An Analytical study of effects of particle force fields on Brownian

coagulation of ferromagnetic nano particles

ROHIT KASLIWAL (08D02025)
Chemical Engineering,
Indian Institute of Technology,
Powai, Mumbai
I. ABSTRACT
Most theoretical predictions of the rate of Brownian-
induced coagulation have considered the effects of
different force fields such as Van der Waals and/or
electrostatic forces. Fe
3
O
4
nano particles possess the
property of ferromagnetism. On addition of
surfactant Poly acrylic acid (PAA) some other force
fields like steric repulsion and/or magnetic interaction
also come into account. This paper quantifies the
effects of these interaction force fields and compare
with simple Brownian motion.
This paper discusses the production of Fe
3
O
4
nano
particles and how addition of surfactant (PAA)
decreases the size from 3-19nm to 2-13nm. This has
been explained using mechanistic model comprising
nucleation, diffusion growth, coagulation and
Ostwald ripening. Only theory has been presented
related to these processes. Collision frequency in case
of coagulation can be modified in presence of external
force field or any inter particle interaction.
The results of analysis show that in comparison with
the flow of particles in the absence of any external
force field, we can see the result has been modified by
a correction factor, W, which comes in the
denominator. The potential energy, (r), can be
positive or negative depending on the different type of
force field, causing attractive or repulsive force
respectively. When (r) is positive (repulsion) like in
case of steric or electrostatic field, W is less than 1
and hence rate increases and opposite when (r) is
negative (attraction). Various interactions potential
have been compared analytically.
II. INTRODUCTION
This report gives deals with two major topics
modeling of nano particles through various
mechanisms and effect of different external force
fields on coagulation rate.
A. Modeling of Nano particles
Iron oxide (Fe
3
O
4
, magnetite) shows super Para
magnetism in the size-range of <20 nm. This
property of iron oxide can be used in many
applications like magnetic resonance imaging
(MRI
VI.5)(5)
(Jun, Y. W, 2008), hyperthermia,
magnetic cell sorting
(6)
(Owen, C. S, 1983) etc. Iron
oxide nano particles can be made by many different
chemical processes like chemical co-precipitation,
thermal decomposition, reverse micelle etc. Among
all the processes the chemical co precipitation is
widely used.




For using the nano particles in real applications,
control on size-ranges are very important and
difficult to achieve. Stability of colloidal dispersion
of the particles is also an important issue for in-
vivo use.
The bulk co-precipitation method produces bare
Fe
3
O
4
nano particles of 3-19 nm in size. On
addition of surfactant (PAA) the size-range goes
down to 2-13 nm. We tried to explain this process
by a mechanistic model considering nucleation,
diffusion growth and coagulation. Classical
nucleation theory
(7)
(Randolph, A. D., 1988) has
been assumed for finding the nucleation rate and
for coagulation Smoluchowskis equation has been
used in modified form
(1)
(Friedlander, S. K, 2000).
In this study we tried to understand and quantify
the effect of surfactant on coagulation and hence
their effect of the final size-distribution of nano
particles.
The formation of spherical nano particles by
synthesis in bulk solvent, method of chemical co
precipitation in this case, can be thought of as
combination of various steps. These steps may
include reaction, nucleation, growth, coagulation
and Ostwald ripening.
B. External force fields
The coagulation process depends on collision
frequency which is modified when particles exert
forces on one other
(2)
(WCH,1999). The common
forces are van der Waals force which is always
present and coulomb forces which is present when
the particles are charged.
This report is organized in following manner. A
brief background to the origin and growth of
ferromagnetic nano particles are presented in
section III. Section B of Theory outlines the
different force fields. After which results and
conclusions are presented in section IV along with
nomenclature and references in section V and VI
respectively.
III. THEORY

A. Modeling of the system
1) Reaction
In general, precipitation reactions are extremely
fast and can be treated as instantaneous.
Without coating agent:
3 2
3 2 3 4 2
2 8 2 ( ) ( ) 4 Fe Fe OH Fe OH Fe OH Fe O H O
+ +
+ + + +

With coating agent:
3 2
3 2 3 4 2
2 8 2 ( ) ( ) 4 Fe Fe PAA OH Fe OH Fe OH PAA Fe O H O
+ +
+ + + +

An aqueous solution containing 2:1 mole of Fe
3+

and Fe
2+
cations reacts with base and forms
intermediate product of ferric and ferrous
hydroxides. These intermediate products (insoluble
in water) react to form Fe
3
O
4
particles in N
2

atmosphere. In presence of coating agent, Poly
(acrylic acid) or PAA, the ferric ion-PAA
conjugates forms. This conjugate reacts with base
and forms PAA coated Fe
3
O
4
particles

2) Nucleation
Classical nucleation theory for homogeneous
nucleation has been used to calculate the nucleation
rate
( )
( )
( ) ( )
hom
2
3 2
3
2
1 3
1 1 3 2
2
16
2 exp
3 ln
2
o
m m
m
I
v v p
n v
kT
kT S
mkT
o to
t
=
( ( (
( ( (
( ( (

(1)
3) Diffusion control growth
For a system with instantaneous surface reaction,
the growth rate of particle is controlled by rate at
which solute diffuses in the continuous solvent
medium. The growth can be represented from
simple mass transfer equation. Nanocrystals have
high surface energy, so that surface reaction can be
reasonably assumed to be fast relative to liquid
phase diffusion. The growth can be represented
from simple mass transfer equation
( )
3
2
4
(4 )
3
i
m A
D d r
r C C
r dt V N
t
t
| |
| |
=
| |
\ .
\ .
(2)
4) Ostwald Ripening
Since smaller particles have higher solubility, they
dissolve in solution converting back to monomer
molecules. These monomer molecules diffuse in
the medium and grow over the existing particle
thereby further increasing the size of particles.
Coagulation happens faster than Ostwald ripening.
Time scale of Ostwald ripening is very large
compared to other processes listed here hence for
present simulation it has not been considered. It is
also expected as it has very less solubility in water.
5) Coagulation
In a bulk system, it can be assumed that particles
move in a random fashion and collide with each
other. These collisions will contribute to growth of
particle. The growth rate of a particle is estimated
using the Brownian collision frequency, as given
by famous Smoluchowskis equation given as
8
3
B
p
k T
q

= (3)
B. External force fields
We consider a particle of radius ai on which a
particle of radius aj is diffusing and the particle of
radius ai exerts a force for which the acceleration
of A(r) on the particle of radius aj. Assuming the
spherical symmetry around the particle of radius ai,
the diffusional flux of aj particles to the surface of
the ai particles is given by
( )
( )
dn A r
J r D n
dr f
= +

(4)
In steady state, the number of particle crossing each
spherical surface concentric with a central particle
is constant and given as
2
2
2
4
( )4
4
r J const F
dn A r r n
D r
dr f
t
t
t
= =
= +
(5)
It is more convenient to express this in terms of
potential function as a function of separation
distances, (r), which is given as
2
4 ( )
B
dn n d
F r D
dr k T dr
|
t = +

(6)
Assuming F constant if we solve this differential
equation we obtain,
2
( ) ( )
exp( ) exp( )
( )
exp( )
4
r
B B
B
n
r r
F
k T k T r
n dx
k T D x
| |
|
t

+
}
(7
2
4 ( )
( )
exp( )
( )
4 ( )
i j
i j
B
i j
a a
i j
Dn a a
F
r
k T
a a dx
x
Dn a a
W
t
|
t

+
=
+
+
=
}
(8)

Comparing this equation, with the flow of particles
in the absence of any external force field, we can
see the result has been modified by a correction
factor, W, which comes in the denominator.
The present system is coated and uncoated iron
oxide in water. So, we choose the forces which are
relevant to this system. The total potential energy
has been calculated by summing up the effect of
the following interactions:
1) Van der Waal forces
Generally present in all colloidal system. This is an
attractive interaction. The van der Waals
interaction energy, V
vdW
is given by
2
2 2
2 2 2
2 4
2 ln 1
6 4
vdW
A a a a
V
r r a r

(
| |
= + +
`
| (

\ .

)
(9)
1
0
( )
exp
6
B
Af x
W dx
k T
(
=
(

}

(10)
r
x
a
=

( )
( )
2 2
2
2
( ) ln 1
2
2 1
x x
f x x
x
(
( = + +
(













Figure 1Schematic representation of two particles
separated by surface to surface distance s and
centre to centre distance r

2) Steric forces
This interaction is repulsive in nature. When a
coating agent is present over the nano particles, the
steric interaction is possible. Steric repulsion
energy between coated particles is given as,
2
1 2 1
2 ln
2
1
2
s
l t l
V d
l
t t
t
(
| |
( |
+ +
=
( |
( |
+
(
\ .

(6)

For
( )
1
2
s
u
>


0
s
V = for
( )
1
2
s
u
s
,





3) Magnetic forces
This is an attractive interaction. We have seen
experimentally, the iron oxide particles are super-
paramagnetic in nature. So we consider the
magnetic interaction in this case. The magnetic
interaction potential (V
m
) between two magnetic
particles is calculated based on saturation
magnetization of the coated particles at the
maximum applied field
(3)
(Rosensweig, 1985). This
magnetic interaction potential is given as,
( )
6 2
3
1
72
o s
m
B
d M
V
k T
r d
t
=
+


4) Electrostatic forces
The electrostatic interaction is repulsive in nature.
This interaction occurs as the iron oxide particles
have positive surface charges. Electrostatic
repulsion energy (V
e
) between two particles is
calculated using the expression
(8)
(Parker C. reist)
below
( ) { }
2 1 2
1 2
4 ln 1 exp
e o o
r r
V s
r r
t k = ee +
+


0.5 5 dk)
( )
2
1 2 1 2
1 2
exp
4
B
e o
s
k T
V r r YY
e s r r
k
t

| |
= ee
|
+ +
\ .

0.5 5 dk(
( )
1
2
2
2
8tanh( )
4
2
1 1 tanh ( )
4
1
o
B
i
i o
B
i
e
k T
Y
r e
k T
r

k
k
=
(
+ (
+ (



The net interaction potential, (r) is thus,
( )
vdw m s e
r V V V V | = + + +


IV. RESULTS AND DISCUSSIONS
A. Van der Waal forces
The correction factor W
-1
was plotted against
A/KT for different substances.
Figure 2 shows that W is less than 1 for various
substances which supports the argument given for
forces attractive in nature

Figure 2 Increase in rate of collision of particles of equal
diameter resulting from action of Van der Waal forces



The above figure is a plot of correction factor vs
diameter of Fe
3
O
4
. Rate is constant i.e it is not a
function of diameter but a function of particle
property which can be seen in the above figure. It
should be noted that W is less than 1.







B. Magnetic forces
Being attractive in nature, it increases the rate of
collision of particles which can be deduced using

Figure 3. W (the correction factor comes out to be
less than 1. For magnetic particles at room
temperature d<= 7.8nm. This estimate shows that
normal magnetic fluids having particle size up to
range 10 nm are on the threshold of agglomeration.



Figure 3 Increase in rate of collision of particles of equal
diameter resulting from action of magnetic forces
C. Steric Repulsion
This interaction is repulsive in nature. When
coating agent (here PAA) is present over nano
particles, the steric interaction is possible. For
grafting density () equal to 10
18
and o equal to 2
nm, the correction factor W has been plotted and
from Figure 4, it should be noted that value of W is
very high for small particles. So these Fe
3
O
4

particles which posses ferromagnetism has a very
low rate of coagulation in presence of high steric
interaction

Figure 4 Decrease in rate of collision because of steric
interaction






The correction factor W depends on length of
absorbed moleculeo .

Figure 5 explain the difference between various o
like 2nm and 0.5nm. As length of absorbed
molecule decreases, the correction factor decreases.



Figure 5 Effect of length of absorbed molecule on W
D. Electrostatic forces
The electric interaction is repulsive in nature. This
interaction occurs as iron oxide particles have
positive surface charges. Using the Debye length to
be equal to 1nm, the plot of correction factor W
and diameter was obtained as shown in Figure 7.
Being repulsive in nature, the interaction potential
comes out to be positive and hence W comes out to
be less than 1 (actually coming out to be nearly
equal to 1).
E. Overall effects
The main aim of this study was to understand
analytically the effects of different particle force
fields or interaction effects of different forces on
rate of collision and to compare them with the
simple Brownian motion.


















Figure 6 Net Interaction Curve

Figure 7 Rate of collision for particles due to electrostatic force.

For Brownian motion, the correction factor was
equal to 1 whereas for attractive forces like Van der
Waal and magnetic forces W comes out to be less
than 1 and hence collision rate increases. The
repulsive forces such as steric interaction and
electrostatic forces have their correction factor
greater than 1 and so the collision rate in case of
these repulsive forces decreases.
Figure 6 is the net interaction curve which is
algebraic sum of Van der Waal interaction energy,
magnetic energy, steric repulsion and electrostatic
energy. It is seen that the net potential energy curve
represents an energy barrier of more than 10 kT.
Because this energy exceeds the average thermal
energy of an particle by an order of magnitude,
statically few particles will cross the barrier, and
the rate of agglomeration should be negligible.
Figure 8 compiles all the interaction forces and
their correction factor variation with diameter of
the particle. Particles were considered to be of the
same size.


























Figure 8 Comparison of correction factor for
different forces against simple Brownian
V. NOMENCLATURE
o Surface tension of water
m mass of molecule
v
m
volume of a molecule
k Boltzmann constant
T Temperature
S Saturation ratio
N
A
Avagadros no.
D Diffusivity
C Concentration of bulk
C
i
Concentration at interface
q
p
Collision frequency
Viscosity of solvent
f friction coefficient
a
i
,a
j
Radius of particles
A
eff
Hamaker constant
o
Permeability of free space
M
s
Saturation magnetization
d Average core diameter
Grafting density
s surface to surface separation
r centre to centre distance
potential energy
V
vdw
Van der waal potential
V
s
Steric energy
V
m
Magnetic energy
V
e
Electrostatic potential














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4) Russel, W. B, Saville D. A, Schowalter, W. R.
Colloidal Dispersions; Cambridge University
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V. J. Colloids Surf. A. 1998, 144, 115-125
7) Randolph, A. D.; Larson, M. A. Theory of
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8) Parker C. Reist, Aerosol science and
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