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What is Spinodal Decomposition?

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 J
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Jestr
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Journal of Engineering Science and Technology Review 1 (2008) 25- 27
Journal of Engineering Science and Technology Review 1 (2008) 25- 27
Journal of Engineering Science and Technology
Lecture Review 1 (2008) 25- 27
Note
JOURNAL OF
Engineering
JOURNAL
JOURNAL OF
OF Science and
Technology
Engineering
Engineering
Review
Science and
Science
Technology and
Review
Technology Review www.jestr.org
Lecture Note www.jestr.org
What is Lecture
spinodal Note
decomposition? www.jestr.org
What is spinodal decomposition?
What
E. P.isFavvas*
spinodal
, 1 decomposition?
and A. Ch. Mitropoulos2
,1 2
E. P. Favvas*
,1 and A. Ch. Mitropoulos
2
1 E. P. Favvas*
Institute of Physical and“Demokritos”,
Chemistry, NCSR A. Ch. Mitropoulos
153 10 Ag.Paraskevi, Attikis,Greece.
2
Department
1 of of
Institute Petroleum
Physical Technology,
Chemistry, Kavala
NCSR Institute of Technology,
“Demokritos”, 153 65 404 St.Lucas,
10 Ag.Paraskevi, Kavala, Greece.
Attikis,Greece.
2 1Institute of Physical Chemistry, NCSR “Demokritos”, 153 10 Ag.Paraskevi, Attikis,Greece.
2
Department of Petroleum Technology, Kavala Institute of Technology, 65 404 St.Lucas, Kavala, Greece.
Department of Petroleum Technology, Kavala Institute of Technology, 65 404 St.Lucas, Kavala, Greece.
Received 17 January 2008; Accepted 20 February 2008
___________________________________________________________________________________________
Received 17 January 2008; Accepted 20 February 2008
Received 17 January 2008; Accepted 20 February 2008
___________________________________________________________________________________________
___________________________________________________________________________________________
Abstract
Abstract
Abstract: Phase separation may occur in a way that the growth is not in extent but in amplitude. Only in the unstable region such a
Abstract
procedurePhase
Abstract: is thermodynamically
separation may occur feasible. In a that
in a way phase
thediagram
growth the unstable
is not in extent region
but inis amplitude.
defined byOnlythe spinodal. When region
in the unstable a system suchhas
a
crossed
Abstract: Phase
procedure thisisseparation
locus, phasemayseparation
thermodynamically in occurs
occur feasible.
a way In spontaneously
that
a the growth
phase without the
is notthein
diagram presence
extent
unstable but of
in aamplitude.
region nucleation step.
is definedOnly in
by theThis
the process
unstableis
spinodal. known
region
When as spinodal
a such
system a has
decomposition
procedure
crossedis this andphase
thermodynamically
locus, commonly results
feasible.
separation to a high
In
occurs phaseinterconnectivity
diagramwithout
spontaneously of
thethe
the unstable two phases.
region
presence The Cahn-Hilliard
is adefined
of by the
nucleation Thisequation
step.spinodal. When
process describes
a system
is known thespinodal
as kinetics
has
of the
crossed thisprocess.
locus, phase
decomposition In this
and note bothresults
separation
commonly processes
occurs to a (nucleation
spontaneously and spinodal)
without
high interconnectivity are two
the presence
of the depicted schematically.
ofphases.
a nucleation step. This process
The Cahn-Hilliard is known
equation as spinodal
describes the kinetics
decomposition and commonly
of the process. In this noteresults to a high(nucleation
both processes interconnectivity of the two
and spinodal) are phases.
depictedThe Cahn-Hilliard equation describes the kinetics
schematically.
of theKeywords:
process. Inspinodal
this notedecomposition,
both processes nucleation
(nucleationand andgrowth.
spinodal) are depicted schematically.
___________________________________________________________________________________________
Keywords: spinodal decomposition, nucleation and growth.
Keywords: spinodal decomposition, nucleation and growth.
___________________________________________________________________________________________
___________________________________________________________________________________________
A pair of partially miscible liquids, i.e. liquids that do not
Amixpairin of all partially
proportions at all liquids,
miscible temperatures, shows
i.e. liquids thatin doa tem-
not
A pair
mix ofinpartially
perature-composition miscible
all proportions atliquids,
diagram i.e. liquidsshows
a miscibility
all temperatures, thatwhere
gap doin not
a phase
tem-
mix perature-composition
in all proportions
separation occurs. at all temperatures,
Gibbs
diagram [1] showed
a miscibility shows
that gapincondition
the a tem-
where phasefor
perature-composition
stability (oroccurs.
separation diagram
metastability)
Gibbs [1] a miscibility
in respect
showedtothat gap where
continuous phase
changefor
the condition of
separation
phase is
stability occurs.
(or theGibbs
thatmetastability)
second [1]derivative
showed
in respect that the
oftothe condition
free
continuousenergy formix-
of
change of
stability
ing to
phase (orisbemetastability)
positive.
that the second inderivative
respectthetosystem
If negative, continuous
of changeof
is unstable.
the free energy Ifofmix-
zero,
phase is
the to
ing that
spinodal the
be positive.second
is defined.derivative
The free
If negative, of the free energy
energyisofunstable.
the system of mix-
mixing,IfΔG mix
zero,,
ing to be positive.
has spinodal
the the following If negative,
generalThe
is defined. the
form: system is unstable.
free energy of mixing, ΔG , If zero, mix
the spinodal is defined.
has the following free energy of mixing, ΔGmix,
The form:
general
has the following general form:
ΔG mix = ΔH mix − TΔS mix . (1)
mix mix mix
Δ G = Δ H − T Δ S . (1)
ΔG mix
For=the
mix
ΔHregular − TΔ S mix . model [2] the entropy of mixing
solution (1) is
mix
the same
For the regularas for solution
the ideal modelmixing;[2]ΔSthe =-R(X entropy AlnX +XlnXBis),
of Amixing
For the
the
whereregular
same XAasand solution
for X theB are
model
ideal the [2] the
molar
mixing; ΔS entropy
mix
fractions
=-R(X of components
of mixing is A
mix AlnXA+XlnXB),
the same
and BasX infor themixture
idealaremixing; ΔS =-R(X AlnX +XlnX B),
where A the
and X theA+X
(X B=1).
molar However,
fractions of the enthalpy
components of
A
A
B
where X
mixing and
B inmay X are the
be written molar
(XAas+X fractions
ΔH mix of components β is A
and the mixture B=1).=X AXBβ, where
However, the enthalpy an in-
of
A B
and mixing
B in themay
teraction mixture
parameter
be written +Xas
(XAlumping B=1).ΔHtheHowever,
mix
energy
=X the
of enthalpy
mixing is of
β contribu-
mix AXBβ, where an in-
mixing may be
tion [3]. Under
teraction written
parameter as
theselumpingΔH
assumptions, =X XBeq.(1)
theAenergy β, where β is an
becomes:
of mixing in-
contribu-
teraction parameter
tion [3]. Under these lumping the energyeq.(1)
assumptions, of mixing
becomes: contribu-
tion [3]. Under these assumptions, eq.(1) becomes:
ΔG = X A X B β + RT ( X A ln X A + X B ln X B ) .
mix
(2)
Δ G mix
= X X β + RT ( X ln X + X ln X ) . (2)
ΔG mix = X A X BAβ +B RT ( X A ln AX A + X A
B ln X B ) .
B B
(2)
Figure 1. A phase diagram with a miscibility gap (lower frame) and a
diagram1. of
Figure A the freediagram
phase energy change (upper frame).
with a miscibility gap The(lowerphase diagram
frame) and is a
Figure the1.temperature
diagram A phase versus
of thediagram
free the change
with
energy molar fraction
a miscibility
(upper gap of a(lower
frame). component phasee.g.
Theframe) andxBa. Note
diagram is
diagram thattemperature
the ofthethediagram
free energyis symmetrical
versus change
the molar around
(upper xBof
frame).
fraction =0.5aThe which
phaseisdiagram
component the
e.g.case
xBis. of
Notethe
regular
the temperature
that the solutionversusmodel.
diagram isthe Linefraction
molar
symmetrical (1)around
is the of phase =0.5boundary.
xaBcomponent which e.g.is Above
thexB.case
Notethis
of line
the
that thethediagram
regular twosolution
liquids are miscible
is symmetrical
model. and
Linearound
(1) isthexthesystem
B =0.5
phase isboundary.
which stable (s).case
is the Below
Above this line
of this
the line
regular there
the two is liquids
solution a metastable
model.
are Line region
miscible(1) is (m).
and Within
thethe phase
system thatis region
boundary. stableAbovethe system
(s). this line
Below is stable
this line
the two to small
there is afluctuations
liquids are miscible
metastable but
and
region is the
unstable
(m).system
Within to is
large
stable
that fluctuations.
region(s). Below Line
the system (2)
this line is the
is stable
thereto spinodal.
is small
a metastableBelowregion
fluctuations this but
line isthe
(m). systemthat
Within
unstable is large
to unstable
region (u).system
the
fluctuations. Regions is (m)
Line (2)and
stable is the(u)
to smallconstitute
fluctuations
spinodal. the miscibility
Below but
thisisline gap.system
unstable
the Within
to large isthat gap the
fluctuations.
unstable (u).system
Line turns
Regions is from
(2)(m) and one
the (u)
phase
spinodal.
constitute to athe
Below two-phase
this line thesystem.
miscibility system Temperature
is unstable
gap. Within that gap (u).(Tthe c) is
Regions the (m)
system upperandconsolute
turns (u) one
from
temperature.
constitute
phase the Abovegap.
to miscibility
a two-phase this temperature
Within
system. that gap
Temperature thethe two(T liquids
system are miscible
turns from one in all
c) is the upper consolute changes in the free energy of mixing (ΔG), at this given temperature, in
proportions.
phasetemperature.
to a two-phase At asystem.
Above given temperature
Temperaturethe
this temperature (T)
(Ttwocthe
) istie theline
liquids (4) miscible
upper
are cuts the in
consolute phaseall respect to
changes in xthe
B are
freeshown
energybyofline (3) in
mixing (ΔG),the at
upper
this frame. Segments (ab)
given temperature, in
boundary
temperature.
proportions. and
Above the
At this spinodal
temperature
a given at points
temperature the two (a, liquids
(T) c) and
the tie (b,lined),
are respectively.
miscible
(4) cuts in theallphaseThe
changesandin(cd)
respect tocorrespond
the free energy
xB are shown toofamixing
positive
by second
line (ΔG),
(3) in atthe derivative
this of ΔG,
givenframe.
upper ∂2ΔG/x
temperature,
Segments
2
>0,
in B(ab)
proportions. At a given temperature (T) the tie line
boundary and the spinodal at points (a, c) and (b, d), respectively. The respect (4) cuts the phase while 2 2
and xsegment
to(cd)B are (bd) by
shown
correspond to
to aaline
negative one,
the ∂upper
(3) insecond
positive ΔG/x B <0. At
frame.
derivative points
Segments
of ΔG, (b) and
(ab)
∂2ΔG/x 2 (d)
B >0,
boundary and the spinodal at points (a, c) and (b, d), respectively. The ∂2ΔG/x 2 2of ΔG, ∂2ΔG/x 2>0,
______________ and (cd)
while B =0. (bd)
correspond
segment to a to
positive second
a negative one, derivative
∂ 2
ΔG/x B <0. At points (b)B and (d)
while∂2segment 2 (bd) to a negative one, ∂2ΔG/x 2<0. At points (b) and (d)
* E-mail address: favvas@chem.demokritos.gr
______________ 2
ΔG/x
2
B =0. B

ISSN:
______________ 1791-2377 ©favvas@chem.demokritos.gr
2008 Kavala Institute of Technology. All rights reserved. ∂ ΔG/x B =0.
* E-mail address:
* E-mail
ISSN:address:
1791-2377 favvas@chem.demokritos.gr
© 2008 Kavala Institute of Technology. All rights reserved.
ISSN: 1791-2377 © 2008 Kavala Institute of Technology. All rights reserved.
25
 E. E.
P. P.
Favvas and
Favvas A. A.
and Ch.Ch.
Mitropoulos/ Journal
Mitropoulos/ of Engineering
Journal
of Engineering
Figure 2 (left). The nucleation and growth process. The columns repre-
sent two adjacent local regions in the solution denoted as “left” and
“right” and the rows five stages of the system denoted by numbers 1, 2,
3, 4, 5; where the first three stages show what will happen when a small
fluctuation occurs and the last two when a large fluctuation takes place.
Black dots represent one of the two components e.g. B. In the 1st row
the solution has been brought in to the metastable region and at the
moment there is not difference in the local concentrations; CBleft=CBright.
In the 2nd row an infinitesimal fluctuation causes a concentration differ-
ence, such as CBleft>CBright, and therefore diffusion is expected to take
place between left and right localities. In the 3rd row the expected diffu-
sion results to CBleft=CBright. Diffusion takes place from left to right i.e.
from higher to lower concentration (down-hill) and the system comes
back to what is depicted on the first row. In the 4th row a large fluctua-
tion causes the formation of a nucleus of a critical size. For presentation
reasons, the figure was drawn such as all component B on the left region
is spent to form that nucleus; therefore CBleft=0<CBright. Down-hill diffu-
sion takes place now from right to left; note, that the higher concentra-
tion is on the right, the nucleus does not intervene. Once some B reach-
es to the left is arrested by the nucleus that grows (5th row). Phase sepa-
ration occurring in this way is known as nucleation and growth and the
fingerprint of that mechanism is the formation of a nucleus.
Figure 3 (right). The spinodal decomposition process. The columns
denoted as “left” and “right” represent two adjacent local regions in the
solution and the rows denoted by numbers “1, 2, 3, 4, 5,” represent five
stages of the system. Black dots represent one of the two components
e.g. B. Note that rows 4 and 5 represent some final stages of the process.
The miscibility-gap and spinodal-region boundaries are ob-
tained by calculating the first and second derivatives of the
free energy, respectively, and setting them equal to zero.
T XA − XB T β
=2 ; = 4 X A X B ; Tc = . (3)
Tc ln X A − ln X B Tc 2R
In Fig.1 (upper frame) it can be seen that the first deriva-
tive is zero at the two free energy minima corresponding to
Science
andand
Science Technology Review
Technology 1 (2008)
Review 25-27
1 (2008) 25-27
The drawing on the 4th row is produced by repeating the 3rd row to an x-
y plane. The 5th row is produced from the 4th row by artwork. The col-
umn denoted as “density” represents the density profile of the system at
a given stage. In the 1st row the solution has been brought, very care-
fully, in to the unstable region. This carefulness is shown in a way that
there is not difference in the local concentrations; CBleft=CBright. Since
there is not concentration gradient, no diffusion between left and right
takes place; the solution remains at the moment one-phase system. The
density of the system at this stage has a flat profile equal to an average
value, let say ρο. In the 2nd row an infinitesimal fluctuation causes a
concentration difference, such as CBleft>CBright, and therefore diffusion is
expected to take place between left and right localities. The density of
the system has now a wavy profile with maxima and minima around the
average density. In the third row the expected diffusion process results
to CBleft>>CBright, however. Diffusion does not take place from left to
right i.e. from higher to lower concentration (downhill), but oppositely
from right to left i.e. from lower to higher concentration (uphill). Note
that if diffusion was taken place normally from left to right (downhill) it
would result to CBleft=CBright; i.e. the system would be gone back to what
is depicted on the first row. This can not be happened because is the
case of a stable system; i.e. contradicts the initial statement that the
system is already in the unstable region (compare also with Fig.2 to see
the difference). The density is large in extent but small in degree; the
arrows show the diffusion direction. As diffusion progresses the density
increases until it reaches a point where becomes equal to the density of
pure B (rows 3-5). Phase separation that occurs in this way is known as
spinodal decomposition and the fingerprint of that mechanism is the
uphill diffusion.
the two miscible phases and the second derivative is zero at
the points of inflexion. Also, both derivatives are zero at the
free energy maximum. For a series of temperatures, the lo-
cus of the free energy minima projected on a temperature-
composition diagram defines the phase boundary and the
locus of the points of inflexion the spinodal (see lower frame
in Fig.1). The maxima coincide to the upper consolute tem-
perature Tc at XB=0.5. Phase separation occurs when the
system is within the miscibility gap. If the system is in the
metastable region the mechanism is by nucleation and
26
26
 E. P. Favvas and A. Ch. Mitropoulos/ Journal of Engineering Science and Technology Review 1 (2008) 25-27
E. P. Favvas and A. Ch. Mitropoulos/ Journal of Engineering Science and Technology Review 1 (2008) 25-27

growth whereas if it is in the unstable region by spinodal
decomposition.
Figure 2 depicts the nucleation and growth mechanism
[4]. Gibbs (Ref.1 p.254) discussed the possibility of the for-
mation of a fluid of different phase within any homogeneous
fluid and showed that the work W required to form (by a
reversible process) an heterogeneous globule in the interior
of a very large mass having initially the uniform phase of the
exterior mass will be:
4 hand side of eq.(6) (i.e. the fourth-order term) stabilizes the
W = 4πr 2γ − πr 3ΔP ,
3
where γ is the surface tension, r is the radius of the nucleus,
and ΔP is the hydrostatic pressure. In the case where a criti-
cal nucleus is formed the first derivative of eq.(4) becomes
zero while the hydrostatic equilibrium is preserved;
ΔP=2γ/rcrit, where rcrit is the radius of the critical nucleus.
When r>rcrit the nucleus grows and when r<rcrit it collapses
because the pressure exerted by the surface is greater than
ΔP. By introducing rcrit in eq.(4) the minimum work Wmin
required to form that critical nucleus is given as:
4 2
Wmin = πrcrit γ .
3 has taken place [9]. Nucleation may also produce high inter-
Figure 3 depicts the spinodal decomposition mechanism
[5]. Cahn and Hilliard [6] utilize the van der Waals equation
for the energy of binary mixture [7] to develop a model for
spinodal decomposition through Fick’s law of diffusion.
where ƒ is the free energy density of homogeneous material
of composition e.g. CB, M is a positive constant [8], and κ is
a positive parameter. The first term on the right hand side of
eq.(6) is the classical diffusion equation where the coeffi-
cient of ∇2CB is the diffusion coefficient D. Since M>0 the
sign of D will be determined by the sign of ∂2ƒ/∂C2B. When
∂2ƒ/∂C2B>0 the solution is stable, D>0, and diffusion (if any)
occurs downhill. When ∂2ƒ/∂C2B<0 the solution has crossed
the spinodal and is unstable, D<0, and diffusion takes place
uphill. It is noted, however, that the second term on the right
(4) system against short distance scale fluctuations when
∂2ƒ/∂C2B<0. Uphill diffusion and consequently spinodal de-
composition requires a large enough distance scale fluctua-
tion (i.e. to move mass over long distances).
In this note an elementary review on the concept of spi-
nodal decomposition was given. The nucleation and growth
mechanism was also presented. Comparing the two proc-
esses it is evident that nucleation is large in degree and small
in extent while spinodal is small in degree and large in ex-
tent. In Fig.2 and 3 the evolution of the density profiles at
various stages of the processes was drawn. It is noted that
spinodal decomposition results to a high interconnectivity of
the two phases. However, the morphology of the resulted
(5) separation is only an indication that spinodal decomposition
connectivity [10]. Besides, fractal morphology is possible to
be induced by both processes. For instance a fractal flake
that grows is an example of a fractally nucleation process
whereas a twin-dragon Peano curve that thickens is an ex-
ample of a fractally spinodal process [11].

∂C B ⎧⎪ ⎜⎛ ∂f 2 ⎞⎫
⎟⎬⎪ ∇ 2 C B − 2Mκ∇ 4 C B ,
Acknowledgments: The authors would like to thank Ar-
= ⎨M (6) chimedes research Project and INTERREG-III ‘Hybrid
∂t ⎪⎩ ⎜⎝ ∂C B ⎟⎪
2
⎠⎭ = D Technology for separation’ for funding this work.

______________________________
References

1. J.W.Gibbs, Collected Works, Yale University Press, New Haven, J.Stat.Phys. 38, 707 (1985); V.M.Agishev and K.M.Yamaleev,
pp.105-115 and pp.252-258 (1948). Iz.Vyss.U.Zav. Fizika 10, 124 (1975); K.R.Mecke and V.Sofonea,
2. E.A.Guggenheim, Proc.Roy.Soc.A 148, 304 (1935); J.B.Thompson, Phys.Rev.E 56, R3761 (1997); J.Zhu, L-Q.Chen, J.Shen, and
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and Sons Inc., New York, Vol.2 p.340 (1967). mun.Part.Differ.Eq. 18, 453 (1993).
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transition in which nuclei of a new phase are first formed, followed by delingen der Koninklijke Nederlandsche Akademie van Wetenschap-
the propagation of the new phase at a faster rate; J.B.Clark, pen te Amsterdam 1, 1 (1893).
J.W.Hastie, L.H.E.Kihlborg, R.Metselaar, and M.M.Thackeray, Pure 8. M is related to the interdiffusion coefficient. For a binary system
App.Chem. 66, 577 (1994). JB=−M·∇(μB-μA), where J and μ are respectively the flux and the
5. IUPAC definition of spinodal decomposition: A clustering reaction in chemical potential of e.g. the B component and M is the mechanical
a homogeneous, supersaturated solution (solid or liquid) which is un- mobility. Changes in the concentration are given by taking the diver-
stable against infinitesimal fluctuations in density or composition. The gence of the flux: ∂CB/∂t=−∇·JB.
solution therefore separates spontaneously into two phases, starting 9. J.W.Cahn, J.Chem.Phys. 42, 93 (1965).
with small fluctuations and proceeding with a decrease in the Gibbs 10. W.Haller, J.Chem.Phys. 42, 686 (1965); see also W.Haller,
energy without a nucleation barrier; ibid. D.H.Blackburn, J.H.Simmons, F.E.Wagstaff, and R.J.Charles, J.
6. J.W.Chan and J.E.Hilliard, J.Chem.Phys. 28, 258 (1958).; J.W.Chan Amer. Ceram. Soc. 53, 34 (1970); G.R.Srinivasan, I.Tweer,
and J.E.Hilliard, J.Chem.Phys. 31, 688 (1959); see also J.W.Chan, P.B.Macedo, A.Sarkar, and W.Haller, J.Non-Cryst. Solids 6, 221
J.Chem.Phys. 30, 1121 (1959); R.B.Heady and J.W.Chan, (1971); W.Haller, D.H.Blackburn, and J.H.Simmons, J. Amer. Cerum.
J.Chem.Phys. 58, 896 (1973); J.W.Cahn, Trans.A.IM.E. 242, 166 Soc., 57 126 (1974).
(1968); J.W.Cahn, Acta Met. 9, 795 (1961); J.W.Cahn and 11. F.Katsaros, P.Makri. A.Ch.Mitropoulos, N.Kanellopoulos,
R.J.Charles, Phys.Chem. Glasses 6, 181 (1965); V.S.Stubican and U.Keiderling, and A.Wiedenmann, Physica B 234-236, 402 (1997).
A.H.Schultz, J. Amer. Cerum. Soc., 51 290 (1968); A.Noviek-Cohen,

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