
ln(1 m)] (1 m)
i
+ (m)
where a
i
and b
i
are known constants, and [(m)[ 2 10
8
,
(D.22) g
=
4
_
l
2
+ k
2
4
i=0
_
a
i
b
i
ln
_
1
k
2
l
2
+ k
2
__ _
1
k
2
l
2
+ k
2
_
i
Substituting back in to the integrodierential equation,
2K[
0
,
0
] =
_
0
d
_
K[, f()]
_
f
()
g
+
g
_
+
g
3
[f() + f
()]
_
(D.23)
177
and dierentiating Equation D.22 with respect to and , we obtain
2K[
0
, f(
0
)] =
_
0
d
_
K[, f()]
_
f
()
_
4( +
0
)
(l
2
+ k
2
)
3/2
4
n=0
_
a
n
b
n
ln
_
1
k
2
l
2
+ k
2
__ _
1
k
2
l
2
+ k
2
_
n
+
4
(l
2
+ k
2
)
1/2
_
4
n=1
n
_
a
n
b
n
ln
_
1
k
2
l
2
+ k
2
__ _
1
k
2
l
2
+ k
2
_
n1
n=0
b
n
_
1
k
2
l
2
+ k
2
_
n1
_
4
0
[
2
2
0
[f() f(
0
)]
2
]
[l
2
+ k
2
]
2
_
4[f() f(
0
)]
(l
2
+ k
2
)
3/2
4
n=0
_
a
n
b
n
ln
_
1
k
2
l
2
+ k
2
__ _
1
k
2
l
2
+ k
2
_
n
+
4
(l
2
+ k
2
)
1/2
_
4
n=1
n
_
a
n
b
n
ln
_
1
k
2
l
2
+ k
2
__ _
1
k
2
l
2
+ k
2
_
n1
n=0
b
n
_
1
k
2
l
2
+ k
2
_
n1
_
8
0
[f() f(
0
)]
[l
2
+ k
2
]
2
_
4
3
[f
() f()]
(l
2
+ k
2
)
1/2
4
n=0
_
a
n
b
n
ln
_
1
k
2
l
2
+ k
2
__ _
1
k
2
l
2
+ k
2
_
n
_
(D.24)
178
Grouping coecients of the series, we obtain Equation 7.18:
2K[
0
, f(
0
)] =
_
0
d
_
K[, f()]
_ _
f
()4( +
0
)
(l
2
+ k
2
)
3/2
4[f() f(
0
)]
(l
2
+ k
2
)
3/2
_
_
4
n=0
_
a
n
b
n
ln
_
1
k
2
l
2
+ k
2
__ _
1
k
2
l
2
+ k
2
_
n
_
+
_
16
0
f
() [
2
2
0
[f() f(
0
)]
2
]
(l
2
+ k
2
)
5/2
+
32
0
[f() f(
0
)]
(l
2
+ k
2
)
5/2
_
_
4
n=1
n
_
a
n
b
n
ln
_
1
k
2
l
2
+ k
2
__ _
1
k
2
l
2
+ k
2
_
n1
n=0
b
n
_
1
k
2
l
2
+ k
2
_
n1
__
4[f
() f()]
3(l
2
+ k
2
)
1/2
4
n=0
_
a
n
b
n
ln
_
1
k
2
l
2
+ k
2
__ _
1
k
2
l
2
+ k
2
_
n
_
(D.25)
179
APPENDIX E
Details of BoundaryIntegral Equation Before Pinching in
Three Dimensions
The integrodierential equation is
(E.1)
1
2
K(
0
,
0
) =
_
S
_
K(, )
g
n
g
K
n
_
dS
which applies on the boundary dened by = f(). The freespace Greens function
for this geometry is
(E.2) g =
1
4 [( cos
0
cos
0
)
2
+ ( sin
0
sin
0
)
2
+ (
0
)
2
]
1/2
The surface integral of Equation E.1 must also include the arbitrarily shaped caps at
= that enclose the liquid volume. However, as , C
L
C
0
L
so K 0 and
therefore
K
n
0. Therefore these boundaries make no contribution to the integral.
The integral along the surface is performed in radial coordinates. The surface area
element is
ds = d
_
d
2
+ d
2
(E.3)
= df()d
_
1 + f
()
2
(E.4)
180
So the integrodierential equation is
(E.5)
1
2
K(
0
,
0
) =
_
2
0
_
df()d
_
1 + f
()
2
_
K(, )
g
n
g
K
n
_
The solute conservation boundary condition can again be used to write
K
n
in terms of
and f() as
(E.6)
K
n
=
f() f
()
3
_
1 + f
()
2
In this case we choose the normal vector to the interface pointing out of the liquid.
The normal vector to the interface is given by
n =
F
[F[
=
F
+ F
_
F
2
+ F
2
(E.7)
=
f
()
+
_
1 + f
()
2
(E.8)
where F = f() = 0 denes the interface. To nd
g
n
,
g
n
= n g =
_
f
()
+
_
1 + f
()
2
_
_
g
+
g
_
(E.9)
=
1
_
1 + f
()
2
_
f
()
g
+
g
_
(E.10)
Since we are trying to nd the surface = f(), let
0
= 0.
g =
1
4
_
( cos
0
)
2
+ ( sin )
2
+ (
0
))
2
1/2
(E.11)
=
1
4
_
2
+
2
0
2
0
cos + (
0
)
2
1/2
(E.12)
181
where the (
0
)
2
term applies for positive and the ( +
0
)
2
term applies for negative
. Let
(E.13) g
_
2
0
d
1
_
2
+
2
0
2
0
cos + (
0
)
2
1/2
Using the trigonometric identity 1 cos = 2 sin
2
2
and performing a change of
variables = 2,
(E.14) g
=
_
0
2d
_
2
+
2
0
2
0
+ 4
0
sin
2
+ (
0
)
2
1/2
Let
(E.15) l
(
0
)
2
+ [
0
)]
2
(E.16) k
2
4
0
Therefore
g
=
4
l
_
/2
0
d
_
1 +
k
2
l
2
sin
2
(E.17)
g
=
4
l
M
_
k
2
l
2
_
(E.18)
where M is a complete elliptic integral of the rst kind. Using the identity
(E.19) M(m) =
1
1 + m
M
_
m
1 + m
_
182
(E.20) g
=
4
_
l
2
+ k
2
M
_
k
2
l
2
+ k
2
_
Using the polynomial approximation for M(m) of [80],
(E.21) M(m) =
4
i=0
[a
i
b
i
ln(1 m)] (1 m)
i
+ (m)
where a
i
and b
i
are known constants, and [(m)[ 2 10
8
,
(E.22) g
=
4
_
l
2
+ k
2
4
i=0
_
a
i
b
i
ln
_
1
k
2
l
2
+ k
2
__ _
1
k
2
l
2
+ k
2
_
i
Substituting back in to the integrodierential equation,
2K[
0
,
0
] =
_
f()d
_
K[, f()]
_
f
()
g
3
[f() + f
()]
_
(E.23)
The integral is split into positive and negative domains, then the negative portion is
changed to an integral over + by performing a change of variables and using the
properties that is odd, f() is even, f
()
g
3
[f() + f
()]
_
+
_
0
f()d
_
K[, f()]
_
f
()
g
+
g
+
g
+
3
[f() + f
()]
_
(E.24)
183
and dierentiating Equation E.22 with respect to and , and grouping coecients of
the series, we obtain Equation 7.22:
2K[
0
, f(
0
)] =
_
0
df()
_
K[, f()]
_ _
4f
()(
0
)
(l
2
+ k
2
)
3/2
+
4( +
0
)
(l
2
+ k
2
)
3/2
_
M
_
k
2
l
2
+ k
2
_
+
_
32
0
(
0
)f
()
(l
2
+ k
2
)
5/2
16
0
[
2
2
0
(
0
)
2
]
(l
2
+ k
2
)
5/2
_
M
d
_
k
2
l
2
+ k
2
__
4
3
[f
() f()]
_
l
2
+ k
2
M
_
k
2
l
2
+ k
2
_
+ K[, f()]
_ _
4f
()( +
0
)
(l
2
+
+ k
2
)
3/2
+
4( +
0
)
(l
2
+
+ k
2
)
3/2
_
M
_
k
2
l
2
+
+ k
2
_
+
_
32
0
( +
0
)f
()
(l
2
+
+ k
2
)
5/2
16
0
[
2
2
0
( +
0
)
2
]
(l
2
+
+ k
2
)
5/2
_
M
d
_
k
2
l
2
+
+ k
2
__
4
3
[f
() f()]
_
l
2
+
+ k
2
M
_
k
2
l
2
+
+ k
2
__
(E.25)
where
(E.26) M
_
k
l
2
+ k
2
_
=
4
n=0
_
a
n
b
n
ln
_
1
k
l
2
+ k
2
__ _
1
k
l
2
+ k
2
_
n
and
M
d
_
k
l
2
+ k
2
_
=
4
n=1
n
_
a
n
b
n
ln
_
1
k
l
2
+ k
2
__ _
1
k
l
2
+ k
2
_
n1
n=0
b
n
_
1
k
l
2
+ k
2
_
n1
(E.27)
Molto più che documenti.
Scopri tutto ciò che Scribd ha da offrire, inclusi libri e audiolibri dei maggiori editori.
Annulla in qualsiasi momento.