THE EFFECT OF VOLUME FRACTION ON PARTICLE COARSENING:

THEORETICAL CONSIDERATIONS*

A. J. ARDELLt

The theory of diffusion-controlled particle coarsening developed by Lifshitz and Slyozov and Wagner
(LSW) is modified to take into account the volume fraction, +, of precipitate. The modification is based
on the supposition that the diffusion of solute to a growing particle (or from a dissolving particle) will
depend on a distance characteristic of the spatial distribution of the particles in the polydisperse assemb-
ly. The characteristic distance chosen for computational purposes is related to the mean free path
between a particle and its nearest neighbor. While this is not the best choice, it serves to make the
problem tractable analytically. Steady-state diffusion under conditions of spherical symmetry is also
assumed.
The modified LSW (MLSW) theory predicts that while the basic t ijs kinetics of the LSW theory are
maintained, the coarsening rate increases with increasing volume fraction, even at very small values of
+. According to the MLSW theory, the theoretical distribution of particle sizes broadens rapidly at
small values of $. In the limit + = 1 the theoretical particle size distribution becomes identical to that
derived by Wagner for the case of interface controlled coarsening. All the results of the LSW theory are
recovered from the MLSW theory in the limit of zero volume fraction.
The results of the MLSW theory are in very good quantitative agreement with the available data on
the coarsening rates of Co precipitates in Cu-Co alloys. The apparent absence of volume fraction effects
on particle coarsening in a number of other alloy systems is discussed in light of the assumptions in-
volved in both the LSW and MLSW theories.

INFLUENCE DE LA FRACTION VOLUMIQUE SUR LE GROSSISSEMENT DES

PARTICULES: CONSIDERATIONS THEORIQUES
La theorie du grossissement des particules control6 par la diffusion, developpee par Lifshitz et Slyozov
et Wagner (LSW), est modifiee pour tenir compte de la fraction volumique # du precipite. La modifica-
tion est basee sur l’hypothese selon laquelle la diffusion du solute vers une particule en tours de croissance
(ou a partir d’une particule en tours de dissolution) doit dependre d’une distance caracteristique de la
distribution spatiale des particules dans le milieu polydisperse. La distance caracteristique choisie pour
les calculs est reliee au libre parcours moyen entre une particule et ses plus proches voisins. Bien que
cette hypothese ne soit pas la meilleure, elle sert a rendre le probleme soluble analytiquement. L’auteur
utilise itgalement l’hypothese de la diffusion en regime permanent dans des conditions de symetrie
spherique .
La theorie LSW modifiee (MLSW) prevoit que, alors que la cinetique de base en t’/3 de la theorie LSW
est maintenue, la vitesse de grossissement augmente quand la fraction volumique augmente, meme pour
les valeurs de 4 t&s faibles. Suivant la theorie MLSW, la distribution theorique des particules s’elargit
rapidement pour les faibles valeurs de 4. Pour $ = 1, la distribution theorique de la taille des particules
devient identique a celle deduite par Wagner pour le cas du grossissement oontri316 aux interfaces. Tous
les resultats de la theorie LSW sont retrouves a partir de la theorie MLSW a la limite pour une fraction
volumique nulle
Les resultats de la theorie MLSW sont en tres bon accord quantitativement avec les valeurs des
vitesses de grossissement des precipites de Co dans les alliages Cu-Co. L’absence apparente des effets de
fraction volumique surle grossissement desparticulesdans certains autres systitmesd’alliages est discutee a
I’aide des hypotheses faites dans les deux theories a la fois.

DER EINFLUD DES VOLUMENANTEILS AN DER TEILCHENVERGRBBERUNG:

TmommIscm UBERLEGUNGEN
Die Theorie der diffusionskontrollierten Teilchenvergroberung von Lifshitz und Slyozov und Wagner
(LSW) wird modifiziert, indem der Volumenanteil 4 der Ausscheidungen beriicksichtigt wird. Die
Diffusion des gel&ten Stoffs zu einem wachsenden Teilchen (oder von einem sich aufliisenden Teilchen
weg) hangt von einem fur die Verteilung der Teilchen in einer polydispersen Anordnung charakteristischen
Abstand ab. Dieser charakteristische Abstand hiingt in unseren Rechnungen mit der mittleren freien
Wegliinge zwischen benachbarten Teilohen zusannnen. Dies ist nicht die beste Moglichkeit, sie erlaubt
jedoch eine analytische Losung des Problems. AuDerdem wird station&e Diffusion unter spharisch
syn n trischen Bedingungen angenommen.
Die modifizierte LSW-Theorie (MLSW) sagt vorher, da5 zwar die ti/3-Kinetik der LSW-Theorie
erhalten bleibt, da5 jedoch die Vergroberungsrate selbst bei sehr kleinen +Werten mit zunehmendem
Volumenanteil der Ausscheidungen zunimmt. Nach der MLSW-Theorie tritt bei kleinen +Werten eine
rapide Verbreiterung der theoretischen Verteihmg der TeilchengriiDen auf. Im Grenzfall 4 = 1 sind die
von Wagner fur grenzflachenkontrollierte Vergroberung abgeleitete und die von der MLSW-Theorie
vorhergesagte TeilchengrGBenverteilung gleich. Alle Ergebnisse der LSW-Theorie werden von der
MLSW-Theorie fur den Grenzfall 4 = 0 geliefert.
Die Ergbnisse der MLSW-Theorie sind in sehr guter quantitativer ifbereinstinnnung mit gemessenen
Vergroberungsraten von C-Ausscheidungen in Cu-Co-Legierungen. Das scheinbare Fehlen eines Volu-
menanteil-Effektes auf die Teilchenvergroberung in einigen anderen Legierungen wird anhand der
Annahmen sowohl der LSW-Theorie als such der MLSW-Theorie diskutiert.

* Received April 21, 1971; revised June 22, 1971.

t Materials Department, School of Engineering and Applied Science, University of California, Los Angeles, California.

ACTA METALLURGICA, VOL. 20, JANUARY 1972 61

62 ACTA METALLURGICA, VOL. 20, 1972

INTRODUCTION spherical precipitate is a valid assumption, the volume

The theory of diffusion-controlled particle coarsen- fraction problem is eliminated by allowing r’ to
ing developed by Lifshitz and Slyozov(l) and Wagnerc2) approach infinity. Perhaps it is not quite obvious why
(LSW) is applicable, strictly speaking, only when the this is so, because a relationship between r’ and 4 has
volume fraction 4, of the dispersed phase is very not yet been established. However, this interpretation
small. Just how small 4 must be is not precisely of equations (1) and (2) is justified in the following
defined by LSW, but they assume it is small enough so section by reasonable arguments which demonstrate
that the mean distance between particle centers is that the LSW theory is, in essence, appropriate to
large compared with the particle dimensions. zero volume fraction of precipitate.
On an intuitive basis one might expect the volume Before proceeding to the present development, it is
fraction of particles to influence the coarsening worth mentioning that attempts to incorporate 4 into
process, because the kinetics are controlled by the the theory of coarsening have been made by Lifshitz
diffusion of solute from dissolving particles to growing and Slyozov, Sarian and Weartf5) and Asimon.‘@
particles. As $ increases the mean separation between Lifshitz and Slyozov treat the volume fraction problem
particles of a given average size decreases and the in terms of what they call “encounters” among
diffusion paths become shorter. It then follows that particles. Their mathematically complex treatment is
the coarsening rates should increase with increasing presented as a perturbation of the zero volume fraction
volume fraction. However, since $ is not a parameter case, and is not readily amenable to experimental
in the LSW theory, this effect is not predicted. verification because it is difficult to decide upon the
The volume fraction of precipitate does not enter necessary level of approximation. Sarian and Weart’s
into the LSW theory because of the manner in which theory is very simple mathematically, but suffers from
the flux of solute to the precipitate is calculated. The an unrealistically oversimplified treatment of the diffu-
general solution to the non-steady-state diffusion sion geometry. Asimow’s treatment of the diffusion
problem of the growth of a spherical precipitate was problem is reasonable, but neither he nor Sarian
solved some time ago by Zener.t3) The nature of the and Weart made any attempt to incorporate their
solution to this problem introduces a number of predicted volume fraction effects into the framework
difficulties when it must be applied in other circum- of the LSW theory.
stances, e.g. the growth of a spherical precipitate dur- In what follows, a modified LSW (MLSW) theory is
ing particle coarsening. However, Zener and otherst4) developed to include the effect of 4 on diffusion-
have demonstrated that when the region of solute controlled coarsening kinetics. The difficulties asso-
depletion is large compared with the radius of the ciated with the diffusion geometry used by Sarian and
precipitate, the concentration gradient at the particle- Weart are avoided by more realistic and appealing
matrix interface is given by assumptions which are similar to those used by Asimow .
Unlike the treatment of Lifshitz and Slyozov, the role
of $ is introduced at the outset of t’he development.
In later sections, some of the available literature data
where c is the concentration of solute at distance are examined in light of the MLSW theory.
R(r < R < co), c, is the concentration at the interface 2. THEORY
of the particle of radius r, and c’ is the concentration 2.1 Di$usio~ geometry
at very large distances from the particle (R = co). Consider a spherical precipitate of radius ri surround-
Equation (l), which is the expression used by LSW, is ed by particles of varying radii. We suppose that
formally identical to the expression obtained by the particles are dispersed “randomly” throughout
assuming that solute diffuses to the spherical particle the matrix in the unoccupied space available to them,
under steady-state conditions. If, in fact, we write so that particle interpenetration is excluded. A two-
down the well-known solution to the problem of dimensional conceptualization of the three-dimensional
steady-state diffusion through concentric spheres of configuration is shown in Fig. 1. We now select a
radii r and r’, i.e. particle, which has radius ri, and inquire which region
of the matrix is likely to act as a source of solute atoms
dc c’ - c,
(2) if the ith particle is growing, or a sink for solute atoms
dR r(1 - V/Y’)
if the particle is dissolving. Whether this particle is
R=r =

where c’ is now the concentration at R = r’, we see instantaneously growing or dissolving depends upon
that equation (1) is recovered in the limit r’ + co. the value of c,~ compared with the value of cl, irrespec-
Provided that steady-state diffusion to an individual tive of the precise diffusion geometry. The value of c’
 ARDELL: ON PARTICLE
0
Cl
FIQ. 1. The Dirichlet region for a two-dimensional dis-
tribution of circular particles. The shaded particles are
nearest neighbors to the ith particle.
is determined by the entire polydisperse assembly of
particles, and is a sort of average property of the
system at a given instant of time. In the LSW theory
the instantaneous growth behavior of a given particle
is independent of the positions of all the other particles,
and in order to arrive at equation (1) it is necessary to
assume that the source (or sink) of solute, the concen-
tration of which is c’, is infinitely far from the particle.
Sarian and Weart assumed that the source (sink) of
solute atoms was related to the mean free path, ,J,
between the ith particle and all of its neighbors.
Except at large volume fractions, il is usually quite
large compared with the average particle size. If we
were to construct a sphere of radius ri + 3,centered on
the ith particle, we would generally expect this sphere
to contain many other particles. It is therefore
unrealistic to assume that the boundary of such a
sphere could fulfill the requirements of a solute source
or sink for the particle at its center. ~u~herrno~, the
solute distribution everywhere within the sphere
could not possibly be spherically symmetrical with
respect to the center of the ith particle.
One of the important hypotheses of the MLSW
theory is that the concentration of solute in the matrix
must approach c’ at a distance from the ith particle
which is somehow associated with the spatial distri-
bution of the other particles in its immediate neighbor-
hood. It is further assumed that the appropriate
distance is a properly chosen average distance between
the ith particle and its immediate neighbor. Apart
COARSENING 63
from certain specific details, this approach is similar to
that used by Asimow.
The most appealing choice for the average distance
is a characteristic distance defined by the Dirichlet
region surrounding the ith particle, such as that oon-
strutted for the particle of radius ri shown in Fig. 1.
The Voronoi polygon in Fig. 1 was oonst~~ted
according to the usual rules, with the exception that
the perpendicular bisectors defining its edges do not
divide the radial lines connecting particle centers, but
instead those connecting the particle surfaces (indicat-
ed by the distance 1, for example). The advantage of
defining the Dirichlet region in this way is that the
edges of the Voronoi polygons (or, in three dimensions
the faces of thevoronoi polyhedra) cannot pass through
any of the nearest neighbors, shown shaded in Fig. 1.
For the purpose of setting up and solving the dif-
fusion problem, we can then define the ~har~eteristi~
radius, r’, at which the solute concentration is assumed
to be c’, as the radius of the circle (sphere) which en-
closes the same area (volume) as the Voronoi polygon
(polyhedron). This is the way the circle of radius
r’ in Fig. 1 was constructed. It is recognized that
other choices are possible, based on an alternate
average distance associated with the Dirichlet region.
Unfortunately, the problem at this point becomes
academic, because an analytical expression for 8,
even for the relatively simple case of a random distri-
bution of point particles in two dimensions, has not
been found as far as the author is aware.
For ~omputat,ional purposes, then, it is necessary to
estimate T’ by other means. A reasonable alternative
to the radius of the Dirichlet region is the radius
related to the mean free path, i, between a particle
and its nearest neighbor. If i can be found for the
polydisperse assembly of particles, then r’ for the ith
particle will be given by
rf = ri + i/2 (3)
We can expect that r’ in equation (3) will generally
~derestimate the value of r’ depicted in Fig. I.
It is now neoessary to find a relationship between 4
and r’. For a polydisperse system of particles an
appropriate relationship is difficult to obtain, How-
ever, when all the particles have the same radius, say
r*, it can be shown(‘) that for randomly distributed
particles (in the sense used earlier) the average center-
to-center distance, 2, between a particle and its
nearest neighbor is
(4
64 ACTA METALLURGICA,
where
I?(#) = coz-z’3e-s &Z (51
s sl
Equations (4) and (5) were derived by adapting
Chandrasekhar’s calculation for point particles@) to
the situation in which the particles have a finite
radius. These equations become increasingly accurate
as $ approaches zero, but when + approaches unity
the approximations used in their derivation are
evidently poor. For example, when $ = 1 (technical-
ly, a physical impossibility for non~deformable,
monodis~rse sphe~cal pa~ieles) ft must equal 2r*,
implying l?(l) = 0 in equation (4). Obviously,
I’(l) # 0 from equation (5). Fortunately, coarsening
is rarelystudiedinsystemscontainingvolume fractions
of particles in excess of 0.5. Even at these relatively
large values of 4, equations (4) and (5) predict that R
is approximately 2.2 r*, which is a reasonable result.
When all the particles are the same size, i can be
found from the relationship
(6)
i
If we assume that from equation (6) is applicable to a
polydisperse assembly of particles, we can immediately
apply equation (3) to obtain
rr r* e*“r($)
-=1+------ (7)
r( rt 6+i3
In the derivation of equation (7) we have made the
important assumption that equation (4), which is
valid for a monodisperse assembly of pztrticles of
radius r*, can be applied to a polydisperse aggregate.
This impIies that r* should be interpreted as the
average particle radius of the polydisperse system,
and that t will not be very different for monodisperse
and polydisperse systems. For various reasons, it is
advantageous to associate r* with what is generally
referred to as the critical radius of the polydisperse
system. The critical radius is defined in such a
manner that those particles with radii equal to r* will
be in unstable equilibrium with the matrix insofar
as these particles will be neither growing nor shrinking
at a given instant of time. It would undoubtedly be
more approp~ate to equate r* with the average
particle radius, P. However, we can anticipate that r*
and a will not be very different, and it is primarily a
matter of convenience to adopt the chosen definition.
Equation (7), then, is the relationship we have been
seeking, since it provides the dimensional parameters
associated with the diffusion geometry for an individ-
ual particle in terms of statistical parameters related
VOL. 20, 1972
to the whole assembly of particles. The di~sion
problem is now reduced to that of diffusion through
concentric spheres of radii r and rli and in order to
make the problem tractable, applicability of the steady-
state solution in the form of equation (2) must be
assumed. The use of equation (2) is hardly justified by
the fact that we can get nowhere without it. However,
it is reasonable to assume that equation (2) will rep-
resent a higher level of approximation than equation
(1) as long as r’ is sufficiently larger than ri, In this
connection, we point out that Greenwood,@) in his
pioneering treatment of the coarsening problem,
assumed that the steady-state diffusion approxim-
ation would be valid provided the particles were far
enough apart so that the diffusion field around each
particle could be considered spherically symmetrical.
Asimow@) simply modified Greenwood’s equations to
account for the fact that spherical symmetry could
not extend indefinitely due to the presence of the
other particles. In essence, Asimow used equation (2)
instead of equation (1) to calculate the concentration
gradient at the particle-matrix interface. Interesting-
ly, SpeighVo) also assumed steady-state diffusion
conditions for particles with cylindrically s~metrical
concentration profiles in his treatment of the coarsen-
ing of grain-boundary precipitates. In this case r’
cannot be allowed to approach infinity because the
concentration gradient depends logarithmically upon
R. A finite upper limit for r’ must be introduced into
the equations, which Speight took as the grain size.
Proceeding, then, if we substitute equation (7) into
(2) (dropping the subscript on r), we obtain the approp-
riate expression for the concentration gradient at the
particle-matrix interface,
dc (c’ - $1
(8)
zi REr
= ~
r
(1 + &a),
where
(9)
and
p = r/r*. (10)
The effect of volume fraction is thus associated with
the parameter b.
The manner in which /l varies with $ is ilIustrated
in Fig. 2 [I’(.#) was obtained by numerical integration
of equation (5)]. It is seen that /3 increases monoton-
ically with $, from zero at 4 = 0 to a value slightly
greater than 25 at 4 = 1. Strictly speaking, B must
approach infinity as 4 -+ 1, but this does not happen
because of the approximate nature of equation (4)
 ARDELL: ON PARTICLE COARSENING 66

r equations (12) and (13) into account,

(14)

which can be expressed alternatively as

- = 3crDsz(p - 1) (1 + BP).
dt

We note from equation (14) that when r = ~*(p = l),

d~/dt = 0, so that the critical radius, r*, martins the
same distinction as in the original LSW theory.
We now transform equation (15) into an expression
for the rate of change of the relative particle size, p,
with respect to the critical particle size, r*. This is
equivalent to finding the time dependence of p, since
T* increases monotonically with time. To this end,
we differentiate p3 with respect to t, and with the
aid of equation (15) and some algebraic manipulation
we obtain

I I I I dP3= -$ 3~D~(f - l)(l + BP) - p3g3 (16)

0.2 0.4 0.6 0.8 -27 i
+
On multiplying both sides of equation (16) by dt/dF,
FIO. 2. Illustratingthe dependenceof the parameter,!J
on the volume fraction, 4. and letting 7 = ln(r*a) we obtain

and (5). In order to estimate the dependence of dP3

- = fp - 1)V + ~~)~ - f” (17)
various parameters (to be ~trodu~ed) on #J in the t&r
Iimiting case of # = 1, we will use the correct value where
/? = co and not the calculated value in Fig. 2.
Y = ~(4) = 3uDQ -$ (18)
2.2 Coarsenilzg theory
From this point on, the MLSW theory is readily As shown by Lifshitz and Slyozov, and also by
developed following the procedures used by Lifshitz IIillert,@n steady state solutions to equation (17) are
and Slyozov. Equation (8) is first related to the flux of possible only if v is constant, the value of which can be
solute to the particle of radius T to yield its growth found by setting dp3/dr and d(dp3/&)/dp equal to
rate, zero.
Before we evaluate v, it should be noted that
equation (18) is the differential form of the coarsening
equation. Integration of equation (18) yields (with
where D is the coefficient of solute diffusion in the Y = cons&)
matrix and Sz is the molar volume of the precipitate. *3 _ 3crDSlt
r*3 - (19)
ro
The factor c’ - G, is written as (c’ - c,) - (c, - ce) -7Ji-’
and the Gibbs-Thomson equation is employed to
express e, - c, in terms of r, i.e. where rs* is the critical particle radius at t = 0 (the
onset of coarsening). Equation (19) tells us immedi-
c, - c, = u/r (12) ately that the rate law for coarsening is unaffected by
where volume fraction considerations, although the rate
constant
(13) 3aDi-2
k’ = k’(c#a)= - , (20)
44)
y is the interfacial free energy of the parti&--matrix
interface, and RT has its usual meaning. Letting will be a function of 4 through the dependence of
T* = a/(c’ - CL), equation (11) becomes, taking ~(4) on 4, which we now derive.
5
66 ACTA METALLURGICA, VOL. 20, 1972

By setting equation (17) and its first derivative with discuss this point briefly later on). The equation that
respect to p equal to zero, we find describes the particle size distribution follows directly
3 from the expression presented by Sauthoff and Kahl-
3P7n2
(21) weit, who show that
* = @pm2 + (lp” fi)p, - 1 = 1 + 2BP, - B
where
(B” + p + 1P - (1 - #0
Pm = (22)
B * where A is a constant. The value of A can be obtained
The new parameter, pm, introduced in equations (21) by normalizing g(p) such that
and (22), is the theoretica relative maximum particle
size of the polydisperse assembly. The theoretical (24)
distribution of particle sizes must go to zero when
Letting
P 2 pm-
From equations (21) and (22), it is easy to show that
as ,4 -+ 0, v --+ 2714 and pm -+ 312. Thus, these results
of the LSW theory are recovered in the limit of zero
equation (24) can be rewritten as
volume fraction. As /3 + CD(#-+ 1)~ -+ 0 and pm + 2.
Consideration of this result in light of equations (19) A f(P¶n)
er(@-= A
and (20) shows that the coarsening rate should in-
(efh%d - gf(O)) = 1
(25)
3 s f(O) 3
crease without limit as the volume fraction increases
towards unity. Furthermore, the maximum particle The fun&ion j’(p) is zero at p = 0 and decreases,
size in the polydisperse assembly approaches twice approaching -CO as p approaches pm. This follows
the critical particle size, so that we can anticipate a from the fact that dp3/dr, from equation (17), is equal
broadening of the theoretical particle size distribution to zero when p = pmex. The value of A is then,
as CJincreases. The complete dependence of v and pm from equation (25), equal to -3. Thus,
upon Q is illustrated in Fig. 3, where it is observed
that v decreases and pm increases monotonically as + g(P) = $exp (S,‘$j$) (26)
varies from zero to unity.
Equation (26) can be inflated analytically only
when p = 0 (# = 0) and ,8 = co (# = 1). For the ease
In order to evaluate the variation of the distribution $I = 0, we obtain (apart from a no~alization constant)
of particle sizes as a function of 4, we can follow the the result of the LSW theory. When @ = CO the
procedures used by Lifshitz and Slyozov, or the particle size distribution is
particularly clear presentation of Hillert. Fortunate-
ly, this has already been done by Sauthoff and ; ps2
(27)
Kahlweit,(12) who arrived at equations (17) and (21)
by entirely different physical arguments (we shall t.0;p>2
Curiously, equation (27) is formally identical to the
‘r- F2.* distribution function derived by Wagner for the
case of interfa~-eontro~ed coarsening, and also to
the ~st~but~on function derived by Hillert for the
case of three-~mensiona1 grain growth, both of which
are governed by PI2 kinetics.
pm Figure 4(a) illustrates how g(p), computed numer-
i .6 ically, changes as a function of 4. The greatest change
in g(p) occurs for small values of 4, as illustrated by the
curves for $ = 0.005 and 0.05. When I?t,is greater
than 0.2, the shape of the distribution curve becomes
1.6

I
*o ,Y--Y
0. I 0.2 0.3 0.4
I a
0.5
”

/
0.6 0.7
I 0.6 *
0.9 1 1 .5
1.0 relatively insensitive to +.
In order to facilitate the comparison between
experimentally determined particle size distributions
Fra. 3. Illustrating the dependence of the parameters Y
and pm on the volume f&&ion, #. and the predictions of the NLSW theory, it is useful
 ARDEL’L: ON PARTICLE COARSENING 67

to describe the theoretical ~s~~b~tion in terms of a

new relative particle size p’ -I r/P, since i: is measured
whereas T* is generally nnkno~~ To this end we
define a new distribution function g’(p’). Since p’ =
p/p, where p(= f/r*) is found from the equation

it is easy to show that g’(p’) = &(pf. The va~at~un

of p’ with $, obtained by numerical integration of
equation (28) is shown in Pig. 5, and g’( p’) is shown in
Fig. 4(b). From Fig. 5 it is observed that p decreases
rapidly from unity (at 4 = 0) and slowly approaches
its limiting value of S/Q, obtained by analytical
integration of equation (28) using g(p) for /J = co
given by equation (27). The ~stribution curves in
Fig. 4(b) are seen to be slightly broader than those in
Fig. 4(a) and their maxima occur at the same value of
p’; which is not the case for the curves in Fig. 4(a).

0.90 -

0.88 I
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 3
d,

Fm 5. Illustrating the dependence of the ratio of the

average par&al radius, f, and the critical partica3rrtdius,
r*, on the volume fraction, 4.

Even though pm’ is theoretically greater than 2 for

# > 0.2 (P?n’ = 2.25 for &,== I), the practical prob-
abihty of finding a particle with r > 1.8 F is theoreti-
cally nil.

In order to put equation (X9) into a useful form, we

must rewrite it in terms of i, since i: is what we deter-
mine experimentally. To this end we again make use
of equation (28), which provides the relation between
P and 4. In terms of the average particle size, the
coarsening equation (19) can be expressed as

p’=r/i
W The rate fondant for coarsening, k(4) is thus
3%. 4. (a) Ill~tr~t~g the dependence of the theoretical
distribution of particle sizes on the volume fraction, 4;
(b) the particle size distributions redefined as functions
of the variable p’ = rjF_
 ACTA METALLURGICA, VOL. 20, 1972

TABLE 1. The variation of the important parameters in the

MLSW coarsening theory with the volume fraction of pre-
cipitate

0.001 0.286 4.683 1.593 0.988 1.390

0.002 0.386 4.218 1.619 0.984 1.526
0.003 0.466 3.912 1.638 0.982 1.632
0.004 0.532 3.680 1.653 0.979 1.723
0.005 0.593 3.493 1.665 0.978 1.806
0.006 0.649 3.336 1.676 0.976 1.880
0.007 0.702 3.201 1.680 0.974 1.951
0.008 0.752 3.082 1.695 0.973 2.018
0.009 0.799 2.975 1.702 0.972 2.081
0.010 0.846 2.880 1.710 0.971 2.143
0.020 1.247 2.245 1.762 0.961 2.672
0.030 1.596 1.883 1.794 0.955 3.123
0.040 1.917 1.638 1.818 0.950 3.536
0.050 2.223 1.457 1.836 0.946 3.925
0.060 2.518 1.316 1.850 0.943 4.298
0.070 2.806 1.203 1.862 0.940 4.659
0.080 3.087 1.110 1.871 0.938 5.011
0.090 3.363 1.031 1.880 0.935 5.355
0.100 3.636 0.964 1.887 0.933 5.693
0.180 4.960 0.731 1.913 0.926 7.323
0.200 6.246 0.592 1.929 0.921 3.891
0,250 7.507 0.499 1.940 0.917 10.422
0.300 8.756 0.432 1.948 0.914 11.930
0.350 9.995 0.381 1.954 0.912 13.422
I I I I 0.400 11.228 0.341 1.958 0.910 14.903
0.02 0.04 0.06 0.08 0 0.450 12.454 0.309 1.962 0.908 16.374
0.500 13.676 0.282 1.965 0.907 17.837
+
0.560 14.896 0.260 1.968 0.906 19.296
(a) 0.600 16.111 0.241 1.970 0.906 20.748
0.050 17.322 0.224 1.972 0.904 22.195
251

as a function of # [k(O) is the rate constant of the LSW

theory, obtained from equation (30) by recalling that
Y(O) = 27/4 and $0) = 11. The ratio

~(#) 27 IT3f#)
---= --
W) 4 44)
is shown in Fig. 6(a) for small volume fractions, and
in Fig. 6(b) for volume fractions up to 0.65. It is
seen in Fig. 6(a) that even at small values of 4, the
effect of 4 is appreciable. The coarsening rate is
twice that of the LSW theory when 4 is only about
0.008, a factor of three times as great when 4 is only
about 0.027, and five times as great when 4 is about
0.073. From Fig. 6(b), a ten-fold increase is predicted
01 I I I I 1 I for 4 ‘U 0.25, and a twenty-fold increase for (b N 0.55.
0 0.1 0.2 0.3 0.4 0.5 .0.6
To facilitate the comparison between the MLSW
4
theory and experimental data, the important para-
(b)
meters /l, Y, pm, j5 and ail are tabulated as a
FIG. 6. Illustrating how the rate constant, k($), for
diffusion-controlled coarsening varies with the volume function of 4 in Table 1.
fraction, r$; (a) at small volume fractions; (b) at volume
fractions up to + = 0.65. 3. APPLICATION TO COARSENING IN Cu-Go
ALLOYS
which, unlike k’($) in equation (20), can be compared
The only data in the literature that the author is
directly with experimental data. To emphasize the
aware of in which a volume fraction effect has defin-
effect of + on the coarsening rate, it is convenient to
itely been observed, are the data of Livingstono3) on
plot the ratio ~(~)/~(O), where
the coarsening of coherent Co-precipitates in Cu-Co
~GcDLR 8yc,D@ alloys. Ardell and Nicholson, in their analysis(14) of
k(0) = -$-- = ~
(31)
9RT Livingston’s data, showed that the interfacial free
)
 ARDELL : ON PARTICLE
wt. XC0 #co
(measured)
0.7 600 0.0039
1.3 600 0.0106
:::: 600
650 0.0168
0.0184
::: 600
650 0.0318
0.0195
Z-
energy, y, calculated from the experimental values of
k, increased with increasing $oo. These data, re-
analyzed in light of the MLSW theory, are presented
in Table 2. Values of k(0) were obt&ned from the
measured rate constants, k(#, from gr~ph~~~y
i~~rpol~~d values of the theo~tio~l ratios in Table 1
at the appropriate vaiues of 4. At T = 6OO”G, the
k(0) values so obtained are nearly constant as pre-
dicted by theory, the only notable exception being
the value for the 3.2% Co alloy (d, =: 0.0318). The
recalculated values of y(new), obtained from the
values of k(0) in Table 2 are seen to be independent
of &o- Furthermore, the new values ere in good
agreement with the vctlue of approximately 196-200
ergs/cm2 obtained by Servi and Turnbull(f5) in their
study of precipitation kinetics in Cu-Co alloys.
4. DISCUSSION
Perhaps the most surprising result of the MLSW
theory is the rapid variation of the coarsening param-
eters in TsbIe I at small volume fractions. This
r&pid variation is due, physically, to the assumption
that only the mean free path between a particle and
its nearest lzeiqhbor affects the value of r’ in equation
(1). The large effect on the coarsening rates predicted
at small values of (F,is in good quantitative agreement
with the data on the Cu-Go system, even though +oOis
oonspjeuo~ly small. This is certainly an encoumg-
ing sign that the MLSW theory is basically correct,
because the assumptions used in the derivation of
equation (7) are increasingly accurate as I# approaches
zero. Moreover, the applicability of the steady-state
solution to the diffusion problem, equation (2),
becomes more realistic as #J approaches zero. It is
worth reiterating that P’~calculated from equation (11,
actually underest~~t~s the value of the “r&ius” of
the Diriohlet region. Therefore, if we could oalmzfato
this radius,we would find that the values of the param-
eters in Table I wauld depend less strongly on +.
This factor would probably improve the overall
agreement between theory and experiment for the
Cu-Co system.
COARSENING 69
k
fcms@3c x lO**f Y
@rgfcW
k(#) k(O)
(calculated) - Old NC?&,
5.37 3.13 304 177
6.75 3.10 382 175
50.90
7.96 20.20
3.07 451
388 1.54
174
13.00
0.83 5.62
0.31 IO20
521 318
199
With respect to other available data on coarsening
kinetics, the agreement between experiment &nd the
prediotions of the MLSW theory does not appear to be
very good. Particle coarsening has beeninvestigated in
a variety of alloy systems in which no effect of volume
fraction on the evening rates has been observed,
In the N-Al system, for example, the y’(Xi&.l)
precipitate coarsening kinetics have been investi-
gated(idJ6) in alloys containing from 9 to 20% y’*
There is no question thsGt the rate constants are
entirely independent of t& over this range. In fact,
in current investigations in this laboratory the y’
coarsening kinetics have been studied in &Boys con-
taining up to 60% y’ and no effect on k has been
observed.u7) This is puzzling, not only from the view-
point of the MLSW theory, but also from that of the
original LSW theory, since the mean particle separ-
ation in most of these alloys is much smaller ths,n the
average particle size.
Other systems in which no volume fraction
effects have been observed include Gu in ,-Fe@*) and
NbC in liquid Fe .f6) The latter system wss studied
by Sttrian and Weart, who specifically looked for 8
volume fraction effeot at very large values of
4NbC (0.60-0.90). They found that t1/3 kinetics were
obeyed over the entire range, but that the rate
constsuts were independent of &,o. However, they
also found that while the number of particles per unit
volume, Z, decreased with time as E-I, in agreement
with W~gner’s(2~ predictions, 2 was also independent
of 4, which is an impossible result. The source of
this inconsistency is not evident.
The results of Speioh and Oriani(ls) on the coorsen-
ing of Cu precipitates in &Fe are somewhat more
disquieting. The range of $o,, in their study w&s
roughly equivalent to th& of #o. in Livingston’s Gu-
Co alloys, and k was found to be clea.rly independent
of the volume fraction, The shape of the Cu pre-
cipitates in this alloy is not spherical, a factor which
would influence the quantitative aspects of the diffu.
sion geometry, but on a semiquantitative basis a
volume fraction dependence of the coarsening rate
70 ACTA METALLURGICA, VOL. 20, 1972

would still be expected. The fact that none is ob- that owing to the difficulties usually encountered in
served is totally inconsistent with the MLSW theory. measuring particle size distributions to a high degree
However, the quantitative agreement with the LSW of accuracy, it is clearly difficult, if not impossible, to
theory is not too good in this case either, because the decide between diffusion-controlled and interface-
values of the interfacial free energy calculated from controlled coarsening on the basis of experimentally
the measured coarsening rates are too large by a measured particle size distributions alone.
factor of approximately eight. On examination of the available evidence, the
In addition to the available data on coarsening MLSW theory appears to fail miserably in explaining
kinetics, it is also possible to compare experimentally the data on the systems containing high volume
observed particle size distributions with the predic- fractions of the dispersed phase. As has already been
tionsof theMLSW theory. In almost every case known pointed out, this is puzzling because the original
to the author, the experimental distributions are LSW theory would not be expected to hold when the
broader than the theoretical distribution of the LSW average particle separation is smaller than the
theory. In the Ni-base y-y’ alloys there is good particle dimensions. According to equation (6), we
evidence that the magnitude of the y-y’ lattice misfit, would expect to find the condition i = r* in a mono-
which varies from one system to another, is at least disperse system when ,5 = 2, or when $ is approxim-
partly responsible for the observed broadening.og) ately 0.04. Even if we double this value to allow for
However, this factor cannot account for the other assorted errors introduced by various assumptions,
observation that in the Ni-AP and Ni-Sic12) systems the values of q$ in the y-y’ alloys studied to date all
the particle size distributions are evidently independ- exceed 0.08, and in the NbC-liquid Fe system studied
ent of 4. by Sarian and Weart the liquid Fe matrix was actually
In at least two systems, isoamyl alchol droplets in the minor phase. Nevertheless, for the y-y’ alloys
watert20) and u-Mn in Mg, fzl) the observed broadening in particular the quantitative agreement between
of the particle size distributions cannot be attributed experiment and the LSW theory is exceptionally good
to coherency strains. Unfortunately, the data on in all respects, save for the aforementioned breadth
these systems are not extensive enough for a quantita- of the particle size distributions. This is viewed
tive comparison with the MLSW theory. However, here as truly remarkable, since the particles are so
it is encouraging that the particle size distributions close together in most of the y-y’ alloys that neither
are broader than predicted by the LSW theory, since equations (1) nor (2) should be valid for describ-
the particles are spherical in both of them and the ing the concentration gradient at the interface of an
effect of volume fraction is the only factor of signifi- individual particle. It simply seems unreasonable to
cance, apart from expected experimental uncertain- expect steady-state diffusion to an individual particle,
ties. under conditions of spherical symmetry, to occur
It is interesting to note that the theoretical particle when 4 is so large. Viewed in this light, the failure
size distributions of the MLSW theory he somewhere of the MLSW theory at high volume fractions is
in between the LSW result for diffusion-controlled easier to accept and understand than the apparent
coarsening and the Wagner result for interface-con- success of the LSW theory.
trolled coarsening, which is identical to equation (27). Finally, it was pointed out earlier that Sauthoff and
This could account for some of the confusion which Kahlweit arrived at results similar to those presented
has arisen as to whether coarsening was actually inter- in this paper using an entirely different type of argu-
face or diffusion-controlled. For example, Smith,(si) ment. They assumed that the diffusion coefficient
who investigated the coarsening of cc-Mn particles in could be expressed (in the present notation) as D =
an Mg matrix, concluded that the u-Mn particle D,(l + @r/r*). In their development, p is left as a
size distributions agreed reasonably well with both disposable parameter, since there is no way to relate
the interface-controlled and diffusion-controlled (LSW) it to any of the processes which occur during particle
theoretical distributions. The values of #a_-Mn in coarsening. Just why the diffusion coefficient should
Smith’s alloy were very small (the order of O.OOl), but depend upon p is not made clear by Sauthoff and
even at these low values perceptible broadening is Kahlweit [one could assume y = yo(l + pp) and
predicted by the MLSW theory. The feeling here is obtain the same result]. Though their theoretical
that the u-Mn particles do grow by diffusion-controlled results are formally identical to those of the MLSW
coarsening, and that the observed breath of the cr-Mn theory, the physical basis for their assumption of a
particle size distribution is at least partly due to particle-size dependent diffusion-coefficient is some-
volume fraction effects. We may conclude from this what obscure.
 ARDELL: ON PARTICLE COARSENING 71

5. SUMMARY AND CONCLUSIONS ent of ~4even though they are generally broader than
The MLSW theory developed in this paper predicts the distribution predicted by the LSW theory.
that particle coarsening rates should increase with Since the assumption of steady-state diffusion to an
increasing volume fraction of precipitate, whereas the individual spherical particle should not be valid when
basic t1i3 kinetics for diffusion-controlled coarsening 4 > 0.08, the breakdown of the MLSW theory is not
are unaffected. Even at very small volume fractions nearly as surprising as the apparent success of the
(4 < 0.01) the effect of 4 on the coarsening rate is LSW theory in describing the data on the y+y’
significant. The theoretical distribution of particle alloys. There is clearly a need for systematic experi-
sizes is predicted to broaden rapidly with increasing mental work on carefully selected alloys so that this
4, and approaches the particle size distribution for incongruity can be resolved.
interface-controlled coarsening in the limit 4 = 1.
6. ACKNOWLEDGEMENTS
The results of the MLSW theory agree with the
original LSW theory in the limit of zero volume frac- The author is grateful to Mr. Pramod Bansal for
tion. performing the bulk of the necessary computer work,
The predictions of the MLSW theory are in very to Professor Didier de Fontaine for valuable discus-
good quantitative agreement with the available data sions on several important points, and to the U.S.
on the coarsening of Co precipitates in Cu-Co alloys. Atomic Energy Commission for their financial support
However, the MLSW theory is inconsistent with the of this project.
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