Advances in Colloid and Interface Science 134–135 (2007) 35 – 71

www.elsevier.com/locate/cis

Gravity as a factor of aggregative stability and coagulation

A.S. Dukhin, S.S. Dukhin ⁎, P.J. Goetz
Electrokinetic Technology, Goldens Bridge, NY 10526, USA

Available online 29 April 2007

Abstract

Gravity is a potential factor of aggregative stability and/or coagulation for any heterogeneous system having a density contrast between the
dispersed phase and its dispersion medium. However, gravity becomes comparable to other stability factors only when the particle size becomes large
enough. Since the particle size may grow in time due to various other instabilities, even nano-systems may eventually become susceptible to gravity.
There have been many attempts in the last century to incorporate gravity in the overall theory of aggregative stability, but the relevant papers
are scattered over a wide variety of journals, some of which are very obscure. Reviews on this subject in modern handbooks are scarce and
inadequate. No review describes the role of gravity at all three levels introduced by DLVO theory for characterizing aggregative stability, namely:
particle pair interaction, collision frequency and population balance equation. Furthermore, the modern tendency towards numerical solutions
overshadows existing analytical solutions.
We present a consistent review at each DLVO level. First we describe the role of gravity in particle pair interactions, including both available
analytical solutions as well as numerical stability diagrams. Next we discuss a number of works on collision frequency, including works for both
charged and non-charged particles. Finally, we present analytical solutions of the population balance equation that takes gravity into account and
then compare these analytical solutions with numerical solutions. In addition to the traditional aggregate model we also discuss work on a fractal
model and its relevance to gravity controlled stability.
Finally, we discuss many experimental works and their relationship to particular theoretical predictions.
© 2007 Elsevier B.V. All rights reserved.

Keywords: Aggregative stability; Gravity; Gravitational coagulation; Surface forces; DLVO theory; Flotation; Collision frequency; Non-Brownian particles;
Population balance equation; Chain coagulation; Fractal; Aggregate breakup

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
2. Historical overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
3. Parameterization of heterogeneous systems. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
4. Pair particles interaction. Corresponding gravity effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
4.1. DLVO surface forces for non-Brownian particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
4.1.1. Electrostatic surface force . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
4.1.2. Molecular surface forces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
4.2. Gravity induced pair interaction forces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
4.3. Classification of the gravitational coagulation modes. Stability diagram . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
4.4. Analytical solution. Stabilization against secondary minima coagulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
4.5. Analytical solution. Acceleration of slow coagulation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
4.6. Numerical solution. Stability diagram . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
4.7. Gravity role in hetero-coagulation and micro-flotation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
4.8. Prevention of coagulation in primary minima in micro-flotation due to gravity. . . . . . . . . . . . . . . . . . . . . . . . . 50

⁎ Corresponding author.
E-mail address: sdukhin@bestweb.net (S.S. Dukhin).

0001-8686/$ - see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.cis.2007.04.006
36 A.S. Dukhin et al. / Advances in Colloid and Interface Science 134–135 (2007) 35–71

5. Probability of aggregates formation and breakup. Corresponding gravity effects . . . . . . . . . . . . . . . . . . . . . . . . . . . 51

5.1. Collision frequency derived from the first principles. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
5.2. Collision frequency assumed from the mathematical reasoning. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
5.3. Collision frequency for simultaneous Brownian and gravitational coagulation. . . . . . . . . . . . . . . . . . . . . . . . . . 53
5.4. Collision frequency for charged non-Brownian particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
5.5. Aggregates breakup frequency . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
6. Population balance equations and corresponding gravity effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
6.1. Smoluchowski solution for Brownian coagulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
6.2. Population balance equation with aggregates breakup. Analytical solution for chain aggregates with small fractal number. . . 58
6.3. Transition from Brownian to gravitational aggregation. Analytical solution . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
6.3.1. Analytical solution by A.S. Dukhin [38,39] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
6.3.2. Analytical solution by Jung et al. [40] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
6.3.3. Comparison of analytical solutions and the following conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
6.4. Transition from Brownian to gravitational aggregation. Numerical solution . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
7. Experimental techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
8. Experimental data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
8.1. Gravity influence on homo-coagulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
8.2. Gravity influence on fractal structures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
8.3. Gravity influence on hetero-coagulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
8.4. Gravity role in the wet classification of micron sized particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
9. Concluding remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
69

1. Introduction Gravity can play an important role on all three levels of

Gravity generates a multitude of effects that affect particle
interactions in heterogeneous systems and consequently influ-
ence the stability of these systems and their evolution in time.
There is no general solution that completely describes all of
these gravity effects. Instead, there are many fragments that
attempt to predict gravity-influenced behavior of a heteroge-
neous system on a particular level of the general DLVO
stability theory. It is well known that this general theory
contains three distinctively different but interlinked levels, as
described below.
Level 1 — Particle pair interaction The potential energy of the
interaction between two particles in a particular dispersion
media U(h) is expressed as function of the distance between
their surfaces h. In some cases, a simple comparison of
gravity related forces with surface forces leads to a prediction
of system stability without any need for a more complicated
analysis. However, Level 1 models by themselves are not
capable of describing the evolution of unstable dispersions.
For this we need to incorporate this potential energy function
in Levels 2 and 3.
Level 2 — Collision frequency At this level we employ the
energy U(h) to compute two frequencies related to the
interaction of aggregates, a collision frequency β and
breakup frequency δ. These two parameters then serve as
kernel functions used at the next level.
Level 3 — Population balance equation The solution of this
equation for a particular pair of collision and breakup
frequencies yields a particles size distribution, which,
importantly, is an experimentally measurable parameter.
analysis. There is no general solution that would consistently
describe gravity effects from one level to the next. There have
been many attempts to analyze the role of gravity on the
behavior of a heterogeneous system on a particular level.
However, there are only a few exceptions when authors describe
the role of gravity on more than one level. These omissions
make presentation of an overview of the role of gravity in
aggregative stability a quite challenging task, which has not
been completely resolved up to date.
The most extensive modern review of all aspects of
aggregative stability given by J. Lyklema [1] introduces a
notion of the “forced pair interaction” (Chapter 3 “Pair
interaction”). This term reflects in general the influence of
external fields, such as magnetic, electric and mechanic, on
aggregative stability. The next chapter (“Dynamics and
kinetics”), written by Minor and van Leeuwen [2], presents
particle–particle interaction in a hydrodynamic field (ortho-
kinetic coagulation) and deposition at filtration.
Gravitational coagulation occupies a very small place in this
most wide-ranging monograph [1].
There are some other monographs and reviews, focused on a
certain kind of ortho-kinetic coagulation. A deep analysis of
ortho-kinetic coagulation in shear flow is given in the well-
known monograph by van de Ven [3]. Application of DLVO
for non-Brownian particles to micro-flotation is described in
the monograph [4] and in the review [5]. There is a rather
complete description of the transport stage for gravitational
coagulation in the review by S. Dukhin and Sjoblom and
Dukhin et al. [6,7].
The best-known work on this subject seems to be review
written by Melik and Fogler [8]. Unfortunately, this review
 A.S. Dukhin et al. / Advances in Colloid and Interface Science 134–135 (2007) 35–71
does not present a complete description of our knowledge in
this field. There are many important works missing in that
review, which mentions only six papers as relevant to this
subject in the table on the first page. Many early works on the
collision efficiency calculations [9–16] are missing, in
addition to several more recent papers, including detailed
analysis for emulsions by Davis [17–23], and works for
fractals [24–28]. Analytical solutions for gravity role in pre-
venting aggregation in secondary and primary minima, as well
as acceleration of slow coagulation [29,30] are completely
missed. Early works on trajectory analysis for hetero-
coagulation and bubble–particle interaction [31–37] by
Derjaguin and S. Dukhin's group that contain many physical
insights in the problem are missing. Several analytical
solutions of the population balance equation [38–40],
including kinetics of chain aggregate formation with breakups
[41], are missing. The last one is important for understanding
fractal formation that can be strongly affected by gravity.
There are also several recent experimental works [42–45],
especially on fractals, which deserve discussion.
In addition, the review by Melik and Fogler is written in a
way that even their followers, such as [46], admitted problems
understanding some derivations.
There is a simple reason why it is so complicated to
combine the works on this subject. The scope of the scientific
fields is very broad. It involves general colloid science,
aerosols, flotation, waste water treatment, general physics,
emulsion science, nano-technology, and many other fields as
well. Consequently, the relevant papers are scattered over a
wide range of publications. Unfortunately, this leads to the
situation where scientists working in different fields have
limited knowledge about similar developments on other areas.
This might explain why some authors attribute certain basic
derivations to the wrong sources. For instance, Fuchs calculated
the critical particle size for the transition from Brownian to
gravitational coagulation forty years ago [12,16]. There have
been similar independent calculations in several papers with no
reference to Fuchs original paper or to each other. There is also a
controversy regarding the expression for the rectilinear collision
frequency. Many authors attribute it to Friedlander [47],
whereas it was actually given first many years earlier in the
1940's by Camp and Stein [9] based on Smoluchowski's theory
for ortho-kinetic coagulation [48].
The situation becomes even more complicated because some
of the relevant papers had been published in obscure journals
prior to the Internet era. For instance, the first analytical solution
regarding the transition from Brownian to gravitational
coagulation [38,39] remains practically unknown.
We want to bring together works from different fields and
establish what is unique for the particular field and what is
common for all of them.
We start with a short historical overview of the main
achievements in the field and then proceed to organize the
theoretical material using the three levels presentation described
above. After this we overview the experimental works and try to
connect them with various theoretical conclusions that might be
relevant for a particular experiment.
37
2. Historical overview
1917. Smoluchowski made the first attempt to estimate the
influence of the directed particles motion on the coagulation
kinetics [48].
1942. Tichomirov et al. — increase in rate of collision of
aerosol particles of equal diameter resulting from action of van
der Waals forces [49].
1943. Camp and Stein, extended Smoluchowski theory for
ortho-kinetic aggregation [9].
1948. Sutherland — first introduction of interception
hydrodynamic interaction induced by sedimentation into the
collision efficiency, assuming small particle size ratio [10].
1957. Melzak introduced population balance equation with
aggregates breakup [50].
1958. S. Dukhin and Derjaguin — correction of the Sutherland
theory by taking into account perturbation of the hydrodynamic
interaction due to the sedimentation of the smaller particles [13].
1960. Derjaguin and S. Dukhin — first mentioning of van
der Waals attraction as a factor that overcomes unlimited
increase of the thin film viscous resistance for hydro-soles [31].
1964. Fuchs — introduced a critical size of particles in
dispersion, above which gravitational aggregation dominates —
namely, 1 μm [12].
1964. Friedlander and Swift introduced a self-similarity
principle and extended it to peri-kinetic aggregation [51].
1973. Spielman and Fitzpatrick — numerical calculation of
the collision efficiency that takes into account van der Waals
forces and hydrodynamic interaction, assuming small particle
size ratio [52,53].
1973. Reay and Ratclif — experimental verification of the
Sutherland equation for collision efficiency due to interception
[14,15].
1973 – Spielman and Cukor – first stability diagram [54].
1977 – Derjaguin et al. – stability diagram for micro-
flotation [55].
1978. Rulyov — analytical calculation of the collision
efficiency that takes into account van der Waals forces and hydro-
dynamic interaction, assuming small particle size ratio [36,37].
1982. Mandelbrot introduced fractal model for flocs [24].
1984. Davis — numerical calculation of the collision
efficiency at any size ratio derived on the base of Jeffrey and
Onishi mobility function [19].
1985 – A. Dukhin – analytical solution for the gravity driven
pair particles interaction [29,30].
1985 – Melik and Fogler – numerical solution for the gravity
driven pair particle interaction [8].
1985. van Dongen and Ernst introduced a broad class of
collision frequencies that would give rise to a self-similar
solution [56].
1986. A. Dukhin — introduction of uniform zone during
sedimentation and analytical solution of population balance
equation (PBE) for transition from peri-kinetic to ortho-kinetic
aggregation using small Peclet number [38,39].
1988. Melik and Fogler — numerical solution of population
balance equation (PBE) for transition from peri-kinetic to ortho-
kinetic aggregation [8].
38 A.S. Dukhin et al. / Advances in Colloid and Interface Science 134–135 (2007) 35–71
1991. Wen et al. — analytical solution for large Peclet
number [57].
1991. Yiantsios and Davis — numerical theory of droplet–
droplet hydrodynamics interaction during gravitational coagu-
lation and proof of weak deformation in a mini-emulsion case,
the pimple prediction [18].
1993. Zinchenko and Davis — numerical calculation of the
collision efficiency for coupled gravity and Brownian effects,
and complete hydrodynamic interaction without additivity
assumption [21].
1996. Wang and Davis — numerical solution of population
balance equation (PBE) for combined peri- and ortho-kinetic
aggregation without additivity assumption PBE [22].
1997. Mishchuk et al. — observe deviation from the
Smoluchowski kinetics for the Brownian coagulation of
emulsions and attribute it to gravitational effects [58].
1998. Folkersma et al. — kinetic experiments at micro-
gravity conditions in space [59].
2000. Jung et al., the second analytical solution for transition
to gravitational coagulation [40].
2001. Mishchuk et al. — micro-flotation domain for bubbles
with retarded and mobile surfaces [60].
2001. Y. Chang and M. Ku, numerical theory for gravity
driven pair interaction of charged particles, methodology for
creating stability diagram [46].
2003–2005. A group from Swiss Federal Institute of
Technology in Zurich performs sophisticated kinetic experi-
ments with fractal aggregates and proves experimentally the
importance of gravity effects [42,43].
3. Parameterization of heterogeneous systems
Real heterogeneous systems, by their very nature, are quite
complex. Two of these complexities are the variation of particle
size and shape within a particular dispersion. Furthermore, the
particles might not even be separate, but linked together to form
some network, or the liquid might contain complex additives. This
inherent complexity makes it difficult, perhaps impossible, to fully
characterize a real colloidal system except in the most simple cases.
However, we do not always need a complete detailed character-
ization; a somewhat simplified picture can often be sufficient for a
given particular purpose. There are two approaches to obtaining a
simplified picture of any real system under investigation.
The first approach is “phenomenological”, in that it relates
only experimentally measured variables, and usually is based
on simple thermodynamic principles. This can be a very
powerful approach, but, typically, it does not yield very much
insight concerning any underlying structure within the system.
The second approach is “modeling”, in which we replace the
practical system with some approximation based on an imaginary
“model system”. This model system is an attempt to describe a
real colloid in terms of a set of simplified model parameters
including, of course, the characteristics which we hope to
determine. The model, in effect, makes a set of assumptions about
the real world in order to reduce the complexity of the
heterogeneous system, and thereby also simplifies the task of
developing a suitable prediction theory.
The first step of the modeling real heterogeneous system for
characterizing aggregative stability is introduction of “disper-
sion medium” and a “dispersed phase”. Dispersion medium is a
continuous phase, which might be liquid or gas. There are
several properties of the dispersion medium that could be
introduced for modeling particular real heterogeneous systems
or phenomenon. In the case of the aggregative stability problem,
dispersion medium is usually assumed to be a Newtonian liquid
[61] with certain dynamic viscosity ηm and density ρm. There is
also a set of parameters that could be important for
electrokinetics or surface forces. However, these two para-
meters are sufficient for describing the dispersion medium in
aggregation kinetic.
Dispersed phase is a collection of separate finite particles in
the dispersion medium. Any model for the dispersed phase
particles must describe the properties of a single primary
particle: its shape, physical and chemical properties, etc.
Colloidal particles are generally irregular in shape, which
makes modeling a rather difficult task. Fortunately, there is one
factor that helps — Brownian motion. All colloidal particles
experience Brownian motion that constantly changes their
position. A natural averaging occurs over time; the resulting
time averaged particle looks like a sphere with a certain
“equivalent diameter”, d, or “equivalent radius”, a, or
“equivalent volume” v. It is for this reason that a sphere is the
most widely and successfully used model for particle shape.
There is a special parameter for characterizing the intensity
of the Brownian motion of the particle with diameter d —
diffusion coefficient D. There is a simple relationship between
these parameters given by the Stokes–Einstein theory of
Brownian motion [61]:
kT
D¼ ð3:1Þ
3p dgm
where k is the Boltzmann constant, and T is the temperature.
Obviously a spherical model does not work well for very
asymmetric particles. Here an ellipsoid model can yield more
useful results [61]. This adds another geometrical property: an
aspect ratio, the ratio of the longest dimension to the shortest
dimension. For such asymmetric particles the orientation also
becomes important, bringing yet further complexity to the problem.
Density of the single primary particle ρp is sufficient for
characterizing dispersed phase material for the purpose of the
kinetic theory.
The model must also reflect any possible polydispersity, i.e.
the variation in properties from one particle to another. Usually
this term assumes variation of the particle size, assuming other
properties identical for all particles. This model is applicable,
for instance, to emulsions, even unstable but with fast coa-
lescence. Another important example is dispersions with
different sizes of the primary particles. This difference can be
a result of grinding, or variation at their synthesis.
Polydispersity of size can be also a result of primary particles
aggregation.
Aggregation occurs due to particles collisions induced either
by Brownian motion, or by gravity, or both. Interaction of two
 A.S. Dukhin et al. / Advances in Colloid and Interface Science 134–135 (2007) 35–71
particles in a course of their collision is a very complex process.
It might lead, or might not, to a creation of an aggregate. This
outcome depends on a variety of factors, such as surface forces,
gravity, hydrodynamic particles interaction, etc. From the
viewpoint of aggregation kinetics theory all these factors are
combined in one parameter — “collision frequency” β.
There is also a possibility of the process that would be
reverse to the aggregation — breakup of aggregates. There is
also a certain probability of this process E that reflects a
combined effect of various forces that affect interaction of
primary particles in the aggregate. Sometimes it is convenient to
associate this probability δ with a single bond as a probability of
the cleavage of the bond.
In the case of polydispersity induced by particles interaction
we must be more careful with the assumption that physical
properties are identical for all particles. It can be still valid for
compact aggregates, but it clearly does not work for weak flocs
that contain a substantial amount of the trapped dispersion
medium. It turns out that this polydispersity of the aggregates
physical properties can be described with the “fractal model”,
which reduces it to the function of the particle size with one or
several additional parameters.
For instance, the size of the fractal aggregate with the
number of primary particles i can be presented [62,63] as a
function of only two parameters kf and df:
1 1=df
ai ¼ a1 ði Þ ð3:2Þ
kf
where df is the fractal dimension. This number changes from
roughly 1 to 3. It equals 3 to coalescing emulsion droplets, 2.05
for reaction limited aggregation and 1.85 or less for diffusion
limited flocculation. Number kf is close to 1 [47].
Consequently, the density of the aggregates does not equal
any longer to the density of the primary particles. Variation of
the density with growing aggregate size can be taken into
account using expression (3.2).
Polydispersity of the particle size, including aggregates, is
certainly the most important feature of the heterogeneous
systems. In order to characterize this polydispersity we use the
well-known conception of the “particle size distribution” (PSD).
There are multiple ways to represent the PSD depending on the
physical principles and properties used to determine the particle
size. For the purpose of the aggregation kinetic theory, PSD on
the volume basis is the most widely used. It can be either
discrete or continuous. It is normalized.
The main purpose of the aggregation kinetic theory is the
description of how the function φ(v) evolves in time. There are
equations that determine this evolution for particular systems.
These are the so-called “population balance equations” (PBE).
4. Pair particles interaction. Corresponding gravity effects
There are a number of papers, which consider the balance of the
forces induced by gravity with surface forces. In some cases this
simple analysis allows us to derive a final conclusion regarding
aggregative stability of the particular system. For instance, gravity
39
induced forces can be stronger than attraction forces that keep
particles together in the secondary DLVO minima. This would
prevent flocculation in the secondary minima and the system
would remain stable. In cases like this, there would be no need of
performing complicated calculations of the “collision frequency”
and solving the “population balance equation”. That is why we
make a very distinctive difference between the pair particles
interaction and collision frequency in this review.
Derjaguin was the first one who mentioned the necessity of
using forces instead of potential energy for describing the
interaction of large non-Brownian particles when gravity
becomes important [64–66].
Many years later Spielman and Cukor [54] introduced a very
convenient way of describing gravity role in the stability of
heterogeneous systems — “stability diagram”. It is two-
dimensional plot with certain dimensionless numbers on its
axis. Different domains of this plot represent various effects that
gravity induces in the colloids based on the analysis of the pair
particles interaction.
This work employs one very strong limitation. It assumes
that particles sizes in the pair are very different. This clearly
restricts applicability of this work to real systems tremendously.
The following developments eliminated this restriction. There
are two different approaches used for achieving this goal.
The most known begins with the work by Melik and Fogler
[8] and then continued in the work of Chang and Ku [46]. These
scientists applied sophisticated expressions for all forces
involved in the pair particles interaction in the gravity field as
known. Consequently they are able to resolve equations only
numerically. The output of these works is a numerical “stability
diagram” for several particular combinations of system
parameters and procedure for deriving such diagram for any
systems. We present this procedure below.
Another approach was chosen in the papers [29,30]. Instead of
using the most general expressions for molecular and hydrody-
namic forces, the author of this paper decided to use much simpler
asymptotical solutions. There is justification for this based first of
all on controversy regarding calculating “retardation” of molec-
ular forces. We present a detailed discussion on this account
below in the section dedicated to the molecular forces.
In addition, there are large uncertainties in the input
parameters, such as Hamaker constant, electric surface potential.
These two arguments bring us to the conclusion that
application of complicated theories might lead to exceeding
the precision limit.
On the other hand simpler asymptotical expressions for
interaction forces allowed achieving an analytical solution for
describing the role of gravity in the pair particles interaction.
This work has been published in an obscure journal almost at
the same time as review [8].
In this section we start with a short overview of surface
forces and particles hydrodynamic interaction.
Then we present an original “stability diagram” by Spielman
and Cukor [54].
Then we present analytical solutions. These ones are available
for preventing aggregation in secondary minima and accelerating
slow coagulation.
40 A.S. Dukhin et al. / Advances in Colloid and Interface Science 134–135 (2007) 35–71
After this we describe the main points of the numerical solutions
and procedure for deriving “stability diagram” for any system.
In the last section we present results on hetero-coagulation.
The most important example here is micro-flotation, which is
bubble–particle interaction. There are a number of papers
published many years ago on this subject by B. Derjaguin,
S. Dukhin and N. Rulyov [31–37]. They unrevealed many aspects
of the gravity influence on pair interaction at that time. Un-
fortunately these works were also not well known on this field.
4.1. DLVO surface forces for non-Brownian particles
There are two different ways of describing pair particles
surface interaction, either in terms of interaction potential
energy or in terms of interaction forces. Potential energy is the
more known term for describing surface interaction and it is
presented in all major monographs on Colloid and Surface
Science. Description of the surface interaction in terms of the
forces is more obscure. It is presented in the Derjaguin
monograph [66] and his review [5] as well as the Melik and
Fogler review [8].
The difference between these two ways of describing surface
interactions is related to the mechanism that determines relative
particles motion. In the case of the small Brownian particles
their surface interaction must be described by the means of the
potential energy. In the opposite case of the relatively large non-
Brownian particles the terms of surface forces are more
adequate. This difference had been formulated by Derjaguin
[64–66], who derived a coagulation criterion for non-Brownian
particles. It differs qualitatively from the traditional coagulation
criterion of rapid Brownian coagulation. Instead of the notion of
the electrostatic energy barrier it employs the electrostatic force
barrier. Fig. 1 illustrates the relationship between the energy
barrier and the force barrier for the more general case when two
minima (primary and secondary) exist.
Comparison of the surface interaction with the gravity
induced effects requires presentation of the surface interaction
in terms of forces, not potential energy, as it was stated many
years ago by Derjaguin [64–66].
We consider two different surface forces: electrostatic and
molecular.
4.1.1. Electrostatic surface force
With regard to the electrostatic surface force, Derjaguin
emphasized [67,68] the significance of formulating DLVO theory
for non-Brownian particles while taking into account a possible
difference of the particle sizes as well as their electric potentials.
The convenient equation for the electrostatic interaction force Fe
was derived initially by Derjaguin [67,68] and later by Hogg et al.
[69]. This case of not very high potentials is known in the literature
as the HHF approximation. It yields the following expression for
the interaction force as a derivative of the potential energy of
interaction between the two dissimilar spherical colloidal particles:
Fe ¼ Kem e0 j½ðw2i þ w2j Þ‘2jh þ 2wi wj ‘jk =ð1  ‘2jh Þ
ð4:1Þ
where h is the distance between particles surfaces, κ is the Debye
parameter, ψi and ψj are dimensionless potentials. Parameter
2pai a
K¼ takes into account the spherical shape and sizes of the
1þa
interacting particles ai and aj respectively according to the
a
Derjaguin approximation [70,61,66], where a ¼ j ; ai zaj .
ai
HHF approximation can be used for a not too large potential,
but possibly above 25 mV. Calculation performed in papers
[71–73] indicates that the error of the HHF theory does not
exceed 10% even for a potential equal to 50 and 74 mV.
Accuracy of the HHF approximation improves with an
increasing difference between particles surface potentials.
This makes it even more attractive for describing hetero-
coagulation.
One of the most peculiar features of hetero-coagulation is
existence of the zone where electrostatic interaction leads to the
attraction of the particles. This occurs at small distances
between particle surfaces when
w2i þ w2j
h b h⁎ ¼ j1 ln ð4:2Þ
2wi wj
In the case of identical particles, when ψ ι = ψ φ = ψ,
electrostatic interaction causes only particles repulsion. Eq.
(4.1) reduces to the well-known equation for the electrostatic
repulsion for homo-coagulation
Fe ¼ Kem e0 jw2 =ð1 þ ‘jh Þ ð4:3Þ
The simplicity of Eqs. (4.1) and (4.3) is the consequence of
the Derjaguin approximation [70,61,66], which is valid only for
thin double layer comparing to the particle size. This may be a
serious limitation for Brownian particles, but not for larger
particles that are the subject of this section.
Fig. 1. Illustrative plots for dependences of the total energy Vint and
corresponding total force Fe + Fm on the shortest distance h between the
surfaces of two spherical particles.
 A.S. Dukhin et al. / Advances in Colloid and Interface Science 134–135 (2007) 35–71
4.1.2. Molecular surface forces
With regard to the molecular van der Waals forces a different
approximation can be used separately for the primary and for
the secondary minimums.
A sufficiently large attractive electrostatic force exists at
rather small distance below 3 nm. At these distances
electromagnetic retardation and screening of the molecular
forces are always insignificant. These factors are negligible for
calculation of the force barrier amplitude as well because the
electrostatic force dominates in that region and potential error in
calculating molecular forces is not very important. Thus, for
describing primary minima and force barrier we can use the
simplest expression for the molecular forces [61,66]:
KA
Fm ¼  ð4:4Þ
12p h2
This simplest expression is not valid for describing the
secondary minimum. It positions at the distances that
substantially exceed the Debye length. Accordingly, this
distance is in the range 20 to 50 nm for typical electrolyte
concentration. It is important to take into account retardation
effect at these large distances [61]. There is a simple analytical
expression for completely retarded molecular forces [61]:
2pBaj a
Fm ¼  ð4:5Þ
3h3 ð1 þ aÞ
The characteristic values of the completely retarding forces
Hamaker constant B lie in the range from 10− 27 to 10− 30 J m.
There is an algorithm for calculating constant B from the values
of constant A presented in the book of Lyklema [61], namely
Eq. (4.6.37).
A situation with transitional region from non-retarded forces to
completely retarded forces is complicated. The most detail
overview of the Colloid and Interface Science — [61] makes a
statement that: “For the transition region between non-retarded
and retarded interaction no analytical expressions are available”.
We would like to comment also on uncertainty with input
parameters for calculating surface forces. In particular, our
estimates of the Hamaker constant are very approximate. There
is clearly uncertainty in the values of the surface potential.
Keeping in mind these uncertainties and above-mentioned
opinions, we should be very cautious with regard to exceeding
precision limits in our calculations. That is why we think that
application of the simple expression for completely retarded
molecular forces for calculating secondary minima is justified.
Other, more detail analytical expressions for partially retarded
molecular forces might lead to exceeding possible precision
limited by uncertainties in theory and input parameters.
The derivative of the total force Fe + Fm in the position of the
secondary minima equals to zero. After combining Eqs. (4.3) and
(4.5) and after derivation, one obtains the following equation
2pj2 B
ðjhmin Þ4 ejh ¼ ð4:6Þ
W2 e
where hmin is the larger of the two possible positive roots of this
equation.
41
Detail analysis performed in paper [89] indicates that this
type of equations does not have solutions always. Right hand
side of Eq. (4.6) might be so large that neither potential barrier
nor secondary minimum exists. Unfortunately we cannot be
absolutely sure that Eq. (4.6) describes transition to this state
correctly. This equation describes molecular retardation as fully
developed. Consequently, it is possible that Eq. (4.6) would
predict no potential barrier and secondary minimum when they
would exist in reality. It is hard to estimate how large this
uncertainty range is. Only numerical calculation would allow
determining its scope.
4.2. Gravity induced pair interaction forces
There are three different forces that gravity exerts on
particles in liquid. Gravity force by itself is the first one:
4
Fg ¼  pgqp a3 ð4:7Þ
3
where g is an acceleration of the earth gravity.
Buoyant force is the second one:
4
Fb ¼  pgqm a3 ð4:8Þ
3
The force of hydrodynamic resistance Fh generated by the
particles sedimentation motion relative to the liquid is the third
one. In the case of isolated particles this force is given by the
Stokes law [61]
Fhisolated ¼ 6pgm auisolated ð4:9Þ
s
where ηm is dynamic viscosity, us is sedimentation velocity.
From these three forces only the hydrodynamic resistance
force is affected by other approaching particles. These other
particles change hydrodynamic flow around the given particles
and this affects the hydrodynamic force that liquid exerts on this
given particle. There are several different approaches for an
approximate description of the hydrodynamic resistance of the
particles pair.
Initially, theoretical development applied simplification by
considering only particles with very different sizes. This
assumption yields a small parameter (particle size ratio),
which can be used for simplifying mathematics. Historically,
these first efforts had been made on aerosols and, especially,
micro-flotation. Gravitational effects are most pronounced in
the bubble–particle interaction (flotation) due to the large
density contrast. Many of these results are easily extended to
liquid based dispersions and emulsions. For instance, a bubble
with the surface retarded by a surfactant is identical to a solid
particle from the hydrodynamic viewpoint.
Sedimentation of the large particle creates a liquid flow
around it. This liquid flow does not affect much other large
particles, which would move almost linearly due to inertia
(Fig. 2, line 1). At the same time fairly small particles move
essentially along the corresponding liquid flow lines (Fig. 2,
line 2). The long-range hydrodynamic interaction causes this
deviation in the trajectory of small particles. It affects trajectory
42 A.S. Dukhin et al. / Advances in Colloid and Interface Science 134–135 (2007) 35–71
Fig. 2. Influence of the particles inertia on the trajectory of their relative motion.
Trajectories of the large (inertial) (line 1) and the small (inertial-free) particles at
the same target distance b.
when the distance to the surface of larger particles is comparable
with its size.
Before two particles collide during differential settling the
smaller particle is located below the larger one (Fig. 3). A
hydrodynamic flow formed around a large particle affects the
approach of a smaller particle to it. In the area below the
equatorial plane of larger particles lines of liquid flow approach
its surface, which means that the radial component of the liquid
velocity is directed towards the larger particle (Fig. 3). This
causes pressing hydrodynamic force (PHF) [74]. While for
Brownian particles the diffusion promotes the particle penetra-
tion through the electrostatic barrier, the gravity and PHF may
play a similar role for non-Brownian particles.
Fig. 3. Illustration to mechanism of pressing hydrodynamic force (PHF).
Above the equatorial plane, lines of liquid flow depart from
the surface of large particles. In the case of the Stokes flow there
is anti-symmetry flow lines
urs ðp  hÞ ¼ urs ðhÞ ð4:10Þ
where θ = 0 corresponds to the front pole of the sedimenting
particle, rising bubble or droplet.
The outward component of liquid flow promotes the small
particle detachment similar to that in which the inward
component promotes the PHF and attachment.
This deviation of the particles trajectories from the linear
path causes change in the collision frequency. It will be an
important factor in the next section that is devoted to the
probability of aggregates formation and breakup.
There is a critical target distance bcr. At b b bcr the particles
accumulate on the collector surface. At b N bcr the particles are
carried off by the flow. It is evident, that the calculation of
collision frequency is essentially reduced to the so-called
“limiting (grazing) trajectory” (continuous curve in Fig. 4).
Further theoretical analysis showed that long-range hydrody-
namic interaction becomes not adequate when the distance be-
tween two approaching particles diminishes. The hydrodynamic
interaction at distances comparable to the size of the smaller
particle is called the short-range hydrodynamic interaction [5,4].
It is in the equatorial plane that the closest approach of a
streamline to the surface of a larger particle is attained. In Fig. 5,
the broken line (curve 1) represents the liquid streamline, whose
distance from the surface of larger particle in the equatorial
plane is equal to the radius of the smaller particle. Under the
influence of the short-range hydrodynamic interaction, the
smaller particle is displaced from liquid streamline 1 so that its
trajectory (curve 2) in the equatorial plane is shifted from the
Fig. 4. Continuous line illustrates the concept of limiting trajectory of particles.
Dashed lines indicate trajectories at b b bcr and b N bcr.
 A.S. Dukhin et al. / Advances in Colloid and Interface Science 134–135 (2007) 35–71 43

papers can be used for calculating hydrodynamic resistance

force acting on each particle in the aggregate.
This calculation depends on the orientation of the pair
particle aggregate. An aggregate consisting of two spheres with
radii ai and aj is classified as an “upright” body from the
viewpoint of hydrodynamics. It was shown in monograph [77]
that the line connecting the centers is parallel to the acceleration
of free fall at the stable orientation of the sedimenting upright
body. The larger sphere with radius ai is located beneath the
smaller sphere with radius aj if

ðqi  qm Þa2i  ðqj  qm Þa2j N 0 ð4:11Þ

Otherwise the smaller particle is located beneath the larger one.

For example, in the case of flotation, when the bubble radius
exceeds the radius of ascending particles and ρi b ρm, and the
particles are thus located beneath the bubbles.
A similar arrangement of the smaller beneath the larger
particles may be observed in the system with a uniform
dispersed phase. If, for instance, the density of the smaller
particles exceeds the density of the larger particles, the smaller
particles will be located beneath the larger particles when
rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
aj qj  qm
Fig. 5. The influence of the finite dimension of particles on their trajectory in the a¼ N ð4:12Þ
vicinity of the larger settling particle. The liquid flow lines corresponding to ai qi  qm
target distances b(a) and bcr are indicated by dashed lines. The continuous lines
are characteristics of the deviation of the trajectory of particles from the liquid If the densities of the particles are equal and exceed the
flow lines under the influence of the short-range hydrodynamic interaction.
density of the liquid, the smaller particles are located above the
large ones at the stable orientation of the aggregate. For this case
surface by a separation larger than its radius. Therefore, no the Stimson–Jeffery solution yields the following expressions
contact with the surface occurs. Correspondingly, b(a1) is not a for the hydrodynamic resistance force acting on each particle in
critical target distance, where b is a distance between small the aggregate:
particles and the center line of the larger particle sedimentation.
Due to the short-range hydrodynamic interaction, the Fhj ¼ 6pgaj us kðaÞc6pgaj us ⁎0:645a ð4:13Þ
distance from the smaller particle to the surface in the equatorial
plane is larger than the distance from the surface to the liquid Fhi ¼ 6pgai us kð1=aÞc6pgaj us ⁎ð1  0:355aÞ ð4:14Þ
streamline with which the trajectory of the smaller particle
coincides at large distances from the bigger particle. It may thus Exact expression for the function λ(α) is very cumbersome.
be concluded that bcr b b(a1). The limiting liquid streamline We use here an asymptotic of this general expression when
(curve 3) is characterized by the particle trajectory (curve 4), particles sizes are not very different, Fig. 6. There is another
which branching off under the influence of the short-range
hydrodynamic interaction, runs in the equatorial plane at a
distance a1 from the surface of the bigger particle.
The value of bcr decreases, first, due to the deflection of the
liquid streamline under the influence of the long-range
hydrodynamic interaction and, second, due to the deflection
of the small drop trajectory from the liquid streamline under the
influence of the short-range hydrodynamic interaction.
Further development of the theory pursued a goal of
removing restriction of the small sizes ratio. If the difference
between particle sizes is not large, the description of their
interaction requires different parameterization. The motion of
two interacting particles is a superposition of the mass center
motion and their relative motion in the frame of references that
is associated with the mass center. When the spheres are very
close, the mobility functions have the asymptotic forms given
by Stimson and Jeffery [75] or Jefferey and Onishi [76]. These Fig. 6. Correction factor λ for Stokes law [75].
44 A.S. Dukhin et al. / Advances in Colloid and Interface Science 134–135 (2007) 35–71

asymptotic solution for the other case of the very different The primary coagulation occurs at a sufficiently low ψ
particle sizes and very small parameter α: potential, when the electrostatic barrier is not high. It
corresponds to low values of the repulsive number NR, and is
kðaÞc4:84a2 ð4:15Þ graphically presented as a domain on the left hand side of Fig. 7.
Increasing ψ and NR lead to a growing electrostatic barrier.
In order to finalize calculation of hydrodynamic resistance
This prevents coagulation in primary minimum, but opens two
forces acting on particles in sedimenting aggregate we must
other alternatives.
specify the unknown sedimentation velocity of aggregate us.
The first one is a secondary coagulation, which is possible at
We can determine it by setting the total bulk force acting on the
high value of the repulsive number. This corresponds to the
aggregate equal to zero, i.e.,
domain on the right hand side top corner of the stability diagram
on Fig. 7.
Fgi þ Fgj  Fai  Faj  Fhi  Fhj
The second alternative at high repulsive number is the
4 absence of coagulation at all. This situation of the stable system
¼ pDqgða3i þ a3j Þ  6pgm us ½ai kðaÞ þ aj kð1=aÞ ¼ 0
3 corresponds to the third domain in the right hand side bottom
ð4:16Þ corner of Fig. 7.
However, there is also the third alternative that is ignored in
This yields the following expression for the aggregate the stability diagrams method. The depth of the secondary
sedimentation velocity: potential minimum decreases with increasing repulsive number.
Consequently, the lifetime of the aggregate formed in the
2Dqga2j ða2 þ 1Þ secondary minimum decays. At some point this secondary
us ¼ ð4:17Þ
9g½akðaÞ þ kð1=aÞ coagulation becomes so weak that it does not affect stability of
the system. Incorporation of this third possibility into the
Eqs. (4.13)–(4.14) make it possible to calculate the forces stability diagram would require substantial revision of the
acting on the particles of an aggregate under steady sedimen- theory following the lines presented below in the Aggregates
tation conditions. breakup frequency section.
Attraction number NA determines which alternative is valid
4.3. Classification of the gravitational coagulation modes. for the particular system. At a fixed NR′ i.e. at invariant ψ, A and
Stability diagram κ, the increase in NA(κa)2 corresponds to the decreasing a, i.e.
to the decreasing sedimentation velocity. The coagulation in the
Spielman and Cukor [54] were the first ones to specify secondary minimum results from a flow too weak to carry the
different types of the gravitational coagulation. They introduced droplet through the secondary minimum. It corresponds to high
the so-called “stability diagram”, which is a graphical values of attractive numbers and to the domain in the right hand
representation of four different types of phenomena induced side top corner of Fig. 7.
by gravity. They introduced two special dimensionless criteria
in order to characterize the relative role of the attractive and the
repulsive forces as well as gravity. The ratio between the
electrostatic repulsive force and molecular attractive force is
characterized by the repulsion number NR
3em e0 w2 a
NR ¼ ð4:18Þ
2A
The attraction number NA reflects the ratio of the attractive
van der Waals force to the hydrodynamic drag force:
A A
NA ¼ ¼ ð4:19Þ
9pgm a us 2pgDqa4
2

where us is the sedimentation velocity expressed according to

Stokes equation.
There are also two modifications of these numbers, which
are used in the preparation of the stability diagram:

NR 3em e0 w2 a
NRV¼ ¼ ð4:20Þ
ja 2Aj
Aj2
NA1 ¼ NA ðjaÞ2 ¼ ð4:21Þ
2pgDqa2
Fig. 7. Stability diagram showing the influence of electrostatic repulsion at
Fig. 7 illustrates the stability diagram. constant potential according to Spielman and Cukor [54].
 A.S. Dukhin et al. / Advances in Colloid and Interface Science 134–135 (2007) 35–71
A similar analysis explains the slope of the boundary
between the “primary coagulation domain” and “stability
domain”. At a fixed NR′ i.e. at invariant ψ, A and κ, the increase
in NA corresponds to decreasing a, i.e. to the decreasing PHF.
Accordingly, the coagulation at primary minima can occur at
smaller ψ with decreasing a (increasing NA(κa)2). It means the
decrease in NR′ along the boundary, i.e. the decrease in its
distance to the ordinate axis with increasing NA(κa)2.
Decreasing NR′ along the border between “secondary
coagulation domain” and “stability domain” explains the slope
of this border. Decreasing NR′ leads to the increasing role of the
attractive force in the vicinity of the secondary minima. With
the increasing attraction, the coagulation at larger sedimentation
velocity (larger particle dimension) becomes possible. This
corresponds to the decreasing NA(κa)2 along the boundary in
the direction of decreasing NR′.
Spielman and Cukor [54] derived the first stability diagram
assuming a very large difference between interacting particles
sizes. It is valid only for small α. This clearly restricts
applicability of this work for real systems. Interpretation of
real experimental data required removing limitation of small α.
There have been two directions for these further developments
[8,29,30].
Historically the first steps in both of them have been done in
approximately the same time 1983–84.
Both directions simply applied more general theoretical
hydrodynamics for describing sedimentation of the pair
interacting particles. These were solutions by Stimson and
Jeffery [75] and by Jefferey and Onishi [76].
The main difference was in describing molecular forces.
There were two choices.
One choice was using a simple asymptotic solution for
molecular forces, which would allow building an analytical
theory.
The other one was using a more complicated version of the
molecular forces theory, which it turn would allow only
numerical solution for gravity coagulation.
The first choice was selected in the works of Bochko et al.
and Dukhin [29,30]. This work is the basis for the next two
sections.
The second choice was selected by Melik and Fogler [8] and
then developed even further in works [46,78]. The main results
are presented in the section below.
4.4. Analytical solution. Stabilization against secondary
minima coagulation
There are analytical solutions for taking into account gravity
effect for describing coagulation in secondary minimum and
acceleration of the slow coagulation [30]. Analytical solutions
are possible due to simplification of the molecular forces
presentation, as has been discussed above. In this section, we
present the main results of these analytical calculations for the
secondary minimum coagulation. The next section presents an
analytical description of the gravity role in slow coagulation.
DLVO theory predicts possibility of the coagulation in the
secondary minimum that appears on the potential energy curve
45
at certain combinations of the electric surface charge and
Hamaker constant. However, experiment does not confirm this
prediction in many cases, which was established by Kruyt [79]
as an experimental fact, although he provided no explanation for
the phenomenon. What is the reason of this discrepancy
between DLVO theory and experiment?
According to the DLVO theory, the electric surface charge
increase leads to the increasing repulsive electrostatic energy.
This might prevent coagulation in the primary minimum.
However, this factor is not sufficient for preventing coagulation
in the secondary minimum.
Incorporation of the gravity in the stability theory allows us
to resolve this problem.
The larger the particle, the deeper is the secondary mini-
mum and the larger the gravity force. Gravity force increases
with increasing particle size faster than the depth of the
secondary force minimum. Therefore, coagulation of rather
large particles in the secondary minimum is impossible, when
the gravity force exceeds the depth of secondary surface force
minima. Although the long-range coagulation is considered in
DLVO, it was not emphasized that the gravitational force
plays a major role with respect to the suppression of secon-
dary minimum coagulation in comparison with the electro-
static repulsion.
While the role of the gravitational fragmentation predomi-
nates with respect to the suppression of secondary minimum
coagulation, the electrostatic repulsion continues to be signif-
icant for the suppression of the primary minimum coagulation
for coarse particles as well. In other words, gravity alone and the
electrostatic repulsion alone are not sufficient for coarse
suspension stabilization. The coarse suspension stabilization
may be achieved, when simultaneously gravity prevents
Fig. 8. Five stages of temporary doublet fragmentation. Force balance is shown
in stage 4 at the moment before the fragmentation of the doublet occurs.
46 A.S. Dukhin et al. / Advances in Colloid and Interface Science 134–135 (2007) 35–71
coagulation in secondary minima and electrostatic repulsion
prevents coagulation in primary minima.
We restrict the analysis with the conditions of small
Reynolds and Stokes numbers. Let us consider the moment
right after two particles collision occurs, Fig. 8. The larger
particle is above the smaller one because it has been settling
faster. Due to differential settling, the doublet rotates and
approaches a stable vertical orientation with the larger particle
situated below the smaller one [77]. We assume here that
particles density is larger than the liquid density.
Restricting the aggregate position to the stable orientation
only, we can calculate the total detachment force that is
induced by gravity on the small particle. This detachment
force Fdet equals to the sum of the hydrodynamic drag force,
gravity and buoyant forces. We can use the exact solution of
Stimson and Jeffery [75] of the problem of the viscous flow
around two spheres for calculating the hydrodynamic drag
force Fh acting on the smaller particle of the aggregate, Eqs.
(4.9) and (4.17). Combining it with expressions for other two
forces (Eqs. (4.7) and (4.8)) we obtain the following
expression for the total gravity induced detachment force
4p kðaÞ  a2 kð1=aÞ
Fdet ¼ Fg þ Fa þ Fh ¼ d ðq  qÞga2j ai
3 a2 kðaÞ þ akð1=aÞ d
It is greater than zero for the entire range of the parameter α
values (from 0 to 1). At the end of the range, i.e. when α = 1, the
total detachment force acting on the particles is equal to zero.
This gravity induced detachment force acts as a stabilizer,
which breaks up the secondary minimum aggregates. It acts
against the total surface force that reaches its maximum in the
secondary minima hmin. Hence, the critical condition for the
temporary doublet fragmentation is:
jFdet jh¼hmin ¼ jFe þ Fm jh¼hmin
This condition becomes valid when the detaching particle
radius exceeds a certain critical value ajcr_2. We can derive a
simple analytical expression for this parameter by neglecting the
electrostatic force at rather large distances between particles that
correspond to the secondary minimum. This has been done in
the work of Dukhin [30] that gives the following expression for
the critical particle size:
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
B
j ¼
acr2 UðaÞ
2Dqgðhmin Þ2
where function Φ
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
að0:645a2  0:355a þ 1Þ
UðaÞ ¼
ð1 þ aÞð0:645  a þ 0:355a2 Þ
The function Φ(α) plot is presented in Fig. 9. The dashed
portion of the plot corresponds to a region where underlying
assumptions are not valid.
Introduction of the critical particle size that determines range
of the gravity importance is an alternative to the “stability
diagram”. The last one operates with a set of dimensionless
parameters. In some sense the notion of the critical particle size
is easier to interpret and to use than complicated dimensionless
numbers.
4.5. Analytical solution. Acceleration of slow coagulation
As we have already noted above, when the orientation of an
aggregate is stable, the hydrodynamic sedimentation interaction
promotes only detachment of the aggregates, i.e. it is a
stabilizing factor.
In the opposite case, when the orientation of the aggregate is
unstable (see Fig. 8) it can accelerate the coagulation processes
by helping to overcome the potential barrier of the surface
forces. This would occur when the larger particle overtakes the
smaller one during sedimentation. In this case, the aggregate
would be oriented in the reverse direction in comparison to that
previously considered. Consequently, the hydrodynamic sedi-
mentation interaction would press the smaller particle against
the larger, i.e. it decreases the height of the surface forces
potential barrier.
The critical condition for the penetration through the
ð4:22Þ electrostatic barrier due to gravity has the same form as in the
case of the particle escaping from the secondary minima,
namely Eq. (4.23). However, the surface force Fe + Fm has to be
calculated for the location of the force barrier hmax instead of the
secondary minimum. This leads to the following equation for
calculating a critical particle size ajcr_barr
4p kðaÞ  a2 kð1=aÞ
Fe ðhmax Þ þ Fm ðhmax Þ ¼ Dqga2j ai ð4:26Þ
3 a2 kðaÞ þ akð1=aÞ
ð4:23Þ where hmax is the barrier distance to the surface.
At typical electrolyte concentrations the molecular forces can
be calculated without taking into account their retardation, i.e.
ð4:24Þ
ð4:25Þ
Fig. 9. Approximate plot of the function Φ(α).
 A.S. Dukhin et al. / Advances in Colloid and Interface Science 134–135 (2007) 35–71 47

with the use of Eq. (4.4). This leads to the following expression dimensionless numbers, their nominations and titles sometimes
of the total surface force: are the same in both papers. However, there is an additional
  multiplier in the equations for those dimensionless numbers,
em e0 w2 j A ai a which is required for generalization over any values of α.
Fs ¼ Fe þ Fm ¼  ð4:27Þ
1 þ ejh 6h2 1 þ a The dimensionless electrostatic repulsive number is intro-
duced in [8] as
After the derivation applied to both sides of this equation one
obtains the following equation for the determination of the em e0 w2 ðai þ aj Þ
location of the force maximum hmax NR ¼ ð4:31Þ
2A

ðjhÞ3 ejh Aj The dimensionless van der Waals attraction numbers are
¼ ð4:28Þ
ð1 þ ekh Þ2 3em e0 w2 introduced in [8] in another form

The value of κhmax is given by the smaller of the two positive 2A a

NA ¼ d ð4:32Þ
roots of this equation. kT ð1 þ aÞ2
Now the critical condition for the penetration through the
electrostatic barrier can be specified as: The dimensionless functions for the attractive force
!
e0 em w j 2
A a2 a kðaÞ  a kð1=aÞ 2
 ¼ 4p 2 Dqga21 a2 2kT ð1 þ aÞ2 AUm
1 þ expðjhmax Þ 6ðhmax Þ2 1 þ a a kðaÞ þ akð1=aÞ fA ¼ d ð4:33Þ
Aa AR
ð4:29Þ
and for the repulsive force
This equation yields an equation for the critical radius
vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
! kT ð1 þ aÞ AUe
u
u 3 e e w 2
j A fR ¼ d ð4:34Þ
ajcr barr ¼ t em e0 w2 ai AR
0 m
 UðaÞ
4pDqg 1 þ expðjhmax Þ 6ðhmax Þ2
where R = 2Rij / aj + ai; Rij is the distance between particle
ð4:30Þ
centers; Um(Rij) and Ue(Rij) are the molecular attractive and
The penetration through the electrostatic barrier occurs for the electrostatic repulsive energies, which are introduced [8].
particles larger than ajcr_barr. Afterwards, the total dimensionless inter-particle force Fs can
be expressed as
4.6. Numerical solution. Stability diagram
1 AðUm þ Ue Þ
Fs ¼  d ¼ NA ðfA  NR fR Þ ð4:35Þ
There are 3 publications that follow the first work on the kT AR
stability diagrams introduced by Spielman and Cukor [54].
These are well-known works by Melik and Fogler [8] and two In order to characterize the relative strength of gravitational
more recent publications [46,78]. All of them apply numerical and Brownian forces, authors of these papers use Peclet number
calculations for deriving stability diagrams. Comparing numer- Pe, which they call a “gravity number” Gr. They are not aware
ical calculations from the papers [46,78] with Ref. [30], it that this parameter had been introduced for the exactly the same
becomes clear, that the numerical approach allows generaliza- purpose decades ago by Fuchs [16].
tion of the theory over any α. This parameter is defined as:
Authors of these papers paid a special attention to the
molecular forces retardation. Instead of using a simple asym- ðusi  usj Þðai þ aj Þ 2pgDqa4i
Gr ¼ ¼ að1  a2 Þ ¼ Pe ð4:36Þ
ptotic expression (4.5) for completely retarded molecular forces 2Dij 3kT
they used a more complicated expression that presumably
describes the transition range of molecular retardation [80,81]. where Dij is relative particle diffusivity.
This eliminates the possibility of an analytical approach and The gravitation role predominates and Brownian diffusion
leaves the numerical approach as the only one available. may be disregarded, when Gr = Pe ≫ 1.
The authors of the recent papers in [46,78] argue that there The gravity parameter NG describes the relative importance
was no proper description of the short-range hydrodynamic of gravitational and attractive forces. It is given as
interaction in [8]. With an exception for the description of
hydrodynamic interaction, the physical and mathematical Gr pgDqa4j
NG ¼ d ð1 þ aÞ2 ð1  a2 Þ ð4:37Þ
models of all three works [8,46,78] are almost the same. NA 3A
Hence, we pay major attention to the work in [8].
The model used in the paper [8] is based on the earliest work by For stability against the primary minima coagulation, the net
Spielman and Cukor [54], although it is not cited. The set of the gravitational force bringing the particles together must be less
48 A.S. Dukhin et al. / Advances in Colloid and Interface Science 134–135 (2007) 35–71
Fig. 10. Gravity induced flocculation stability diagram according to Melik and
Folger [8].
than the maximum net repulsive force keeping the particles
separated. It occurs when
 
GðRij; aÞ
NG b max ðNR fR  fA Þ ðh ¼ 0Þ ð4:38Þ
AðRij Þ
It is obvious that this condition and condition (11) in Ref.
[30] are almost identical. In both cases the conditions are
formulated for the front pole of particle (θ = 0). In both cases, the
total inter-particle force is determined by the electrostatic
repulsion at the barrier location. A difference exists due to
multiplier G / A(Rij), where A(Rij) is the Hamaker function
[80,81], specified for the location of the barrier and G is the
hydrodynamic correction function [82].
This condition (4.38) interconnects NG and other parameters
and enables one to determine the boundary between the domain
of stability and domain of coagulation in primary minima.
Once a particle pair has flocculated, they can either remain
flocculated or re-disperse. To determine whether de-flocculation
is possible, the alignment of the particle pair with the principal
straining axis θ = π is considered. Under these conditions,
gravity is pulling the particles apart. Consequently, if the net
gravitational force that pulls the flocculated particles apart is
greater than the maximum net attractive force keeping the pair
flocculated, de-flocculation occurs.
 
GðRij; aÞ
NG N max ðfA  NR fR Þ ðh ¼ pÞ
AðRij Þ
This condition is formulated for the secondary minima and
for the rear pole of the larger particles as in [30]. It is obvious,
that this condition is similar to condition (14) in [30] or Eq.
(4.23). The condition (4.39) interconnects NG and other
parameters with respect to the secondary minima and enables
one to determine the boundary between the domain of the
stability and the domain of coagulation in secondary minima.
The results of this stability analysis are presented in Fig. 15
in [8], as a stability plane κ(a1 + a2) / 2 versus N, which is
divided into 3 domains, similar to the stability diagram of
Spielman and Cukor [54]. The advantage of this diagram given
as Fig. 10, is a possibility to estimate the α influence, when the
flocculation type is predicted. Accordingly, the work of Melik
and Fogler [8] was perfected later [46]. Two main equations in
[46] coincide with Eqs. (4.38) and (4.39) with one distinction
only. G(R) is specified in [46] with the use of a more exact
theory of Jefferey and Onishi [76]. As result there is a large
similarity of the stability diagrams on the κa–NG plane, namely
Fig. 15 in [8] and Fig. 5 in [46]. The diagrams are specified for
the same set of parameters, that makes their comparison
informative.
The displacement of the boundary between the domains of
the primary and secondary flocculation corresponds to the
doubled decrease of κa. The difference in boundaries between
the domain of stability and the domain of primary floccula-
tion is even smaller. In Fig. 9 in [46] the boundaries between
domains are calculated for large difference in parameter ν,
which characterizes the magnitude of the retardation. It is
seen, that the retardation may cause doubled decrease in κa
value. α influence on the boundary between domains is char-
acterized in Fig. 10 in [46]. Its influence is much larger than
the retardation influence, namely NG within the boundary
differs about 10 times.
No attention to the possibility of particle escaping from the
primary minima was paid in [8,46]. This may be justified, if its
depth is unrestricted. The initial model of surface forces with an
infinitely deep primary energy minima in DLVO theory was
replaced by a model with the potential well of a finite depth in
the works of Frens and Overbeek [83,85] and Martinov and
Muller [84]. When a solid particle surface is hydrophilic, the
distance of the maximal approach between 2 particles δ exceeds
the doubled thickness of a solvation layer. A larger δ and
accordingly a smaller maximal attractive force make a smaller
hydrodynamic detachment force (e.g. smaller Qij) sufficient for
the detachment from the primary minima. This is illustrated by
curves a, b and c in Fig. 11 and this is considered in detail in
[78], where Qij = πΔρgai4(1 + α)2(1 − α2).
The plane NR–Qij is chosen in [78] as convenient for the
characterization of the hydrodynamic detachment from primary
minima. At a weak electrostatic repulsion, i.e. at small NR (e.g.
NR b 3 × 102) the PHF is sufficient to overcome the barrier and
the coagulation occurs within the primary minima (Fig. 11). At
larger electrostatic repulsion, i.e. at larger NR the penetration
through the barrier becomes impossible. However, the floccu-
ð4:39Þ lation at secondary minima is possible, if the gravity force is not
large. This is the reason why the domain of the secondary
minima coagulation occupies the left higher corner only. With
increasing Qij, i.e. with the increasing of the sedimentation
velocity, the hydrodynamic detachment from the secondary
minima occurs. This is the reason why the gravity stabilizes a
suspension and why the stability domain occupies the right
higher corner in Fig. 11.
 A.S. Dukhin et al. / Advances in Colloid and Interface Science 134–135 (2007) 35–71
Fig. 11. Gravitational coagulation stability diagram for κ(a1 + a2) / 2 = 1000;
α = 1/2; ν = 1/15; [(a) δ = 1.5 nm; (b) δ = 0.75 nm; (c) δ = 0.15 nm], Qiao and Wen
[78].
The stabilization due to gravity is realized at smaller NR, when
the flocculation at primary minima is possible as well, if the
hydrodynamic detachment from the primary minima does not
occur. The outcome depends on the primary well depth. The depth
of the force well depends on δ and accordingly the boundary
between the domain of the primary minima flocculation and the
domain of the stability depends on δ (Fig. 11).
Let us compare the analytical theory [30] with numerical
theories [8,46,78].
All of them apply rather exact and similar models for
describing the hydrodynamic interaction. These are the
Stimson–Jeffery model [75] in the analytical paper [30], and
the Jefferey–Onishi model [76] in the numerical papers
[8,46,78]. It is unlikely that the difference between these
hydrodynamic models is essential.
There is no difference in the methods for deriving equations,
which determine boundaries between various stability domains.
As a result, the derived equations are identical, although their
appearance is different. This difference is associated with a
different parameterization. Analytical theory uses critical size
values acr for determining stability domains, whereas numerical
theories rely on the dimensionless numbers NR and NA.
However, all results of the work in [30] may be transformed
to the same parameterization as numerical theories by relating
acr to NR and NA.
The main difference between analytical and numerical
theories is description of the molecular retardation. Implemen-
tation of the retardation into the theory makes mathematics too
complex for an analytical solution. Only a numerical solution
becomes possible. This certainly limits our ability for deriving
some general conclusions. There are two more disadvantages
associated with this numerical approach. We mentioned above
that there are some doubts regarding validity of the molecular
forces retardation theory. In addition, there are several other
49
theoretical assumptions involved that might not be valid for
particular real systems. For instance, assumption about the
constant potential is not universal [1]. The charge invariance is
possible, or even charge invariance for one kind of particles, and
the potential invariance for another one [1].
On the other side, analytical approach might lead to
oversimplification. It is difficult to estimate the errors caused
by the approximate description of the retardation.
This brings us to the conclusion that both approaches should
be developed in parallel. Comparison of the results would allow
us to gain much better understanding on the validity ranges and,
at the same time, formulate much more general conclusion
using analytical expressions.
4.7. Gravity role in hetero-coagulation and micro-flotation
Term ‘hetero-coagulation” specifies various aggregative
processes in the dispersions and emulsions with several
dispersed phases. The most important phenomenon of this
kind is micro-flotation — coagulation in the systems containing
bubbles. Interaction between bubbles and dispersed particles is
strongly affected by gravity. There is a large bulk of literature on
this subject. Here we represent part of it, especially for micro-
flotation. This term has been widely used by Derjaguin, S.
Dukhin and Rulyov for describing bubbles interaction with
micron and sub-micron particles [5,86].
Although gravity induced hetero-coagulation was consid-
ered as a mechanism of micro-flotation already in 1960 [31], the
systematic elaboration of the theory started after many years
[32–35] and continues [4,60]. There are many differences
between gravitational homo-coagulation and micro-flotation
with respect to both hydrodynamic interaction and surface
forces. However, there is a lot in common as well. In particular,
the 3 types of the coagulation (stabilization) are inherent in both
gravitational coagulation and micro-flotation.
Micro-flotation theory assumes that the bubble rising and
corresponding hydrodynamic field around are known, while the
particle deposition from this hydrodynamic flow onto bubble
surface has to be quantified.
In the area above the equatorial plane, lines of liquid flow
approach the bubble surface, which means that the radial
Fig. 12. Directions of PHF and hydrodynamic detachment force at particle–
bubble interaction during micro-flotation.
50 A.S. Dukhin et al. / Advances in Colloid and Interface Science 134–135 (2007) 35–71
component of the liquid velocity is directed towards the bubble
(Fig. 12). The approach of the particle to the bubble is
accompanied by drainage from the liquid film between them.
This is possible due to the increase of pressure in the film, which
retards the approach of the particle to the bubble surface,
provides drainage and causes PHF. Both PHF and gravity are
pointing to the bubble surface near its front pole (Fig. 12).
Near the rear pole the gravitational force is directed away
from the bubble and this changes its sign (FG d
= − FG
p
). The
detachment hydrodynamic force (DHF) points away from the
bubble surface near its rear pole. In the extreme cases of Stokes
and potential flows there is anti-symmetry in the liquid velocity
distribution with respect to the equatorial plane. Accordingly,
the maximum DHF arises near the rear pole since the maximum
PHF exists near the front pole.
Van der Waals forces are mainly repulsive, i.e. the Hamaker
constant is negative, A b 0 in flotation conditions. As both bubbles
and particles have the same (negative) charge, a question arises in
framework of classical DLVO, what is mechanism of particle/
bubble attachment. Derjaguin answered this question on the base
of his theory of hetero-coagulation [67,68]. It predicts that the
change of the direction of electrostatic force occurs (curve 4 in
Fig. 13) at the distance smaller than h⁎ according to Eq. (4.2).
When ψ1 = ψ2, there is electrostatic repulsion at any distance
and at any electrolyte concentration. Usually it decreases with
the increasing electrolyte concentration. Accordingly, the
gravitational homo-coagulation is possible at high electrolyte
concentration and it is impossible at low ones. An opposite
regularity is inherent in micro-flotation, according to DLVO.
A decrease of the electrolyte concentration and an increase
of the potential ratio are favorable for micro-flotation caused
by electrostatic attraction. The zone of the attractive total
surface force for p/b interaction is even narrower than
estimation by Eq. (4.2), because of the addition of the repulsive
molecular force Fm(h). At a large distance, the total surface
force Fs(h) = Fm(h) + Fe(h) is always repulsive because both its
components are repulsive. In other words, there is a force barrier
with height Fsmax at relatively large distances and a force well
with depth Fsmin at relatively small ones. Qualitatively the
situation is illustrated in Fig. 13 [60]. Two different cases
appear. In the first case molecular forces exceed electrostatic
ones at all distances, and even in the region of electrostatic
attraction the total force is repulsive (curves 1 and 2) or equal to
zero (curve 3). The electrostatic attractive force dominates at
certain distances and causes a negative well in the total surface
force (curve 4).
Near the upper pole of the bubble the total pressing force
p
Fpr = FH + FG is negative; however, to compare it with surface
forces it is convenient to show its value with the opposite sign
(see Fig. 13, curve 5).
The condition necessary to overcome the force barrier and to
have attachment can be presented [5] as
max
Fme þ Fpr V0: ð4:40Þ
Although, conditions (4.23) and (4.40) for the calculation of
the critical radius and for the onset of either stabilization or
coagulation are identical, a large difference arises at their
specification. In the homo-coagulation case the penetration
through the barrier occurs near the lower pole, while in the
micro-flotation case it occurs near the upper pole of the bubble.
A large peculiarity for PHF is possible, that will be discussed in
the next section.
The most significant distinction is the peculiarity of the
influence of the electrolyte concentration change on micro-
flotation. The transformation of curves in Fig. 13 in the sequence
1, 2, 3, 4, 5 occurs with the monotonous decrease in electrolyte
concentration. The micro-flotation promotion by means of
electrolyte concentration decrease is its main regularity, predicted
by hetero-coagulation theory. Accordingly, it deserves a
consideration.
At fixed surface potentials of particle and bubble, the
existence of the minimum of the negative force depends on the
electrolyte concentration. The electrolyte concentration
corresponding to curve 3 will be referred to as the first
characteristic concentration, C1cr.
At concentration larger than C1cr the penetration through the
barrier is impossible, because the force barrier exceeds PHF.
This becomes possible at a smaller concentration, although it
may lead to further detachment.
4.8. Prevention of coagulation in primary minima in micro-
flotation due to gravity
Another effect where gravity plays an important role is the
prevention of coagulation at primary minima during micro-
flotation. The detachment will not take place at electrolyte
concentrations lower than C1cr if the detachment force Fdet is
min
smaller than the maximal attractive surface force F me [60]
min
Fme þ Fdet V 0 ð4:41Þ
min
where F me is realized at the minimum of the Fme(h) curve.
At concentration slightly below C2cr, which corresponds to
curve 4 in Fig. 13 there is no detachment, because the
detachment force is equal to the net attractive surface force at
the concentration C2cr.
Fig. 13. Qualitative scheme of DLVO forces for a bubble and a particle with the
same sign of surface charge as a function of h, Mishchuk et al. [115].
 A.S. Dukhin et al. / Advances in Colloid and Interface Science 134–135 (2007) 35–71
At concentration slightly below C2cr, the detachment is
prevented for one particle size only. At concentration lower than
C2cr, a micro-flotation domain exists. For particles that are larger
than the value of their upper boundary, the detachment occurs.
For particles that are smaller than the value of their lower
boundary, the electrostatic force barrier exceeds the PHF and
this excludes the possibility of attachment. The attachment
without further detachment takes place only when the particle
size is between these boundaries.
There is a large difference in the hydrodynamic velocity
distribution for rising bubbles at small (Re b 1), and at large
(Re N 300) and at intermediate dimensions. At not very large
Re, the bubble surface is almost immobile due to its re-
tardation by surfactants or other impurities [4,87]. Accord-
ingly, the Stokes velocity distribution is valid at smaller Re.
At Re N 300, the bubble surface is mobile, if the surfactant
concentration is not sufficiently high for its immobilization.
Levich [88] proved that the velocity distribution is potential
in this case.
The large difference in bubble states with immobile and
mobile surfaces leads to the larger difference in the normal
components of velocity, which decreases with the decreasing
distance to surface up to zero. This causes a large difference
in PHF, because it is proportional to the value of the nor-
mal component of velocity at the distance of about a particle
diameter [4,5,87]. In turn, this velocity depends on the re-
duced distance, i.e. on small ratio (a1/a2) 2 , where a1 and a2
are the radii of the particle and the bubble respectively. For
large bubbles (about 1 mm), which are used in flotation of
larger particles, the PHF is proportional to a1/a2. For smaller
bubbles (about 100 μm), used in micro-flotation of small
particles, the PHF is proportional to (a1/a2) 3 , i.e. much smal-
ler. This leads to an important conclusion, that the electro-
static repulsions may essentially hamper micro-flotation,
because PHF is weak. On the contrary, the PHF may suppress
the influence of the electrostatic repulsion on the flotation,
because the PHF is much stronger, when bubble surface is
mobile.
This agrees with the modeling for micro-flotation domain in
[60]. It almost disappears, when the bubble surface is retarded
according to Fig. 8 in [60]. This agrees with the micro-flotation
experience. It was found by many groups that micro-flotation is
enhanced near an iso-electric point. The review of those papers
is given in [4,5,60].
The prediction of an existence of either both primary
and secondary minima or the primary minima alone is im-
portant for the application of the theories for the gravitational
homo-coagulation and hetero-coagulation. The analytical so-
lution of this problem is given in [89] with respect to homo-
coagulation.
5. Probability of aggregates formation and breakup.
Corresponding gravity effects
There are two completely different approaches for deriving
collision frequency expression. Historically the first one
was based on first physical principles of hydrodynamic, elec-
51
trodynamics, statistical mechanics. It usually leads to rather
complicated mathematical expressions that do not allow solu-
tion of the population balance equation. This is why the
second approach came to life. It is based on purely math-
ematical consideration. A scientist pursuing this approach
simply tried various simple mathematical expressions for the
collision frequency that allow analytical or numerical solution
of the PBE. We present here a short overview of both these
approaches.
5.1. Collision frequency derived from the first principles
The first attempt of estimating collision frequency induced
by directed motion of particles was made by Von Smoluchowski
[48]. He derived the following equation relating β with the
velocity gradient of the fluid du / dy:
4 du
bij ¼ R3ij ð5:1Þ
3 dy
This work by Smoluchowski was the basis for incorpo-
rating gravity into the collision frequency. Apparently it was
done first by Camp and Stein in 1943 [9] who presented
the following widely used expression for rectilinear collision
frequency:
2gpDq 3
bgij ¼ R2ij jui  uj jEij ¼ R jdi  dj jEij ð5:2Þ
9gm ij
where u is a Stokes sedimentation velocity for particles of
diameter di.
This expression is often attributed mistakenly to other
authors.
Parameter Eij is “collision efficiency”. It reflects influence of
the hydrodynamic interaction and surface forces on the
coagulation kinetics. Coagulation follows a “fast kinetics”
route when electrostatic repulsion does not hamper the particle
attachment and each collision results in aggregation.
Rectilinear model ignores completely hydrodynamic parti-
cles interaction and contribution of the surface forces. There
have been a number of attempts to incorporate these factors into
the “collision frequency”. In this review we ignore all attempts
dedicated to the particles deformation. We present here only
results regarding influence by gravity induced hydrodynamic
interaction on the “collision frequency”.
Historically, the first efforts had been made for aerosols and,
especially, flotation. Gravitational effects are most pronounced
in the bubble–particle interaction (flotation) due to the large
density contrast. Many of these results are easily extended to
liquid based dispersions and emulsions. For instance, a bubble
with the surface retarded by a surfactant is identical to a solid
particle from the hydrodynamic viewpoint.
Initially, theoretical development applied simplification by
considering only particles with very different sizes. This
assumption yields a small parameter (particle size ratio),
which can be used for simplifying mathematics.
Later developments eliminated this assumption.
52 A.S. Dukhin et al. / Advances in Colloid and Interface Science 134–135 (2007) 35–71
The deviation of the particles trajectories from the linear path
under influence of the hydrodynamic interaction causes a
change in the collision frequency. The dimensionless multiplier
E in the expression for the collision frequency (5.2) that reflects
this effect equals:
b2
E¼ ð5:3Þ
a2
where b is the maximum radius of the cylinder around the
bigger particle, which encompasses all particles that
would deposit on the larger one (Fig. 3). The particles
moving along the streamline at the target distance b accu-
mulate on the surface of a bigger particle (Fig. 3 as indicated
by a dashed line). Otherwise, the particles are carried off
by the flow. It is evident that the calculation of collision fre-
quency is essentially reduced to the so-called “limiting
(grazing) trajectory” (continuous curve) and, correspondingly,
to the target distance.
Such calculations were presented for the first time by
Sutherland [10]. They were based on the consideration of liquid
streamlines and finite size of spherical particle collision due to
interception
3a21
E0 ¼ ð5:4Þ
2a22
where a1 and a2 are the radii of smaller and larger particles.
Later, S. Dukhin and Derjaguin proved the theorem that the
particle concentration would remain constant if the velocity
field is solenoidal [13]. They quantified the influence of the
gravitational deposition of smaller particles on the surface of
larger ones with the following expression:
3a21 Dqa21
E0 ¼  ð5:5Þ
2a22 qa22
where Δρ is the density difference.
Further theoretical analysis showed that long-range
hydrodynamic interaction becomes not adequate when the
distance between two approaching particles diminishes.
The hydrodynamic interaction at distances comparable to
the size of the smaller particle is called the short-range
hydrodynamic interaction [4–6]. The value of bcr decreases,
first, due to the deflection of the liquid streamline under the
influence of the long-range hydrodynamic interaction and,
second, due to the deflection of the small drop trajectory
from the liquid streamline under the influence of the short-
range hydrodynamic interaction. Therefore, the collision ef-
ficiency is expressed as the product of two factors, E0 and
E1, both smaller than unity. The first one represents the
influence of the long-range hydrodynamic interaction and
the second, the influence of the short-range hydrodynamic
interaction.
Later, Spielman [90] and Goren [91,92] incorporated van
der Waals attraction into the theory of small particle deposi-
tion from laminar flow on the surface of a larger particle. Their
numerical results served as an important component of the
micro-flotation theory derived by Derjaguin–Dukhin–Rulyov
[5,86].
As a next step, Rulyov [36,37] obtained the following ap-
proximate analytical equation for the collision efficiency using
the same basic physics:
Aa22
E ¼ E0 E1 ðW Þ; W ¼ ð5:6Þ
27us pgm a41
where A is the Hamaker constant.
The function E1(W) is plotted in [36,37] and can be
approximated according to the work in [37]. It leads [5] to the
equation
a1:4
E ¼ 0:11 1
A1=6
a22
Examination of Rulyov's approximation in the work in [6]
indicates that it agrees well with results of papers [52,53]. The
impression arises that coagulation is possible at any small (but
finite) value of the Hamaker constant, because E dependence on
A is very weak. However, further fragmentation is possible at
sufficiently small A.
Further development of the theory pursued a goal of
removing restriction of the small sizes ratio. If the difference
between particle sizes is not large, the description of their
interaction requires different parameterization. The motion of
two interacting particles is a superposition of the mass center
motion and their relative motion in the frame of references that
is associated with the mass center. When the spheres are very
close, the mobility functions have the asymptotic forms given
by Jefferey and Onishi [76].
Davis [19] incorporated these asymptotic forms into the
equation for the particles trajectories. His results agree with
Rulyov's results for the small particle size ratio a1/a2 ≪ 1.
Davis also suggested an equation for the collision frequency
of the emulsion droplets that takes into account the difference in
viscosity of the media ηm and droplet ηp:
 
g
2 g p þ 1 gpDq
bgij ¼ R2ij jui  uj jEij ¼  g  R3ij jdi  dj jEij ð5:7Þ
m
3 3 g þ 2 gm
p
m
In addition, Davis and his co-authors Zinchenko and Zhang
[17,21] created a procedure for calculating collision efficiency
Eij that takes into account simultaneously gravity, Brownian
effects and hydrodynamic droplets interaction.
There is a version presented by Reed et al. [93], which is very
similar to the Sutherland solution [10] but with no, at least
mentioned, restriction of the sizes ratio:
3y2c
E0 ¼ ð5:8Þ
2ða1 þ a2 Þ2
where yc is the size of the smaller particle. It seems to us that it is
actually identical to the Sutherland solution, which is 30 years
earlier with all applied limitations discussed above.
 A.S. Dukhin et al. / Advances in Colloid and Interface Science 134–135 (2007) 35–71
Later, Zhang and Davis [17] used the Batchelor expression
[94] for the speed of the particles relative motion. They modified it
for spherical emulsion drops. It turns out that the collision
efficiency approaches a finite value as the drop becomes equi-
sized (a1/a2 → 1). However, the collision rate goes to zero in this
limit because the relative velocity of two drops approaches zero.
The unique peculiarity of the results is that the non-zero collision
efficiency occurs in the absence of attractive molecular forces due
to liquid mobility inside the droplet.
There are several more recent works studying interaction in
fractal systems. Interaction between primary particles and
fractal aggregate is the primary goal. We mention here just
two models that found their way to other studies.
This first one is by Han and Lawler [95] who suggested the
following numerical solution for the curvilinear collision
efficiency between particle and aggregate:
There are authors, for instance authors of paper [101], who
dp
Epa ¼ exp 3:4 þ 0:62 log g þ ð3:5  1:2log gÞ ð5:9Þ
da
8A
where g ¼ , A is the Hamaker constant, us is the settling
3pus da2
velocity of the aggregate with size da.
This model has been used in several modern studies related
to fractals. It does not take into account flow through the fractal
aggregate, yet.
There is another model which takes into account internal
flow through the aggregate–advection. It has been developed by
Xiaoyan Li and Logan in paper [45]. They used Brinkman's
model for describing aggregate permeability. Their expression
is valid for the small particle size ratio
 
53
physical principles one could just suggest some mathematical
expression for this parameter that would allow further solution
of the population balance equation.
This approach was very popular in aerosol science, especially
in the Soviet Union. These works were summarized in the book
by Voloshchuk and Sedunov that was published 30 years ago in
the USSR [98,99]. Unfortunately this book is not available in
English. One of the expressions that they suggested had been used
in the paper [100] for describing aggregation of erythrocytes.
It seems to us that this approach has reached its culmination
so far in the work by Van Dongen and Ernst [25]. They
suggested the following expression for the collision frequency:
bij ¼ av il jvl where v V 2; jNNi; v  lV1 ð5:11Þ
The two parameters χ and μ provide fundamental information
about the reactivity between clusters of different sizes.
consider that the van Dongen and Ernst model is sufficient to
specify most of the important aspects of the coagulation
kinetics; specifically, the shape of the cluster size distribution
and the time evolution of size classes and moments. They agree
that there is substantial cost of ignoring the analytical details of
the collision frequency. They express hope that some missing
constants could be found from the experiment.
There are several papers that report results on gravity
influences coagulation kinetics using van Dongen–Ernst
collision frequencies, for instance, [101,102].
5.3. Collision frequency for simultaneous Brownian and
  gravitational coagulation
9pda2 u 1  tanhn n 1  exp  2s3 ð1  eÞafilt gda1b
bpa ¼ h  i In comparison with a large amount of researches devoted to
4a 2n2 þ 3 1  tanhnn calculation collision frequency either Brownian or gravitational
ð5:10Þ aggregation, very little works have been done when both,
Brownian motion and gravity, are important simultaneously.
where The first work on this subject as far as we know, had been
done by Fuchs 40 years ago [12,16]. He formulated a question
da
n ¼ pffiffiffiffiffiffiffiffi regarding critical particle size that separates Brownian and
2 jagg gravitational coagulation dB–g. Coagulation kinetics would
only be Brownian when particle size is much smaller than dB–g,
Permeability κagg according to Brinkman [96] equals: whereas for larger sizes it would be purely gravitational.
" rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi # In order to estimate the value of this number Fuchs compared
dp2 4 8 diffusion and hydrodynamic fluxes of particles onto a selected
jagg ¼ 3þ 3 3
72 1e 1e center. He came up with 1 μm as an approximate particle size
that separates Brownian and gravitational kinetics modes.
Parameter dp is the diameter of primary particles, ε is the porosity This simple calculation has been repeated in several more
of the aggregate. Meaning of other parameters is given in the recent works, apparently without knowing that it had been done
original paper. 40 years ago. His conclusion regarding this value of the critical
Difference in particle densities is accounted for in the theory particle size has been confirmed experimentally recently by
of gravitational coagulation in [97]. Morbidelli's group [42,43].
This success of the Fuchs approach tells us that we can use a
5.2. Collision frequency assumed from the mathematical similar procedure for calculating collision frequency. There is a
reasoning dimensionless number that characterizes the ratio between
diffusion and hydrodynamic fluxes — Peclet number, Pe
As we mentioned above, there is also a completely different [61,88]. Diffusion dominates over convection when this number
approach to specifying collision frequency. Instead of using is small. We can determine the Peclet number of the coagulation
54 A.S. Dukhin et al. / Advances in Colloid and Interface Science 134–135 (2007) 35–71
phenomena as a parameter that relates Brownian and sedimen-
tation fluxes on the particular center particle. This yields the
following expression:
pDqgd14
Pe0 ¼
24kT
Index “0” for Peclet number and particle diameter reflects the
initial time moment. We determine this parameter at the initial
stage of the aggregation process.
If particles are small, Brownian diffusion dominates
aggregation kinetics and Peclet number is small. Increasing
size of the particles leads to increasing Peclet number due to
larger contribution of sedimentation into the particles collision
frequency.
We would get Fuchs estimate for dB–g assuming that the
Peclet number equals 1.
This parameter depends on the size very strongly. This
means that transition from Brownian to gravitational coagula-
tion is very sharp on the size scale.
This also means that Fuchs estimate is valid for practically
any particles independent of their density. For instance, in the
case of emulsions density contrast can be 100 times less than for
rigid oxide particles. This would lead to an increase of dB–g for
emulsions, but only 3 times. It looks like 1 μm is a universally
good estimate for the transition range.
Peclet number remains small at the initial stages of the
transition from the Brownian to gravitational aggregation. We
can use it as a small parameter and present “collision frequency”
as a two terms expansion [39]:
bg ðv; v VÞ ¼ bd ðv; v VÞ½1 þ Pe0 j~v  ~v Vj
where volume of particles is normalized by the volume of initial
particles φ.
Expression (5.13) assumes additivity between Brownian and
gravitational coagulation. The same assumption was used by
Wang and Davis [22] 9 years after A. Dukhin [39] and by
Reddy, Melik and Folger [103]. Expression (5.13) ignores also
hydrodynamic interaction. In the earlier work by Reddy, Melik
and Folger [103], hydrodynamic particle interaction was
disregarded as well.
There is theoretical justification for both these assumptions.
It comes from the most detailed numerical calculation of the
collision frequency, which had been performed by Zinchenko
and Davis and presented in work [21]. They took into account
both, gravity and Brownian effects, with complete hydrody-
namic interactions. Unlike previous studies on the collision
frequency, a numerical solution was valid for the arbitrary
Peclet number, thus covering the whole range of sizes in a
typical dispersed system (Fig. 14).
A key finding is that the synergistic effects of Brownian
motion and gravity sedimentation give much higher coagulation
rates than either mechanism acting alone or predicted by the
additivity approximation in the Peclet range 10 b Pe b 104 with
its maximum around 102.
At the same time, this numerical calculation confirmed
that the error of the “additivity approximation” is negligible
for the small Peclet number below 1. This is justification for
describing transition from Brownian to gravitational coagu-
lation when Pe b 1 using additivity approximation, as it was
done in [39].
Expression (5.13) allows us to achieve analytical solution of
ð5:12Þ
the population balance equation and derive some general
conclusions regarding transition from Brownian to gravitational
coagulation.
There is also analytical expression for collision frequency for
the opposite case of large Peclet numbers when gravitational
coagulation dominates. It had been done in work [104].
The case of the weak gravity and strong Brownian
aggregation was investigated in [105].
The calculations in [104] for combined Brownian and
gravitational coagulation were accomplished without account
for hydrodynamic interaction.
5.4. Collision frequency for charged non-Brownian particles
The seminal work by Spielman and Cukor [54] contains the
numerical theory for collision frequency in addition to their
stability diagram (Fig. 7). Capture efficiency is predicted from
the numerical calculation of the limiting trajectory. As the
limiting trajectory touches the collector surface (larger particle)
at its rear pole (Fig. 4), this is used for the limiting trajectory
identification in numerical calculation. The integration starts at
this point and continues back along it up to the determination of
the target distance bcr at a sufficiently large distance from the
collector, where the trajectory reduces into a straight line
(Fig. 4). The ratio 2E/3(a1/a2)2 is calculated as function NR and
ð5:13Þ NA. The results of the calculation for κa = 10 in assumptions
about constant potential or constant charge are reproduced in a
well-known monograph [108], namely Fig. 11.9.
The regularities inherent in frequency dependences on NR
and NA characterized in this figure are obvious. For any fixed
Fig. 14. The collision efficiency as a function of the relative Peclet number for
drop with ai/aj = 0.25 and no inter-droplet forces. The solid line is the exact
solution of Zinchenko and Davis [21], the dotted line represents the additivity
approximation, the dashed line is the Brownian collision efficiency, and the
dashed–dotted line is the gravitational collision efficiency [22].
 A.S. Dukhin et al. / Advances in Colloid and Interface Science 134–135 (2007) 35–71
NA value, E is maximal for NR = 0 and decreases with increasing
NR, because the electrostatic repulsion increases. For any fixed
NR value E decreases with increasing NA. This occurs, because
the fixed NR corresponds to the fixed surface forces, while
increasing NA means decreasing velocity (decreasing PHF).
With a decrease in PHF, the penetration through the electrostatic
barrier becomes possible for the smaller portion of the collector
surface near its front pole.
In micro-flotation, the Reynolds number varies within a
broad range that is accounted for in the Rulyov theory for
micro-flotation of charged particles. He elaborated the theory
for the rising bubbles with completely retarded surface at
Re b 100 and for rising bubbles with mobile surface, when the
potential velocity distribution is valid [88]. The results are
presented in the factorized form
E ¼ E0 ða1 =a2 ; ReÞUðWs ; L; W1 =W2 ; jaÞ ð5:14Þ
Ws differs from NA due to the numerical multiplier only,
L = εΨ2a22 / 24πa13U.
This equation reduces to the simpler equation for uncharged
particles derived in an earlier paper [106]. Both papers [106]
and [107] contain figures describing the frequencies for many
combination of numerous parameters.
5.5. Aggregates breakup frequency
There is a theory created mainly for a simpler kind of
aggregate, namely for doublet. There is a special time parameter
introduced for characterizing the frequency of doublet frag-
mentation — fragmentation time τd. Chandrasekhar [109]
derived a theory for calculating this parameter considering the
doublet fragmentation as the particles diffusion away from the
potential minimum generated by their attraction. The
corresponding timescale of this process equals:
 
6pgm a31 Umin
sd ¼ exp  ð5:15Þ
kT kT
where Umin is the depth of the potential minimum.
Later, Muller suggested a more general theory for deriving
the formula of the aggregates average lifetime [110,111]. He
considers the equilibrium in a system of doublets and singlets
(i.e. the numbers of doublets decomposing and appearing are
equal). Both processes are described as a standard diffusion
flux J of the singlet particles in the force field of the central
singlet particle. Each doublet is represented as a central
immovable singlet particle surrounding with a spherical
layer where the second singlet is “spread”. This spherical
layer corresponds to the region of the potential energy mini-
mum. The diffusion flux J of “escaping” singlet particles is
described by the equation used in the Fuchs theory of slow
coagulation [16]. The first boundary condition corresponds to
the assumption that the escaping singlet particles do not
interact with other singlets. The second condition reflects the
fact that the potential minimum contains exactly one singlet
particle.
55
When separation between the singlets in a doublet is small,
the singlet particle diffusivity decays because of the increasing
hydrodynamic resistance during particle approach. Muller used
a convenient interpolation formula for describing this influence
of hydrodynamic interaction on the mutual singlet particles
diffusivity [110]. This hydrodynamic interaction causes the
main difference between the more exact Muller solution and
Chandrasekhar solution given by Eq. (5.15).
Retardation and screening [112–114] of the molecular forces
of attraction were treated [115] as a factor, which tends to
deteriorate secondary minimum aggregation in emulsions.
Doublet fragmentation time is calculated in [115] as a function
of droplet dimensions, electrolyte concentration, and the Stern
potential with and without accounting for the retardation of
molecular forces.
While doublet of emulsion droplets is considered in [35], the
fragmentation of an aggregate, consisting of solid particles, is
considered in [116]. Both approaches are similar to Muller's
work [110].
There is a useful relationship derived by Shilov in [116] for
the ratio of the constant collision frequency β to the constant
breakup frequency of a single particle connecting bond δ:
b 4pa21 h Umin i
¼ ‘ kT  1 ð5:16Þ
d j
Existing works on this subject ignore gravity effect. It is
possible to incorporate it in this theory for the case of the
secondary minimum following work. Gravity reduces depth of
the secondary minimum and eventually can break the bond.
6. Population balance equations and corresponding gravity
effects
The most known population balance equation has been
derived by von Smoluchowski [117] as a conservation law of
the dispersed phase in every element of the system volume:
Z
duðv; tÞ 1 v
¼ bðv V; v  v VÞuðv  v V; tÞuðvVÞdvV
dt 2 Z0
v
 bðvdv VÞuðv; tÞuðv V; tÞdvV ð6:1Þ
0
where φ(v) is a unary distribution function for particles, β is
collision frequency. The first integral in this equation reflects
increasing number of the aggregates with volume v due to
aggregation of particles with volumes v′ and v − v′. The second
integral describes a decreasing number of particles with volume
v by aggregation with particles of volume v′. There are several
major limitations of this equation.
First of all only binary collisions are taken into account.
Secondly, fluctuations of the dispersed phase content are
neglected.
Third, it neglects the possibility of aggregates breakup.
56 A.S. Dukhin et al. / Advances in Colloid and Interface Science 134–135 (2007) 35–71
Fourth, it does not take into account directed motion of the
particles. It assumes that a particle undergoes only random
Brownian motion.
The third restriction has been removed by Melzak [50], who
suggested a more general PBE that takes into account aggregates
breakup.
Z errors could be useful for describing real aggregation
duðv; tÞ 1 v
¼ bðvV; v  vVÞuðv  vV; tÞuðv VÞdv V
dt 2 Z0
v
 bðvdv VÞuðv; tÞuðvV; tÞdv
Z v0
þ dðv þ v VÞuðv þ vVÞdvV dðvÞuðvÞ ð6:2Þ
0 gation serves as a fundamental basis for an analytical solution that
The two additional terms on the right hand side of Eq. (6.2)
reflect the increasing number of particles with volume v due to
breakup of the aggregates with volume (v + v′) and the decreasing
number of the particles with volume v due to their breakup.
Incorporation of the directed particle motion in addition to the
Brownian motion is more complicated. Particle size distribution
becomes a function of the position of the particular volume
element in the system. Historically it was considered a big
change that a special terminology was suggested for distinguish-
ing between aggregation induced by only Brownian motion —
“peri-kinetic”, and directed particles motion — “ortho-kinetic”.
From a mathematical point of view, an additional term
appears at the left hand side of the PBE equation. This term
would reflect variation of the particles number in the element of
volume due to particles passing it with certain velocity Y Y
V ð r; tÞ.
Vector Y r denotes position of the element in the system. As a
result, the PBE equation for the case of negligible aggregates
breakup becomes the following:
duðYr; v; tÞ
þ divJ ðu; tÞ
dt
Z
1 v
¼ bðv V; v  vVÞuðY r; v  vW; tÞuðYr; v VÞdv V
2 0
Z v
 bðvdv VÞuðY r; v; tÞuðY r; v V; tÞdv
0 collision radius for the pair of particles and represents the
where J is the flux density of the particles with volume v. It
consists of two terms: diffusion and convection:
duðmÞ
J ðuðmÞÞ ¼ D þ V uðmÞ
dx
In addition, gravity or any other directed motion of particles
would also affect “collision frequency” β and “breakup
frequency” δ. There are several ways to take this into account,
as will be described below.
Neither of the population balance equations mentioned
above can be solved exactly. Any possible solution is asso-
ciated with a certain “theoretical error”. Clearly we would like
to minimize this error. However, it is important to recognize
that there is also “modeling error”, which we make when
substituting a model heterogeneous system for the real one.
When the “theoretical error” becomes less than the “modeling
error”, further improvement of theoretical solution becomes
meaningless.
Modeling error of the complex heterogeneous systems is
quite large in many cases. This means that even very
approximate theoretical solutions with rather large theoretical
phenomena. This is especially important for a few existing
analytical solutions that are less accurate than numerical
solutions, but much more general and simple. That is why we
describe these analytical solutions in more detail.
The Smoluchowski solution for Brownian peri-kinetic aggre-
takes into account gravity. That is why we present here a short
overview of this historically first PBE solution.
6.1. Smoluchowski solution for Brownian coagulation
The classical understanding of coagulation kinetics is given
by von Smoluchowski [117]. Computer simulations [26–28]
serve as a means to test the validity of the mean field approach.
In order to solve the population balance equation, one
must specify “collision efficiency”. Smoluchowski suggested
an approximate way to achieve this for Brownian peri-kinetic
aggregation. He calculated the number of particles colliding
with imaginary stationary central particle within a unit time. He
assumed that each collision would lead to the aggregation. This
is the so-called “fast aggregation process”.
Then, an allowance can be made for the fact that the central
particle itself is one of many similar particles undergoing
Brownian motion and so the appropriate collision frequency can
be derived. We present these results below for discrete
presentation of the particle size distribution. Collision frequency
between particles of fraction i and j equals:
bdij ¼ 4pRij ðDi þ Dj Þ ð6:5Þ
where Di and Dj, and ni and nj are the diffusion coefficients and
ð6:3Þ number concentrations, respectively. The term Rij is the
center-to-center distance at which the particles may be assumed
to be in contact. For spherical particles
di þ dj
ð6:4Þ Rij ¼ ð6:6Þ
2
This assumption plus Einstein expression for the diffusion
coefficient (Eq. (3.1)) yields the following expression for the
“collision frequency”
ð2kT =3gm Þðdi þ dj Þ2
b dij ¼ ð6:7Þ
di dj
If the dispersed phase is monodisperse, the initial collision
frequency can be easily calculated because only identical
 A.S. Dukhin et al. / Advances in Colloid and Interface Science 134–135 (2007) 35–71
primary particles contribute to it. This leads to the following
equation for the total particle concentration N(t):
 
dN ðtÞ 4kT
 ¼ NT2 ¼ KF N ðtÞ2 ð6:8Þ
dt 3gn
where KF is known as the coagulation rate constant and has
a value of approximately 6.13 · 10− 18 m3 s− 1 for aqueous
dispersions at 25 °C.
The most noteworthy feature of Eq. (6.8) is that it does not
include the particle size because the size terms cancel from Eq.
(6.7) when di = dj. As the particle size increases, the diffusion
coefficient decreases, but the collision radius increases. These
opposite effects balance each other exactly for equal particles.
Collision frequency of the Brownian coagulation is not very
sensitive on the particles size in general, even for particles of
different sizes. The term (di + dj)2 / didj in Eq. (6.7) is very close
to 4, provided that the sizes do not differ too greatly. For
instance, if sizes are different by a factor of 3, the size term in
Eq. (6.7) has a value of about 5.
The simple Eq. (6.8) yields the following expression for the
total number of particles as a function of time
N0
N ðtÞ ¼ ð6:9Þ
1 þ KF N0 t
where N0 is the initial concentration of the primary particles.
There is a characteristic coagulation time τsm, during which
the number of particles reduces by half:
1 This concept does allow us analytical description of at least
ssm ¼ ð6:10Þ
KF N0
It is also possible to calculate the concentration of single
particles and aggregates assuming the collision frequency being
for all collisions. The derivation is reproduced in many text-
books, for example in [118,119].
The role of Brownian movement in the coagulation process
decreases with increasing particle size. The influence of the
differential settling begins to dominate and more general
population balance equation must be used — Eq. (6.3).
Unfortunately, there is no known analytical solution of this
equation.
However, there is one particular simplification, which
makes possible some analytical analysis of the ortho-kinetic
gravitational coagulation. It is introduction of the “zone with
the uniform dispersed phase”. The next section describes this
important notion.
As we mentioned before, the population balance equations
by Smoluchowski and Melzak assume that the amount of
dispersed phase remains constant in every element of the system
volume during aggregation. This assumption becomes invalid
due to gravity. If the dispersed phase is more dense than the
dispersion medium, the top layers of the system become
gradually depleted with particles due to their sedimentation. At
the same time the bottom layers of the system become enriched
with particles that build up deposit. If the dispersed phase is
57
lighter than the dispersion medium (emulsions), the situation
would be reversed. Fig. 15 illustrates existence of these 3 zones,
which are important for proper description of the aggregation
under influence of gravity.
Consequently, particle size distribution becomes a func-
tion of the space coordinate, or a depth in the solution. The
population balance equation gains an additional term, see
Eq. (6.3).
There is, however, an intermediate zone where the particles
flow in and out of each volume element that compensates each
other. Condition of the constant and uniform dispersed phase
content holds in this zone. This simplifies PBE tremendously.
Particle size distribution becomes again independent of the
special coordinate and the “div” term on the left hand side of Eq.
(6.3) becomes 0. This means that in this intermediate zone Eq.
(6.3) simply reduces to the Smoluchowski equation (Eq. (6.1)),
if we would neglect aggregates breakup.
This concept has been introduced for the first time by A.
Dukhin [38,39]. It was re-introduced independently 10 years
later by Kumar et al. [120].
According to this concept we can apply the Smoluchowski
equation for describing coagulation kinetics in the uniform zone
even under influence of gravity, which would only affect the
value of the “collision frequency” β g:
Z
duðv; tÞ 1 v g
¼ b ðvV; v  vVÞuðv  vV; tÞuðv VÞdv V
dt 2 Z0
v
 bg ðvdv VÞuðv; tÞuðvV; tÞdv V ð6:11Þ
0
some aspects of gravity-influenced coagulation phenomena, as
we will show below. This analytical solution requires
appropriate expression for the “collision frequency” β. The
next section describes several different approaches for deter-
mining this parameter with contribution from gravity.
Introduction of the “uniform zone” is also very important
for experimental verification of the theoretical developments.
Fig. 15. Illustration of the various zones appearing during sedimentation: 1 —
depleted zone; 2 — uniform zone; 3 — deposit.
58 A.S. Dukhin et al. / Advances in Colloid and Interface Science 134–135 (2007) 35–71

It is stressed by Kumar and others in their work [120],
especially for emulsions. They pointed out that: “In fact, most
of investigators have not specified from where they drew the
samples or which type of coalescence they were studying”
[120]. Consequently, they make reasonable critical remarks
about the state of the experiment. They point out that
interpretation of many experimental works regarding droplet
coalescence is uncertain, because the coalescence role was not
isolated from the trivial droplets loss due to sedimentation.
After considering different means for eliminating this loss,
they conclude that the utilization of the uniform coagulation
zone provides the simplest and most reliable method for
achieving this goal.
We can conclude that introduction of the uniform zone yields
substantial benefits for both, theory and experiment. We
illustrate this conclusion in the following sections.
6.2. Population balance equation with aggregates breakup.
Analytical solution for chain aggregates with small fractal
number
Gravity can break aggregates if bounds between parti-
cles are weak. This effect can be described in terms of
the pair interaction, see above. At the same time it affects
kinetics of the system evolution and might be presented in
terms of the modified population balance equation and cor-
responding solutions. Such equation has been suggested
50 years ago by Melzak [50], see Eq. (6.2). It is quite
complex mathematically, that is why various simplifications
are used. For instance, one can assume a constant collision
frequency β following Smoluchowski arguments. In addition,
we can also assume a constant breakup frequency δ. Discrete
presentation of the Melzak equation with these assumptions
follows:
There are several recent publications on the subject of the
chained aggregates, for instance [123]. The chain formation in this
work is a result of coagulation of particles that are oppositely
charged. There is a clear influence of the gravity on this coagulation
process.
Existence of oppositely charged particles is not a necessary
condition for the chain formation. There is a number of much
earlier works that observed chain formation by particles with
the same charges. These older works are practically unknown
and forgotten. The first detailed experiments of the kinetics on
the chain aggregates formation known to us had been
conducted in Germany by Prof. Sonntag's group [116,124]
in the 80's. The initial theoretical description of this process
had been suggested independently by Shilov [124] and Muller
[125].
They compared probability of a primary particle attaching
to one of the chain end with probability of its attaching to
the interior parts of the chain. It turns out that in some cases
the first probability is much greater than the second one.
Primary particles would attach predominantly to the ends of
the chains, which would lead to their growth. This happens,
in particular, when there is potential barrier preventing
irreversible particles coagulation and rather shallow second-
ary minimum. The chain length will grow the increasing
probability of the primary particles attachment to the interior
of the chain. Eventually this probability becomes equal to the
probability of the attachment to the ends. At this length the
primary particle would attach to the interior of the chain and
a new chain would start growing. This is the mechanism of
fractal growth.

dui 1 X i1 X
l Xl
¼ b uij uj  bui uj þ 2d uiþj  ði  1Þdui
dt 2 j j j¼1

ð6:12Þ

The meaning of the breakup frequency δ depends on

the scheme of the aggregate breakup. We know 3 diffe-
rent schemes from the literature, which are presented in
Fig. 16.
As far as we know the first scheme had been introduced by
Russian scientist Voloshchuk in his book that is available only
in Russian [98,99]. He develops kinetic theory for this scheme
that might be realistic only for aerosols.
The second scheme was suggested again by Russian
scientists 30 years ago [121].
Both these schemes and related kinetics were discussed in
some details by Lushnikov and Piskunov in the paper that is
available in English [122].
From our viewpoint, the most interesting is the third
scheme — formation and breakup of the linear chain aggr-
egates. It is relevant for understanding the mechanism of
fractal formation. Fig. 16. 3 models for aggregate fragmentation.
 A.S. Dukhin et al. / Advances in Colloid and Interface Science 134–135 (2007) 35–71 59

Muller, Martynov and Shilov [116,121,125] calculated torically the first one was given by A.S. Dukhin [38,39] and
evolution of the total amount of particles in time. The more Melik and Fogler [8] in the mid-80's. The second one was
convenient presentation of this result had been suggested in suggested about 15 years later by Jung et al. [40]. These
paper [41]: solutions are completely independent that is why their agree-
h i ment, as we will show below, is even more valuable.
2 ð2g1Þt
N0 g2
ðg  1Þ exp  gðg1Þssm
¼ h i ð6:13Þ 6.3.1. Analytical solution by A.S. Dukhin [38,39]
N ðtÞ g þ ðg  1Þexp  ð2g1Þt This solution is valid for the “zone of uniformed dispersed
gðg1Þssm
phase”. The particle size distribution φ(v, t) and its zero
where parameter γ equals the ratio of the initial number moment N(t) were expanded in a series respective to small
particles to the number of aggregates in the stationary state Ns: parameter Pe0

N0 2bN0 uðv; tÞ ¼ u1 þ Pe0 u2 þ N ð6:17Þ

g¼ ¼ pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi ð6:14Þ
Ns d þ 4dbN0  d2
2

N ðtÞ ¼ N1 þ Pe0 N2 þ N ð6:18Þ

The time, which is required for achieving a stationary state,
τst equals:
where
gðg  1Þ Z
sst ¼ ssm ð6:15Þ l
ð2g  1Þ N1 ¼ u1 ðv; tÞdv ð6:19Þ
0
The stationary state is not equivalent to the equilibrium state
because the evolution of the system continues due to the Z l
redistribution of the particles within aggregates and the
N2 ¼ u2 ðv; tÞdv ð6:20Þ
appearance of the new particles bonds. 0
Later analysis showed [41] that evolution of the total number
of particles is not adequate for proper description of the chain Here φ1 and N1 are terms corresponding to the Brownian
formation kinetics. It is independent of the scheme of the chains aggregation only.
breakup [122]. This means that the theory should describe more Substituting functions (6.17) and (6.18) into population
parameters. This was done in paper [41]. This paper presents balance Eq. (6.1) yields a linear equation for N2(t). This
analytical solution of the Melzak equation for the stationary equation contains functions N1(t) and φ1(v, t) that are known.
state that can be achieved due to the balance between chain Function φ1(v, t) can be found in monograph [98] for different
formation and breakup. initial distribution. Solution of the linear equation for N2(t)
Paper [41] employs the method of “generating function” requires an initial condition for particle size distribution. The
suggested in paper [122]. It is shown that the “generating two different initial PSD (exponential and monodisperse) are
function” for the stationary particle size spectrum obeys the used in work [39].
Riccati equation. Solution of this equation yields the following The final result is given as a time function of the total number
expression for concentration of chains with i number of primary of particles during transition from Brownian to gravitational
particles: aggregation.
0qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi 1i
For exponential initial PSD:
dB 1 þ 4bN0
d  1 C
usi ¼ @qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi A ð6:16Þ

b 1þ d þ1 4bN0 N0 tPe0 ðt=ssm þ 2Þ

N ðtÞ ¼ 1 ð6:21Þ
1 þ t=ssm 4ssm ðt=ssm þ 1Þ
Role of gravity on the kinetics of the chain formation in this
theory is included in the “collision frequency” β and “breakup For monodisperse initial PSD:
frequency” δ. " !#
There is discussion of the relevant experiment in the N0 t lnð1 þ 2t=s sm Þ
N ðtÞ ¼ 1  Pe0 
Experimental data section. 1 þ t=ssm 4ssm 8ð1 þ t=ssm Þ2
ð6:22Þ
6.3. Transition from Brownian to gravitational aggregation.
Analytical solution The first interesting conclusion following from these equa-
tions is that transition from Brownian to gravitational ag-
There have been two analytical solutions of PBE, which gregation is invariant to the shape of the initial particle size
describe the role of gravity in the coagulation kinetics. His- distribution. The terms proportional to the Peclet number differ
60 A.S. Dukhin et al. / Advances in Colloid and Interface Science 134–135 (2007) 35–71

only 2 times even at t = τsm. The difference in these term decays
quickly with time, since
lnð1 þ 2sÞ
limðsYlÞ ¼0
8ð1 þ sÞ2
Thus, the heterogeneous system, in effect, “forgets” its initial
state; and at the time of transition from Brownian aggregation to
gravitational, initially different systems become identical.
This conclusion agrees with idea of a “self-preserving
distribution” by Friedlander [47] for Brownian aggregation. It
turns out that this feature of the particle size distribution might
have a much wider validity range.
These assumptions allow the author to come up with
analytical expressions for mean particle size, standard devia-
tion and total number of particles versus time. We present here
ð6:23Þ only the expression for the total number of particles, because it
can be compared with the result of the previous analytical
solution.
 
1  2exp3Z0 3
N ðtÞ ¼ N0 expf9ðZ  Z0 Þg ð6:27Þ
1  2exp3Z
where Z depends on standard deviation: Z = ln2 σ.
Authors of this paper have compared this analytical solution
with the numerical one and got a very good agreement.

6.3.2. Analytical solution by Jung et al. [40] 6.3.3. Comparison of analytical solutions and the following
There are several distinctive differences between this conclusions
approach and the previous one. First of all authors of this It is possible to compare predictions regarding evolution
work consider only gravitational coagulation. They use of the total number of particles coming from both analyti-
collision frequency as defined by the Smoluchowski–Camp– cal solutions. Authors of the second solution presented their
Stein theory — Eq. (5.2) with collision efficiency that takes into prediction in graphical format. It is reproduced in Fig. 17.
account hydrodynamic interaction following the work of Reed They. used dimensionless time that can be presented as the
et al. [93] — Eq. (5.8). We mentioned before that it is identical following:
to the Sutherland approach [10] from our viewpoint. p ffiffiffiffiffiffiffiffiffiffi
They used the Momentum Method formulated by Lee in 3
~t ¼ t pPe0 4p=3
paper [126]. He showed that the population balance equation ð6:28Þ
3ssm
would lead to three ordinary differential equations for the first
three moments of particle size distribution. These three moments
We can convert the expression from the first analytical
can be related to the parameters of the particles size distribution
solution, Eq. (6.21), to this dimensionless time. For the times
with a particular shape for complete description of the kinetic
that exceed substantially Smoluchowski times, this new
process. They chose a log-normal distribution defined as the
expression would look like the following:
following:
"  4=3 #

N0 4p ~
N ðtÞ ln2 ðv=vg ðtÞÞ 1 N ðtÞ ¼ 1 t ð6:29Þ
uðv; tÞ ¼ pffiffiffiffiffiffi exp ð6:24Þ 1 þ t=ssm 3
3 2plnrðtÞ 18ln2 rðtÞ v

where vg(t) is the geometric mean particle volume, σ(t) is the When dimensionless time equals 1, gravity would reduce the
geometric standard deviation based on the particle radius. total number of particles by 14.8% in addition to Brownian
A set of the differential equations for vg(t), σ(t) and N(t) does
not offer any analytical solutions yet. These forced an additional
assumption. In an attempt to derive an analytical solution, they
disregard the volume of the smaller particle in comparison to the
larger particle in the expression for collision efficiency:

v 2=3 jib0 v 2=3 ~

yc2 jv 2=3  ~ v 2=3

where b0 is the correction coefficient, which is to be calculated by:

Z
duðv; tÞ 1 v g
¼ b ðv V; v  v VÞuðv  v V; tÞuðv VÞdv V
dt 2 Z0
v
 bg ðvdvVÞuðv; tÞuðv V; tÞdv V ð6:25Þ
0

RR 2=3
Fig. 17. Evolution of the total number of particles according to the Jung et al.
yc2 jv 2=3  ~
v juðv; tÞuð~
v; tÞdvd ~
v [40] analytical theory presented by solid lines. Dashed lines illustrate that this
b0 ¼ R R 2=3 ~ 2=3 ~ ~ ð6:26Þ second analytical solution predicts reduction of the total particles number
v v uðv; tÞuðv; tÞdvd v somewhere between 10 and 15% when dimensionless time is 1.
 A.S. Dukhin et al. / Advances in Colloid and Interface Science 134–135 (2007) 35–71
coagulation. This prediction of the first analytical solution
agrees perfectly with the second analytical solution. We
illustrate this statement with dashed lines in Fig. 17. It is seen
that the second analytical solution predicts this number
reduction somewhere between 10 and 15%.
This agreement between two analytical solutions that
are based on completely different approaches makes both of
them much more reliable. We can use them for making certain
predictions regarding the role of the gravity in the coagulation
process.
For instance, we can introduce a critical time for this
transient, which should be about the same for all heterogeneous
systems. Terms that are proportional to the initial Peclet number
become substantial when time approaches a certain critical
value τcr. In order to define a definite time moment we can
follow the same principle as was used for introduction of the
Smoluchowski time. The last one is defined as a time moment
when the total number of particles reduces by half. Similarly we
can introduce τB–g as a time moment when gravity reduces the
total number of particles by half. This yields the following
expression for this critical time:
2ssm 3gm
sBg ¼ ¼ ð6:30Þ
Pe0 Dqgud0
This parameter determines also the validity time range of the
Smoluchowski theory for Brownian aggregation.
One might argue that sedimentation instability would
manifest itself prior to the changes described in this theory. In
other words, it might be possible that the “zone of uniform
dispersed phase” would disappear before this transition
would take place. In order to resolve this issue, we could
compare the critical time τB–g with the time of sedimentation
instability τsd:
sBg d0
c ð6:31Þ
ssd ul
l Fortunately we have found a definition of all parameters in their
where ssd ¼ . previous paper [22].
us
Transition time is shorter by a hundred times than sedimen-
tation time for micron sized particles at 1% volume fraction,
assuming l equals 1 cm or more. Smaller values of l are not
practically interesting. This restriction on l creates a small
parameter d /l ∼ 0.0001 in the right hand side of Eq. (6.31). For
smaller particles this ratio is even smaller that is why transition
time becomes comparable with sedimentation time only for
extremely dilute systems.
Therefore, we can conclude that there is enough time for
experimental observation of the transition from Brownian to
gravitation aggregation in the “zone of uniformed dispersed
phase”.
6.4. Transition from Brownian to gravitational aggregation.
Numerical solution
The most sophisticated numerical solution of the popula-
tion balance equation has been performed by Wang and
61
Davis [23]. It extends their preceding work [22]. The purpose
of this work was description of the emulsion droplets coa-
lescence kinetics for a very wide range of droplet sizes. This
would include both Brownian and gravitation coagulation
mechanisms.
The most important is that they managed to avoid “additivity
approximation” for specifying collision frequency. They used a
very detailed description of the collision frequency calculated
by Zinchenko and Davis in work [21]. This work took into
account complete hydrodynamic droplets interaction and does
not apply “additivity approximation” for combining together
Brownian and gravitational mechanisms of the relative particles
motion.
Relationship between these mechanisms was characterized
by the Peclet number, which they defined as the following:
2pDqg ai ðai þ aj Þðai  aj Þ
2 2
Peij ¼   ð6:32Þ
3kT 1 þ ai
aj
Their numerical procedure applied no restrictions on the Peclet
number. They present the result in the range of the Peclet from
0.0001 to 1,000,000.
They also used the Peclet number for the initial emulsion Pe0
defined by Eq. (5.12).
It is important to realize the difference between the initial
Peclet number Pe0 and the Peclet number at a certain time
moment Peij(t). For instance, some of the conclusions by Wang
and Davis' paper [23] are formulated for the initial Peclet,
instead of the time dependent Peclet. In particular, the gravity
effect would become important eventually for any small initial
Peclet number due to gradual growth of the time dependent
Peclet number.
Regarding their calculation, it is hard to convert their data in
our symbols because their procedure of introducing dimension-
less time has not been described clearly enough in the text.
Fig. 18. The average drop radius at t = 50τb as a function of Pe0 for a dispersion
with an initial distribution having a standard deviation of 0.2. The upper curve is
the result using exact collision efficiencies, and the lower curve is the result
using the additivity approximation [22].
62 A.S. Dukhin et al. / Advances in Colloid and Interface Science 134–135 (2007) 35–71
It turns out that their characteristic time for Brownian
coagulation (τb) is actually double the Smoluchowski time.
If this assumption is valid, then Fig. 18 shows a plot of the
average radius at t = 100τsm as a function of the initial Peclet
number.
When Pe0 → 0 (Brownian effects alone), the calculated value
is aav = 6.8a0, whereas the calculated values using the exact
collision efficiencies are aav = 17.1a0, 7.7a0, and 7.0a0,
respectively for Pe0 = 10− 1, 10− 2 and 10− 3.
The calculated values using the additivity approximation are
aav 9.1a0, 7.0a0, and 6.8a0, respectively, for the same Peclet
numbers.
Thus, neglecting gravitational effects or inaccurately ac-
counting for them using the additivity approximation leads to a
significant under-prediction of the droplet growth for Pe N 0
(10− 2). This determines the limits of the analytical solution
presented above that is based on the additivity approximation.
Actually coagulation evolves faster than predicted by analytical
theory after the Peclet exceeds roughly 0.01.
We can also compare the value of the critical time τB–g
established in paper [39] with this numerical solution. In order to
do this we should define a similar critical time for the numerical
solution τB–g
num
. We can assume that this time depends on
Smoluchowski time and initial Peclet number on the same way
as for the analytical solution, but with unknown multiplier A:
ssm
Bg ¼ A
snum ð6:33Þ
Pe0
We can use some of the Wang and Davis conclusions for
determining the value of A. For instance, they stated that
gravitational effects become important at time t = 50τb = 100τsm
if the initial Peclet number Pe0 N 0.01. This means that
coefficient A is approximately 1 and the value of the critical
time for the transition from Brownian to gravitational
coagulation according to the numerical solution equals:
ssm
cr ¼
snum ð6:34Þ
Pe0
It is only 2 times shorter than the prediction of the analytical
solution [39]. We consider this as a good agreement, keeping in
mind all assumptions involved in defining these parameters.
This research is a culmination of characterizing gravity
influence on rapid coagulation.
There are several other papers that use various expressions for
collision efficiency that are derived following the mathematical
approach described above. It is possible to compare some of these
results with the analytical solution [39].
For instance, authors of paper [101] followed Van Dongen
and Ernst's path [56] and solved numerically PBE for constant
kernel and sedimentation rate that increases linearly with the
cluster size. They came to the conclusion that the total particles
concentration decays like the power law of time during the
transition period:
N ðtÞft a ab0 ð6:35Þ
This result does not agree with the analytical solutions.
This example shows the importance of the analytical solution
as the reference point for verifying the underlying assumptions
of the numerical solutions.
7. Experimental techniques
Experiments of the fast coagulation kinetics are usually
performed with very dilute systems. Characteristic times of this
process in the concentrated systems are too short for reliable
monitoring. This points towards optical methods as the most
suitable for this purpose.
There is a detail description of the earlier techniques for
studying kinetics of aggregation phenomena in the book
authored by Sonntag [119] in 1987. Some of these methods
yield only global information on the state of aggregation;
others give a detailed picture of the particles and flocs size
distribution.
There has been substantial progress achieved since that time
in instrumentation. For instance, modern light scattering
instruments are able to monitor not only particle size, but also
can be used for quantifying fractal dimension. One of the most
sophisticated kinetic studies using light scattering has been
made in recent years in the Swiss Federal Institute of
Technology in Zurich [42,43]. In an earlier work [42], they
used small-angle light scattering, but more recently [43] —
dynamic light scattering. Their results will be discussed in the
next section.
There is one limitation of optical methods — they do not
produce any information on the rheological properties of the
aggregates. Rheological size can be very different from the
optical size because large flexible aggregates can twist under
stress. Parts of the aggregate could behave as separate particles
from a rheological viewpoint. Sedimentation applies shear
stress on the aggregates boundaries that is why rheological size
is relevant for the subject of this review.
There is a relatively new technique that yields some
information on the micro-rheological properties of the struc-
tured systems. Instead of light it uses ultrasound as a carrier of
information regarding particles properties. Ultrasound applies
longitudinal stress to the system and, consequently, brings
information on rheological properties. Characteristic space
dimensions are related roughly to a quarter of the ultrasound
wavelength. Modern instruments work at frequencies up to
100 MHz, which corresponds to the wavelength of 15 μm. This
means that this technique yields information on rheological
properties on the scale of a few microns.
Acoustic spectrometer measures two parameters: attenuation
of ultrasound and sound speed. We have shown that attenuation
of the frequency spectra can be used for characterizing the
strength of the inter-particle bonds in the aggregates. There is a
detailed description of this method in book [127]. There is also a
description of the experiments illustrating how this method
reveals the difference between aggregation and flocculation. It
is in Chapter 8.
It is our opinion that a combination of optical and acoustic
methods would lead to a much more complete understanding of
the coagulation phenomena.
 A.S. Dukhin et al. / Advances in Colloid and Interface Science 134–135 (2007) 35–71
8. Experimental data
There have been several experimental studies of the gravity-
affected coagulation during the last two decades. These
publications are scattered between different Journals and their
authors are usually not aware about other works. As far as we
know this is the first time all these results are presented at one
place.
We try to arrange these experimental works following the
nature of the systems. Consequently we come up with several
different sub-sections presented below.
8.1. Gravity influence on homo-coagulation
First of all the work by Folkersma, Diemen and Stein will be
discussed [59,128,129]. They used turbidity measurements and
even performed an experiment in space for observing the effect
of micro-gravity environment. They also used centrifugation for
studying the effect of higher gravity.
These coagulation experiments were performed under 1 g and
1 μg conditions during flight in sounding rockets for dispersions
of polysterone, quartz and amorphous silica particles. The
influence of gravity was observed for suspensions of quite large
particles (N ∼1 μm). However, under μg conditions the observed
coagulation rate constant approached the Smoluchowski theoret-
ical value for this parameter. This indicates high precision of the
measurement on one side. On the other side it points towards
gravity as a factor affecting the deviation from Smoluchowski's
theory. A similar conclusion follows from the observation at 1 g
gravity conditions. Deviation from Smoluchowski kinetics
decreases with the decreasing of the density contrast, i.e. with
decreasing gravity role.
In experiments [59], the enhancement of particle sedimen-
tation either at transition from μg condition to 1 g conditions or
at the increasing density in 1 g condition retards the coagulation
kinetics. Authors of this work treat this observation as a
contradiction with the theory gravitational coagulation. They
consider the increase in the collision frequency as due to the
differential settling as a single mechanism gravity role in the
coagulation. They are not aware, that the same differential
settling may cause the escaping of particles from the secondary
minima, which would lead to decreasing coagulation rate. It is
strange that this mechanism, described in [8,30,54], is ignored
and these references are not cited. As this mechanism may be
the reason of the reduction of the coagulation rate due to gravity
that manifests itself in their experiment, the author's efforts to
interpret their interesting experimental data are mainly in vain.
They employ convection as a factor that might explain their
observations.
However, this explanation has been later disapproved by Sun
and Qiao [130].
Another observation of the gravity-affected coagulation has
been reported in the paper by Frojmovic et al. [155]. They
studied kinetics of the blood platelets coagulation. Kinetics rate
was substantially higher than that calculated for Brownian
coagulation. It depended strongly on the origin of the platelets.
Human blood platelets coagulate much faster than canine or
63
rabbit blood. It turns out that reconciliation of the theory and
experiment is possible only when coagulation efficiency would
be corrected for gravity induced platelets interaction. It was
done using the additivity assumption, which is presented here
with Eq. (5.13). Gravity almost doubles the coagulation rate for
human platelets, but is less important for two other platelets
types.
Interpretation of this coagulation experiments had been
complicated by the fact that platelets are not spherical. Their
geometry is very peculiar due to the presence of pseudopods
that extend from the platelet into the solution and increase the
probability of the platelets collision. Interaction of these
pseudopods masks gravity effects if bloods platelets are used
for the kinetics coagulation study. Other objects would be more
preferable for this topic.
The best objects for studying coagulation are emulsions. The
main peculiarity and benefit of studying emulsion are the way
they build up an aggregate. It is a compact new particle, or even
a new drop. The last one occurs when droplets coalesce within
the aggregate. This is the most desirable route of aggregation for
verification kinetic theory. It was stated in papers [131–133]
that emulsion follows this path of aggregation when coales-
cence time τc is shorter than Smoluchowski time τsm:
ssm NNsc ð8:1Þ
The droplets disappear within the agglomerate due to a
coalescence more rapid than a new droplet attaches to the
agglomerate when Eq. (8.1) is valid. Hence, the fractals do not
grow because aggregates consist of two droplets all the time.
The droplet size grows, but the number of the individual
particles within the aggregate does not [131–133].
In the opposite case, when the coalescence inside the
agglomerate cannot prevent the growth of particles number, the
flocs may form, similarly to a dispersion or aerosols.
Condition (8.1) indicates applicability boundary for the
kinetics of emulsion destabilization, considered in this section.
Unfortunately, the practical use of condition (8.1) is compli-
cated, because there is no commercial device for measuring τc,
while its calculation is known only for some model systems.
The link between the chemical nature of an adsorption layer,
its structure, and the coalescence time is not yet quantified. A
premise for such quantification is the theory of a foam-bilayer
lifetime [134–138]. The main notions of this theory are similar
to the theory of Derjaguin and co-workers [139,140]. However,
the theory [134–138] is specified for amphiphile foam films, it
is elaborated in detail, and proven by experiment with water-
soluble amphiphiles, such as sodium dodecyl sulfate [141]. As
the dependence of the rupture of the emulsion film on surfactant
concentration is similar to that for a foam film, the modification
of the theory with respect to emulsion may be possible.
Although this modification is desirable the specification of a
theory for a given surfactant will not be trivial, since the
parameters in the equation for the lifetime [134–138] are
unknown and their determination is not easy.
There are two more potential problems that might complicate
using emulsions for testing kinetic theories — mobility of their
64 A.S. Dukhin et al. / Advances in Colloid and Interface Science 134–135 (2007) 35–71
surface and deformability of the droplet. Fortunately, there are
some ways of eliminating or avoiding this problem. It can be
done either theoretically, or by proper treatment of the particular
system.
For instance, the role of the droplet surface mobility on the
short-range hydrodynamic interaction and the collision fre-
quency was a subject of work [17]. However, there is no need
for using this more complicated theory. The droplet surface can
be completely retarded by adding surfactant. This would reduce
the spherical droplet to a solid particle from the hydrodynamic
viewpoint.
The peculiarity of emulsion droplets, their deformation, is
more complicated and deserves special attention. Only recently
essential progress is achieved in the understanding and
quantifying the role of the deformation [142–144]. Yiantsios
and Davis [18] created a method (YD) for investigation of a thin
emulsion film evolution under action of a lubrication arising
from gravitational coagulation. They derived an equation for
distance dependence at the early droplet deformation. They
consider the film rupture to be more a natural evolution than
instability. According to the YD theory the droplet deformation
does not influence the grazing trajectory in mini-emulsions.
This justifies an introduction of a simple method to calculate
the collision efficiency in mini-emulsions.
However, with decreasing surface tension or increasing
droplet dimension (transition to macro-emulsions) the droplet
deformation can influence the collision efficiency. As a general
comment, the importance of droplet deformation in mini-
emulsions was over-estimated for many years. It was shown
only recently in paper [17] that the transition to the charged
droplets and lower electrolyte concentrations prevents droplet
deformation.
Taking into account the weak influence of droplet deforma-
tion on rapid coagulation, we can conclude that rapid Brownian
and gravitational coagulation cannot be significantly affected by
droplet deformation in mini-emulsions. Meanwhile droplet
surface is homogeneous in contrast to solid particle surface and
the droplet satisfies the spherical model much better than many
solid particles.
Thus, the mini-emulsion can be used as a model system for
the evaluation of the state of the theories of coagulation. Their
polydispersity is not a serious obstacle as it is demonstrated in
[23]. It is a purely mathematical problem, which may be solved
using PBE.
The first step is verification of the collision efficiency in
mini-emulsion. Although extensive studies have been made on
the impact of two drops at high velocity, there is perhaps only
one experimental paper devoted to hydrodynamic interaction
between 2 drops at not a large difference in droplet dimensions
in low Reynolds number flow [20]. In spite of a rather large
droplet dimension (about 700 μm) the settling velocity of an
isolated drop was sufficiently small and accordingly Re was
less, than 1, because of small density difference of the drop
phases and the matrix fluids and the high viscosity of the chosen
matrix fluids. This large droplet dimension enables one to
measure small droplet horizontal displacement at their approach
of each other during settling.
Experimental results demonstrated that hydrodynamic inter-
action significantly reduces the relative velocity of two
nearby drops and causes two drops to flow around each other
with curved trajectories. The theory predicts that the effect of
hydrodynamic interactions increases as drop separation de-
creases, the size ratio decreases and the viscosity ratio increases,
which are also confirmed.
A large attention to collision efficiencies for droplets of
almost equal dimensions was paid in atmosphere science. It
is believed [145] that this kind of collisions plays a major
role in the earlier stage of the gravitational coagulation,
when droplets grew up to 20 μm due to condensation. Both
the theory and a review of the experimental data are given in
[145].
The next step is verification of the kinetic theory that
describes evolution of the particles ensemble. To our
knowledge, there is only one experimental work devoted to
this subject for emulsions — [58]. Three different oils were
used (toluene, dichlordecane and isolating oil) for preparing
oil in water emulsion. Mean droplet diameters were about
2 μm. There were several volume fractions tested in the
range from 0.4% to 1%. Measurement technique was turbidity
measurement.
Time of the sedimentation instability for this emulsions
exceeds the time of aggregation approximately 10 times, as-
suming droplet size of 2 μm, φ = 0.01, l = 1 cm and Δρ = 0.1 g
cm3. This means that the necessary condition for observing the
transition from Brownian coagulation to gravitational is valid.
The authors of this paper observed indeed the deviation
from the Smoluchowski law for peri-kinetic coagulation, as
it is shown in Fig. 19. It is seen that coagulation evolves faster
than the Smoluchowski law for lower volume fraction 0.4%
and 0.7%. This is in agreement with the prediction of the
theory.
Evolution of the most concentrated emulsion with 1% oil
contradicts the theory because it is slower than the Smolu-
chowski rate. However, the position of this experimental curve
Fig. 19. Time dependence of the optical density of the emulsions with different
volume fraction of the transformation oil measured in [58], 1, 1′ — 0.4%, 2,
2′ — 1%, 3, 3′ — 0.7%. Dashed curves are plotted according to the
Smoluchowski theory.
 A.S. Dukhin et al. / Advances in Colloid and Interface Science 134–135 (2007) 35–71
indicates that the basic underlying assumption regarding the
relationship between optical properties and dispersed phase
properties becomes invalid for this high concentration because
it lies between curves with lower volume fractions.
It seems to us that this work can be considered at least as a
preliminary qualitative confirmation of the predictions for
transition from Brownian to gravitational coagulation.
8.2. Gravity influence on fractal structures
One of the most detailed investigations of the fractals
coagulation kinetics has been done by the Swiss Federal Institute
of Technology in Zurich. We know their two papers published in
recent years [42,43]. In the first paper they used small-angle light
scattering and obscuration measurement for characterizing
polystyrene latex coagulation. They arranged conditions of
flocs formation for studying fractal aspects of this phenomenon.
It turns out that after roughly 100 min the kinetic curve exhibits
deviation from the Smoluchowski law. The flocs size accelerates
its growth with time. They explained this effect with flocs
sedimentation that would speed up their growth. In order to justify
this assumption they varied density of water using heavy water
D2O. This test confirmed that observed deviation from the
Smoluchowski law occurs due to gravity.
This experiments confirms a 20 year old prediction of the
analytical theory formulated in paper [39]. Decreasing the total
number of particles comparing to the Smoluchowski law is
equivalent to increasing their size due to gravity induced
additional collisions.
In order to compare this experiment with analytical theory
[39], we should somehow estimate the value of the particle size at
a certain time t using the expression for total number of particles.
We can do this using the expression that relates size of the fractal
aggregate ai with the number of primary particles in it i [146]:
ai ¼ i1=df a1 ð8:2Þ
where a1 is the radius of primary particles and df is the fractal
dimension.
The total number of particles at the time moment when they
have average size ai would be approximately equal to the ratio
of the number of the primary particles to the number of the
particles in the single fractal aggregate:
N0 N0
N ðtÞ ¼ ¼  df ð8:3Þ
i ai
a1
Substituting this expression in the analytical equation for the
total number of particles at time t (Eq. (6.21)), we would get the
following equation for calculating the size of the fractal
aggregate at times much larger than the Smoluchowski time:
 
ai Pe0 1=df
¼ 1t ð8:4Þ
a1 4ssm
The radius of the primary particles in work [42] was 145 nm,
volume fraction 2 ⁎ 10− 5 and fractal dimension was 1.63. The
65
calculated Smoluchowski number was about 1 s. Deviation
from the Smoluchowski law occurs after about 100 min.
Substituting all these numbers into Eq. (8.4) would lead us to
the conclusion that gravity would cause about 1% change in the
particle size. This can be considered as the beginning of the
gravity influence on the coagulation kinetics.
We should mention here that actual experimental observed
deviation in the particle size was much larger than 1%. This
means that some of the theoretical assumptions in work [39] are
not valid. Experimentally observed kinetics of gravitational
aggregation are substantially faster than theoretical prediction.
There is one assumption that is clearly not valid. Analytical
solution [39] assumes homogeneous particles with fixed
density. It is not the case for fractals. Density changes during
coagulation. This leads to large particle volume and, conse-
quently, larger collision frequency. Apparently this effect
overweighs reduction of the density and settling speed.
This means that the approach of paper [39] should be
extended by taking into the account the variable particle density
during coagulation.
There is another possibility of comparing this experiment
with the theory. One can use Fuchs' procedure for calculating
critical size value for transition from the Brownian coagulation
to the gravitational according to the Collision frequency for
simultaneous Brownian and gravitational coagulation section.
Authors of paper [42] used this possibility without knowing that
it was suggested 50 years ago by Fuchs.
Fuchs' procedure for calculating the critical size simply
assumes that Pe = 1 and uses this equation for calculating critical
size. His calculation brought him to the conclusion that
sedimentation becomes comparable with diffusion when size is
about 1 μm.
The same calculation for the latex in work [42] yields a
slightly larger size — 2.5 μm. Critical size increases due to a
much smaller density contrast. Fuchs assumed a density
contrast of about 1, whereas it is about 20 times smaller in
work [42].
This value of the critical size that marks transition to the
gravity-influenced coagulation is very close to the experimen-
tally observed values in paper [42].
This agreement between theory and experiment allows us to
derive some conclusions regarding hydrodynamic properties of
these latex flocs. Expression for the Peclet number (Eq. (5.12))
has been derived assuming Stokes law for hydrodynamic flow
pattern generated by sedimenting flocs. This assumption is true
only when there is no flow through the flocs, their hydrody-
namic permeability equals 0.
There are other works that use the same assumption for
estimating gravity effects, for instance paper [102]. Unfortunately
this assumption is not always valid. It is known that advection is
an important feature of the fractal flocs [62].
One of the most convincing evidence of the advection is
given in the paper by Xiaoyan Li and Logan [45]. They
investigated the process of small particles adsorption by the
settling porous fractal flocs. They prepared these flocs from red-
dyed latex micro-spheres with initial size of 2.85 μm. These
flocs were introduced on top of the vessel that contained smaller
66 A.S. Dukhin et al. / Advances in Colloid and Interface Science 134–135 (2007) 35–71
fluorescent latex micro-spheres with size of 1.48 μm. Settling
aggregates sweep smaller particles.
They proved with no doubts that the advection is a very
important feature of this interaction.
First of all the measured settling velocity of the flocs was on
average nearly 3 times faster than that from Stokes' law.
Secondly, the measured collision efficiencies between
settling fractal flocs and small particles were 10 times greater
than those predicted by the curvilinear collision model (Han and
Lawler [95]) for impermeable spheres. Although greater
permeability of fractal aggregates increased the collision
frequencies between the flocs and suspended particles, the
observed β values were still 2 orders of magnitude lower than
those predicted by the rectilinear model. It is explained by larger
macro-pores of the fractal flocs, which increase hydrodynamic
permeability but decrease probability of particles collision with
the interior walls.
It should be pointed out that the primary particles size in
this work is 10 times larger than of the latex particles from
the previously described experiment by a Swiss group [42].
This might explain why advection exists in the Xiaoyan Li–
Logan experiments and does not in the experiments of the Swiss
group.
The last experimental work illustrates very clearly all
hardships of the coagulation kinetics theory for fractal flocs.
The internal hydrodynamic permeability makes hydrodynamic
flow induced by sedimentation much more complicated for
quantitative description. In addition, the interior of the flocs
might be accessible for particles. There is very little known
regarding their probability to adsorb on interior walls of the
flocs.
These complications make rigid aggregates and especially
emulsions much more attractive objects for verifying the kinetic
theory of coagulation, including gravity effects.
There is one special case of fractals — linear chain. The
fractal number approaches 1 for such structures. This type of
coagulation offers some theoretical advantages in terms of
interpretation, as it is stated in Section 6.
There are a number of experimental studies of the chain
coagulation [123,124]. Earlier works by a German–Russian
group [124] deal with homo-coagulation, chain formation by
the particles of the same material and same surface properties. A
more recent work [123] targets hetero-coagulation and chain
formation due to the difference in surface charges. There are
two types of particles that are oppositely charged.
Unfortunately authors of this recent publication are not
aware of the earlier studies on this subject, theoretical and
experimental. They are not also aware that the electrostatic
interaction might change sign even for the same sign of the
interacting objects surface charges. We discuss this aspect of the
hetero-coagulation in the next sections. Nevertheless, this paper
presents very interesting results on the chain coagulation.
Gravity is considered as an important factor that affects strongly
this process.
In particular, gravity leads to the restructuring of the large
chain aggregates with low fractal number around 1.2. It causes
their compaction. In order to confirm that gravity is the factor
indeed, authors of this work performed a test with matching
density. They used heavy water for adjusting the density of the
liquid with polystyrene particles.
Results with matching densities differ dramatically from the
original data.
First of all the coagulation process slows down, which agrees
with the theoretical prediction given in Section 6.
Secondly, aggregates become more compact. Fractal number
increases up to 1.8.
Finally, authors conclude that “…sedimentation effects, when
present, play a key role in the structure evolution….”
8.3. Gravity influence on hetero-coagulation
There are a number of systematic studies performed with the
particles of different nature and sizes, when the electrostatic
interaction is negligible, for instance papers [14,15]. The
monodisperse latex or glass spherical particles were used in
these experiments. The radius ratio was very small. The
dependence E ∼ a2− 2 (size of the larger particle) was confirmed
in [14,15]. The dependence E ∼ a1.51 (size of the smaller particle)
was established in [14,15]. The combination of the long-range
hydrodynamic interaction and the short-range hydrodynamic
interaction leads to the dependence E ∼ a1.4
1 . Thus, the theory of
short-range hydrodynamic interaction is confirmed by investi-
gations [14,15].
The direct observation of the grazing trajectory of latex
particles (0.9 μm) in the vicinity of the rising bubble with
radius 15 μm was accomplished [147,148]. The cell was
attached to the microscope stage, which was capable of moving
vertically in the same velocity as that of the rising bubbles in
the cell.
Okada et al. [147,148] visualized the trajectory of a particle
and its attachment to the rising bubble surface. They found an
agreement with the calculations with an account for pressing
hydrodynamic force (PHF). They observed a strong dependence
of the collection efficiency on the ratio of electric surface
potentials between the bubble and particles. This parameter
increases with increasing deviation between surface potentials.
It becomes 30 or more times higher when at least one of the
potentials is small.
They have not observed detachment. This, perhaps, may be
interpreted as the manifestation of the attractive electrostatic
forces at a small distance, while at a large distance there is an
electrostatic barrier.
Recent experiments of the bubble interaction with mica
surface [149] provide a rigorous experimental proof of the
charge reversal at the transition to small distance between
surfaces. This experiment employs a modified surface force
apparatus. Double layer repulsion has been detected at a
relatively large distance between surfaces. This indicates that
there is a negative surface charge at the air–water interface,
because the mica surface is negatively charged. However, when
the bubble is pressed closer to the mica, charge regulation
effects cause the reversal of the sign and the double layer force
becomes attractive. This causes the “adhesion” of the bubble to
the mica, even when a wetting film remains between them.
 A.S. Dukhin et al. / Advances in Colloid and Interface Science 134–135 (2007) 35–71
Consequently, a finite force is required to pull the bubble from
the mica.
Fielden et al. [150] observe a similar weak adhesion that may
have been due to the same effect. They make an AFM mea-
surement of the force between a hydrophobic glass sphere and an
air bubble.
Usui et al. [151,152] reported attractive forces between
dissimilarly negatively charged argon bubbles and mercury
drops.
Taking these results altogether, authors of paper [149] conclude
that: “…this observation also adds weight to the conjecture of
“contactless flotation” due to S. Dukhin and co-workers, who
suggested that particle/bubble attachment may occur due to the
presence of a force minimum at finite separation….”
8.4. Gravity role in the wet classification of micron sized
particles
Classification of suspension on the classes of narrowly
distributed, desirably almost monodispersed particles is a
challenge in many industrial processes. The classification in
liquid media (wet classification) offers advantages in some
cases, especially for small particles. Aggregative stability plays
a very important role in this process. Coagulation in either
primary or secondary minimum could preclude classification at
all. Classified particles would build aggregates, which would
lead to a broader particle size distribution. It turns out that
gravity is an essential factor that might prevent this negative
effect of the aggregative instability.
There is an old experimental study on the classification of
artificial diamonds [29]. It turns out that classification of the
small particles with dimension less than 1–2 μm differs
substantially from the classification of larger particles.
Particles smaller than 1–2 μm form hetero-aggregates with
larger particles of the main fraction. This makes their
classification very complicated, but possible at lower electrolyte
concentration due to stronger electrostatic repulsion.
In contrast to the smaller particles, the formation of a rather
narrow fraction of larger particles is possible even at higher
electrolyte concentration.
Authors of paper [29] suggested that gravity could explain
this difference in classification between smaller and larger
particles. Gravity would prevent coagulation in secondary
minimum for larger particles, as it is discussed in Section 4.
It generates hydrodynamic particle interaction when par-
ticle size exceeds some certain value given by Eq. (4.24).
Usually this critical size lies in the range of 1–2 μm. These
theoretically predicted values are in agreement with an
observed difference in classification between small and large
particles.
9. Concluding remarks
The roots of the modern theory of aggregative stability are
the DLVO description of the pair particles interaction and
Smoluchowski–Fuchs kinetic theory of the particles ensemble
evolution. Neither takes into account gravity. This certainly
67
limits the applicability of these theories because gravity would
obviously affect particle interaction and ensemble evolution of
large particles. This will occur even when the initial particle
dimension is so small that gravity role in their coagulation is
negligible. With increasing particle dimension by a process of
Brownian coagulation gravity would eventually affect pair
particles interaction, collision frequency and the evolution of
the particle size distribution.
How long is this transition time from Brownian coagulation
to Brownian-gravitational coagulation?
How does it depend on the initial mean particle dimension
and, moreover, on the initial particle size distribution?
What is the critical value of the particle size and density
volume fraction when the transition from Brownian to
Brownian-gravitational coagulation occurs?
What mechanism of gravity affects aggregative stability?
Why gravity may either enhance or reduce the aggregation rate
depending on particle properties and on other conditions?
There were attempts in the course of the last 100 years to
answer these questions and to incorporate gravity into the
aggregative stability theory. Our review of these studies allows
us to conclude that substantial progress has been achieved in
both theory and experiment. We present these works organizing
them according to the three levels of the classical stability
theory: 1) pair particles interaction; 2) collision frequency;
and 3) population balance equation.
Analysis of pair interaction clarifies whether gravity
promotes destabilization or stabilization for a given system.
There are some analytical results [30], which are less known
than the numerical approach [46,54,78].
Analytical analysis of the pair particles interaction predicts
the critical particle size above which gravity dominates over
surface forces. It looks like there is consensus that 1 μm is a
good estimate of this critical size for many real systems. This
number comes up in many independent works. When particle
size exceeds this critical value, gravity could either prevent
aggregation in secondary, and even in primary minimum,
essentially stabilizing system. On the other hand, when
electrostatic barrier is not high enough, gravity could speed
up slow coagulation, essentially destabilizing the system.
Numerical approach introduces a set of dimensionless num-
bers for achieving the same goal as the analytical one. This
method of “stability diagram” proposed in [54], initially was
applicable to an extreme case of a bi-disperse system with a
very large difference in particle dimension only. The further
development of this method [46,78] makes it possible now
to apply it to a polydisperse system. This was achieved due
to extension of theory for coupled colloidal and hydrodyna-
mic interactions over any value of particle dimension ratio α
[30,46,78].
After the mechanism of gravity effect on stability (instabil-
ity) is identified with the use of either a “stability diagram” or
critical particle size, the next step is the quantification of the
collision frequencies. There is an analytical equation for these
parameters, derived when the electrostatic interaction may be
disregarded. Although these equations are mainly valid for the
small Reynolds number [10,11,13,36,37], there are some results
68 A.S. Dukhin et al. / Advances in Colloid and Interface Science 134–135 (2007) 35–71
for the intermediate range of Re values as well [106]. A large
progress is achieved in theory for joint Brownian and
gravitational coagulation [21] without any restriction on Peclet
number and without usual assumption, known as additivity
approximation. More serious difficulties were met, when the
electrostatic interaction affects collision frequency. Here the
numerical approach became helpful [8,107].
Although the knowledge of the collision frequency yields a
crude estimate for the aggregation kinetics, variation of the
particle size in time makes this estimate very uncertain. More
sophisticated description employs “population balance equa-
tion”. Collision frequency serves as a kernel for integrals that
reflect evolution of the particular particle size fraction.
There are two independent analytical solutions of the population
balance equation with gravity [38–40] for the fast coagulation. It
estimates the critical time for the transition from Brownian to
gravitational coagulation with the following equation:
ssm
scr c
Pe0
The initial analytical solutions found confirmation in later
numerical solutions [23]. This work of Davis' group is a
culmination in characterizing gravity influence on rapid
coagulation. They succeeded to describe the evolution in time
for droplet size distribution even when it becomes very broad
during a rather long time. Unfortunately, this success is valid
mainly for mini-emulsion.
This progress can be extended towards suspensions, when at
least 2 conditions are satisfied:
• Theory of pair interaction in reviewed theories disregards a
possible surface heterogeneity of solid particles [153,154].
The incorporation of the surface heterogeneity in the stability
diagram and in collision frequency is a special problem,
which is not considered in this review. The collision
frequency theories usually utilize an assumption that a
particle is spherical and its surface is homogeneous and
smooth. As soon as all these assumptions do not cause
essential errors, the equations for collision frequencies may
be used as kernels for the population balance equation, when
it is applied to suspensions.
• The second condition is that the density of the formed ag-
gregates is known and it does not change with the aggregate
increase. Perhaps, it is possible when the aggregates are
dense. Another example is chain aggregates with small fractal
number [41].
On the early stage of destabilization the fractals are not
formed. Accordingly, this review is addressed to this stage with
respect to suspension.
Our review of many studies dedicated to the coagulation
kinetics allows to conclude that there is a substantial progress
achieved in both theory and experiment. From the theoretical
viewpoint, there are several different types of systems de-
pending on the structure of aggregates. Historically the first one
corresponds to the dense rigid aggregates or coalescing emulsion
droplets. More recently another type of the system with porous
aggregates that include substantial amount of dispersion media
attracts more attention. It is area of fractal systems. In principle,
the first type of system could be considered as extreme fractal
dispersion with fractal dimension 3. However, the introduction
of the dense aggregate as a new particle with the same density
and other properties of primary particles leads to so many
theoretical simplifications that this model certainly deserves the
right for independent existence.
There is also a strong motivation for creation of the kinetic
theory for such fractal systems from the experiment. The most
sophisticated experiment on this field [42] has been performed
for these fractals. Unfortunately, existing theories are not
applied directly for describing this experiment because they do
not take into account variation of the aggregates density and
volume fraction with size. This experiment indicates that
gravity might play an even more earlier and important role for
fractal than for dense aggregates.
There are also experimental works on fractals with
advection. Creating of the kinetic theory for these fractals is a
much more complicated task.
At the current stage, existing theory might be most useful for
emulsion science. Modeling of the emulsion evolution may
result in the quantification of the emulsion film stability,
namely, establishment of the coalescence time dependence on
the physico-chemical properties of the surfactant adsorption
layer, its structure and the droplet dimension. This quantifica-
tion can form the basis for optimizing selection of demulsifiers
and their synthesis for emulsion technology applications instead
of the current empirical approach.
List of symbols
Symbol Meaning
A Hamaker constant
a1 Primary radius
ai Radius of the i-th fraction of the particles, or of the
aggregate consisting of i primary particles
acr_2 Critical particle radius, above which gravity prevents
coagulation in secondary minimum
acr_barr Critical particle radius, above which gravity eliminates
potential barrier of the surface forces
B Hamaker constant of the completely retarded surface
forces
b Distance between small particle and center sedimen-
tation line of the larger one.
D Diffusion coefficient
Dij Diffusion coefficient of the relative Brownian motion
of the particles from the i-th and j-th fractions, or of
the aggregates containing i and j numbers of primary
particles
d1 Primary diameter
di Diameter of the aggregate consisting of i primary
particles
dmax Maximum particle diameter
df Fractal dimension
dB–g Critical diameter of the transition from Brownian to
gravitational coagulation
 A.S. Dukhin et al. / Advances in Colloid and Interface Science 134–135 (2007) 35–71 69

Fe Electrostatic surface interaction force Δρ Density contrast

Fm Molecular surface interaction force σ Geometric standard deviation
Fg Gravity force τsm Smoluchowski time
Fb Buoyant force τsd Sedimentation time
Fh Hydrodynamic drag force τB–g Critical time of the transition from Brownian to
Fdet Detachment force gravitational coagulation
Fs Total surface interaction force ψ Electric surface potential
Gr Gravity number, which is identical to the Peclet φ volume fraction of dispersed phase
number φ(v) Volume fraction of the aggregates with volume v
g Earth gravity acceleration
h Distance between particles surfaces
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