Journal of Membrane Science 192 (2001) 55–70

Mathematical model for encapsulation by

interfacial polymerization
Jiang Ji a,∗ , Ronald F. Childs b , Mahesh Mehta a
a Koch Membrane Systems Inc., 850 Main Street, Wilmington, MA 01887-3388, USA
b Department of Chemistry, McMaster University, Hamilton, Ont., Canada L8S 4M1
Received 11 December 2000; accepted 25 April 2001

Abstract
A general model for encapsulation by diffusion- and reaction-controlled interfacial polymerization under nonsteady-state
boundary conditions has been developed. Special models for either diffusion-controlled or reaction-controlled interfacial
polymerization under both steady- and nonsteady-state boundary conditions can be obtained by simplifying the general
model. These special models agree with the similar models in the literature. The general model developed is consistent with
the experimental data reported in the literature. This work significantly extends existing theories for the encapsulation by
interfacial polymerization and provides an important guideline for the effective control of the thickness and porosity of the
capsule wall prepared by interfacial polymerization. © 2001 Elsevier Science B.V. All rights reserved.
Keywords: Microcapsules; Controlled release; Encapsulation; Interfacial polymerization; Modeling

1. Introduction very important to the effective control of capsule wall

Microcapsules consisting of a core (liquid or solid)
and a permeable or non-permeable wall have been
widely used in release and transfer control [1–3]. The
capsule core may contain active compounds such as
catalysts, drugs, anti-fouling compounds or toners,
which are surrounded by a suitable wall material that
regulates release. The controlled release of the capsule
contents strongly depends on capsule wall thickness
and porosity [4]. Interfacial polymerization is one of
most important methods used to make microcapsules
[1–3]. A clear understanding of how a variety of fac-
tors, such as monomer concentration, diffusion and
interfacial reaction, influence the capsule formation is
∗ Corresponding author. Tel.: +1-978-694-7264;
fax: +1-978-694-7015.
E-mail address: jij@kochind.com (J. Ji).
structure (thickness and porosity) and release perfor-
mance. Although a large amount of work has been
reported in this area, no satisfactory general model is
available [1–9].
Pearson and Williams [6] studied encapsulation
involving the interfacial polymerization of an isocy-
nate with a diol. They developed a theoretical model
that was solved numerically for both steady- and
nonsteady-state interfacial polymerizations involving
a consideration of monomer diffusion and the rate of
interfacial reaction. The model was consistent with
the experimental data obtained in the early stages of
the polymerization. The complexity of the numeri-
cal method used has reduced the significance of the
model, as a result it is not commonly used.
Warburton [5] developed an alternative model for
encapsulation involving multiple emulsions. This
model assumes that the physical chemistry of curved

0376-7388/01/$ – see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 3 7 6 - 7 3 8 8 ( 0 1 ) 0 0 4 9 5 - 1
56 J. Ji et al. / Journal of Membrane Science 192 (2001) 55–70
Nomenclature
A0 constant defined in Eq. (8)
((m4 kg)/(kmol2 s))
B0 constant defined in Eq. (9)
((m5 kg)/(kmol2 s))
C0 constant defined in Eq. (10)
((m7 kg)/(kmol2 s))
CA (r, t) concentration of monomer A in the
capsule wall at position r and time t,
as shown in Fig. 1 (kmol/m3 )
CA (r0 , t) concentration of monomer A at the
outer surface of the capsule wall at
time t, as shown in Fig. 1 (kmol/m3 )
CB (Ri , t) concentration of monomer B in the
capsule core at time t, as shown in
Fig. 1 (kmol/m3 )
D diffusion coefficient of monomer A
in the capsule wall (m2 /s)
D0 constant defined in Eq. (11)
((m8 kg)/(kmol2 s))
DM constant defined in Eq. (4)
(D M = D P M U /ρ P ) (m5 /(kmol s))
E0 constant defined in Eq. (12)
((m9 kg)/(kmol2 s2 ))
F0 constant defined in Eq. (13)
((m6 kg)/(kmol2 s2 ))
k apparent reaction rate constant
(k = δk r ) (m4 /(kmol s))
kI constant defined in Eq. (2)
(m7 /(kmol2 s))
kr second order reaction rate
constant (m3 /(kmol s))
K partition coefficient of monomer A
between the capsule wall and the
continuous aqueous phase
Mi molecular weight of component
i (kg/kmol)
P average degree of polymerization
r radial coordinate normal to the
spherical surface, as shown in
Fig. 1 (m)
S membrane area (m2 )
t polymerization time (s)
vP volume of the capsule wall,
zone II in Fig. 1 (m3 )
X thickness of the capsule wall (m)
Greek symbols
β ratio of water molecule to monomer
A diffused together from the outer
surface of the capsule wall to the
reaction zone as shown in Fig. 1
δ thickness of the reaction zone,
as shown Fig. 1 (m)
γ reaction ratio given in Eq. (34)
ϕ volume fraction
ρP density of the capsule wall formed by
the interfacial polymerization (kg/m3 )
Subscripts
0 reaction- and diffusion-controlled
polymerization
A monomer A
B monomer B
D diffusion-controlled polymerization
max maximum value
min minimum value
P average polymer
R reaction-controlled polymerization
U repeat unit of the polymer
V void
W water
Z a small molecule formed from
each condensation reaction
surfaces can be related to that of planar surface. In this
model, both the diffusion and interfacial reaction are
again considered. Instead of the thickness of capsule
wall, the interface rigidity, which is a function of the
degree of crosslinking, was used to characterize the
capsule formation. Although an analytical solution
was obtained by Warburton, no direct correlation of
the interface rigidity to the capsule wall thickness was
given. This limits the usefulness of the model in that
the release rate of the active core material across the
capsule wall is inversely proportional to the capsule
wall thickness [4].
Janssen and te Nijenhuis [7–9] have described an
encapsulation technique involving the polyconden-
sation of terephthaloyl dichloride with diethylenetri-
amine at the interface of an oil-in-water emulsion.
They considered a spherical capsule as a plane and
proposed a diffusion controlled model to describe
the encapsulation. This model was in agreement with
 J. Ji et al. / Journal of Membrane Science 192 (2001) 55–70
experimental results for short polymerization times
with the thickness of the capsule wall linearly increas-
ing with the square root of polymerization time. How-
ever, this model incorrectly predicts that the capsule
wall thickness approaches infinity when the polymer-
ization time approaches infinity. This is a result of us-
ing a planar geometry instead of a spherical one in that
a material balance on the core material is impossible.
A new general model is needed which can correctly
handle the mass balance of the core material to
overcome the problems discussed above. More
importantly, such a theoretical model should correctly
describe and predict the encapsulation by interfa-
cial polymerization not only in the early stages but
also in the entire course under either nonsteady- or
steady-state boundary conditions. Furthermore, the
new model should be simple and easy to use.
Recently, we reported the fabrication of thin-film
composite polysulfonamide membranes by interfa-
cial polymerization of an aliphatic diamine with an
aromatic disulfonyl chloride [10]. The thickness of
the thin-film barrier layer formed by interfacial poly-
merization was found to first increase and then level
off with polymerization time. In order to describe
the formation of the flat sheet thin-film composite
membrane, a general model was developed which
considered both diffusion- and reaction-controlled in-
terfacial polymerization under nonsteady-state bound-
ary conditions [11]. The model was in agreement
with the experimental data, and predicted a result that
would be expected at infinitive polymerization times.
In the current work, the same methodology developed
in our previous work [11] is used to develop a general
model for the encapsulation by both diffusion- and
reaction-controlled interfacial polymerization under
nonsteady-state boundary conditions. The model
developed is fitted with the experimental data reported
by Janssen and te Nijenhuis [9].
2. Theory
2.1. A general model for both reaction- and
diffusion-controlled interfacial polymerization
under nonsteady-state boundary conditions
2.1.1. Model assumptions
In an encapsulation, the capsule core is first loaded
with a monomer, such as a diacid chloride (here called
57
monomer B) in an organic solvent, then immersed
in an continuous aqueous phase containing a second
monomer, such as a diamine (here called monomer A)
[7–9]. Typically, the organic capsule core is insoluble
in the continuous aqueous phase. Reaction between
monomers A and B to form a polymer occurs at the
interface between isolated organic and continuous
aqueous phases. The actual process of the encapsula-
tion by interfacial polymerization is complex. Thus,
some simplifying assumptions are made to facilitate
model development and solution. The assumptions
are the followings.
1. The system considered here is the encapsulation
of a dispersed organic phase containing monomer
B by interfacial polymerization with monomer A
in a continuous aqueous phase. The concentration
of monomer A in the continuous aqueous phase is
uniform [7–9,11]. The concentration of monomer
B is uniform in the organic capsule core up to the
reaction zone and constantly changes with time
during the polymerization [7–9,11]. Reaction takes
place in a reaction zone of constant thickness,
δ, in the organic phase adjacent to the interface
[11–19].
2. The capsule wall formed by interfacial polymer-
izaton has a spherical geometry with an inside
diameter, R, and outside diameter, r0 . The capsule
wall consists of micro voids and a dense polymer
phase [7–9].
3. Only monomer A, with associated water molecules,
is limited by diffusion from the outer surface of
capsule wall to the reaction zone close to the inner
surface of the capsule wall [7–9]. All of monomer
A arrived at the reaction zone reacts with monomer
B to form a polymer. The diffusion coefficient of
monomer A, with the associated water molecules,
is assumed to be constant in the newly formed
polymeric capsule wall [7–9,11–13], and the diffu-
sion rate of monomer A in the micro voids is much
faster than in the dense polymer phase [7–9].
4. If the flat sheet geometry in the previous work
[11] is replaced with the spherical geometry, the
assumptions (2, 3, 4, 7, 9, 10) made in the pre-
vious work regarding the model development are
still valid for the present work.
A detail discussion on the model assumptions is
given in our previous work [11].
58 J. Ji et al. / Journal of Membrane Science 192 (2001) 55–70
Fig. 1. A schematic representation of the model at time t.
2.1.2. Model development
In terms of the model, some of the key terms and
a schematic presentation is given in Fig. 1. A full
list of symbols is given at the end of the paper. The
coordinate r is fixed at r = 0 at the center of the cap-
sule core. As the polymerization proceeds, a spherical
thin-film shell forms, and the reaction zone which
is initially located at r = r0 , is found at r = R(t)
at time t. Monomer A first partitions into the newly
formed polymeric capsule wall and then diffuses
to the reaction zone where a second order reaction
occurs. A typical concentration profile at time t, is
illustrated in Fig. 1. Since R(t) varies with time, this
becomes a moving boundary problem.
The following equations can be formulated based on
the assumptions given above. At time t, the formation
of polymeric capsule wall due to the second order
reaction is given by
PρP ϕP dvP
= kr CA (R, t)CB (R, t)δS (1)
MP dt
where P is the average degree of polymerization, ρ P
the density of the newly formed polymeric capsule
wall, MP the average molecular weight of the polymer,
dv P /dt is the volume growth rate of the capsule wall,
kr the second order reaction rate constant, CA (R, t) is
the concentration of monomer A in the reaction zone
at time t, CB (R, t) the concentration of monomer B
that reacts with monomer A in the organic phase, δ
the reaction zone thickness, S = 4π R 2 is the capsule
area, and dvP = −S dR is the volume of the newly
formed capsule wall. The minus sign is due to the fact
that the capsule wall grows towards the center in an
opposite direction of the r-axis, because dv P is always
larger than zero. The average molecular weight, MP , is
defined in the same way as in our previous work [11].
Substitution for dv P in Eq. (1) and rearrangement
then gives
dR kI
− = CA (R, t)CB (R, t) (2)
dt ϕP
where dR/dt is the growth rate of the capsule wall
formed by interfacial polymerization. On the basis of
 J. Ji et al. / Journal of Membrane Science 192 (2001) 55–70 59

assumption 3, the growth rate must be related to the D0 = ϕP2 kI CB (r0 , 0)MU r04 − ϕP3 kI ρP r04 (11)
diffusion rate of A to the reaction zone, expressed as
E0 = DM CA (r0 , 0)kI r03 [ρP ϕP − CB (r0 , 0)MU ] (12)
PρP ϕP dvP
F0 = DM CA (r0 , 0)kI ϕP ρP (13)
MP dt
S[CA (R, t) − CA (r0 , t)] Substitution of Eqs. (2) and (7) into Eq. (4) and rear-
=− (3)
((R − r0 )ϕV )/DV + ((R − r0 )ϕP )/DP rangement give a growth rate of the capsule wall as

As discussed in our previous work [11], Eq. (3) is dR E0 − F0 R 3

= (14)
simplified to the following equation: dt A0 R 4 + B 0 R 3 + C 0 R + D 0
dR DM [CA (r0 , t) − CA (R, t)] Substitution of Eq. (14) into Eq. (2) and rearrangement
− = 2 (4) gives
dt ϕP R − r0
ϕP
Similarly, a volume fraction of polymer in the capsule CA (R, t) = −
kI CB (R, t)
wall is obtained as follows [11]:
E0 − F 0 R 3
M U ρW × (15)
ϕP = (5) A0 R 4 + B 0 R 3 + C 0 R + D 0
βMW ρP + MU ρW
Defining α = r0 /Rmin and ω = R/Rmin , integration of
and a volume fraction of voids in the capsule wall is Eq. (14) gives a relation between the reaction time, t,
given as follows, ϕV = 1 − ϕP . and the radius of the newly formed capsule wall, R, as
A material balance on monomer B in the capsule
A0 Rmin
5 B0 Rmin
4
core gives t= I4 + I3
E0 E0
4πR 3 4π(r03 − R 3 )ϕP ρP P C0 Rmin
2
D0 Rmin
CB (R, t) + + I2 + I1 (16)
3 3MP E0 E0
4πr0 CB (r0 , 0)
3
where
= (6)
3
ω y4 1
Under nonsteady-state conditions, Eq. (6) determines I4 = dy = (α 2 − ω2 )
α 1−y
3 2
CB (R, t), the concentration of monomer B at (R, t).  
1 (1 − α) /(1 + α + α 2 )
2
The first term on the left hand side of Eq. (6) is the + ln
amount of monomer B (kmol) left in the capsule core 6 (1 − ω)2 /(1 + ω + ω2 )
 
at time t, the second term is the amount of monomer B 1 2ω + 1
+ √ arctan √
(kmol) converted into the polymer. The right hand side 3 − 3
is the amount of monomer B (kmol) in the dispersed  
1 2α + 1
organic phase at time t = 0. − √ arctan √ (17)
3 − 3
Rearrangement of Eq. (6) gives

ω
r3 (r 3 − R 3 ) ϕP ρP y3
CB (R, t) = 03 CB (r0 , 0) − 0 3 (7) I3 = dy = α − ω
R R MU α 1−y
3
 
In order to simplify the above equations, we define the 1 (1 − α)2 /(1 + α + α 2 )
+ ln
following constants: 6 (1 − ω)2 /(1 + ω + ω2 )
 √ 
1 ω 3
A0 = −ϕP3 kI ρP (8) − √ arctan
3 −2 −ω
B0 = ϕP3 kI ρP r0 + ϕP DM MU (9)  √ 
1 α 3
+ √ arctan (18)
C0 = ϕP3 kI ρP r03 − ϕP2 kI CB (r0 , 0)MU r03 (10) 3 −2 − α
60 J. Ji et al. / Journal of Membrane Science 192 (2001) 55–70

ω  
y 1 (1 − α)2 /(1 + α + α 2 ) 2.2.1.1. Reaction-controlled interfacial polymeriza-
I2 = dy= ln
α 1−y (1 − ω)2 /(1 + ω + ω2 )
3 6 tion. If the rate of interfacial polymerization is much
  slower than that of monomer diffusion (k I  D M ),
1 2ω + 1
− √ arctan √ the growth rate of the capsule wall is controlled
3 3 by the rate of interfacial reaction. In this situation,
 
1 2α + 1 CA (R, t) ≈ CA (r0 , t), and Eqs. (1)–(22) are still
+ √ arctan √ (19) valid. However, in Eq. (16) only a term related to the
3 3
interfacial reaction remains, thus we have A0 /E0 ≈ 0,

  C0 /E0 ≈ 0, D0 /E0 ≈ 0, and
ω
dy 1 (1 − α)2 /(1 + α + α 2 )
I1 = = ln B0 ϕ P MU BR
α 1−y
3 6 (1 − ω)2 /(1 + ω + ω2 ) = =
 √  E0 kI CA (r0 , 0)r0 [ϕP ρP − CB (r0 , 0)MU ]
3 E R
1 ω 3 (23)
− √ arctan
3 −2 − ω
It should be noted that Eqs. (7), (14)–(16), and (23)
 √ 
1 α 3 can be independently derived from Eqs. (2) and (6)
+ √ arctan (20) based on the assumptions specified in this section and
3 −2 −α
the general assumptions made in Section 2.1.1.
The thickness of the newly formed capsule wall is
2.2.1.2. Diffusion-controlled interfacial polymeriza-
given by X = r0 − R. When the reaction time, t,
tion. If the rate of interfacial reaction is much faster
approaches infinity, CB (R, ∞) approaches zero, the
than that of monomer diffusion (D M  k I ), the
capsule wall approaches the maximum thickness, as a
growth rate of the capsule wall is controlled by the
result of R approaching a minimum value, Rmin
rate of monomer diffusion to the reaction zone. Under
 1/3   this condition, C A (R, t) ≈ 0, and Eqs. (3)–(22) are
E0 CB (r0 , 0)MU 1/3
Rmin = = 1− r0 (21) still valid. However, in Eq. (16) only terms related
F0 ϕP ρ P
to monomer diffusion remain, and are changed as
Rmin can be obtained experimentally, and as such follows
Eq. (21) is important as it correlates Rmin with E0 ϕP3 ρP
A0
and F0 . And the maximum capsule wall thickness is =−
obtained as follows, Xmax = r0 − Rmin . E0 DM r03 CA (r0 , 0)[ϕP ρP − CB (r0 , 0)MU ]
The reduced thickness of the newly formed capsule AD
= (24)
wall is defined as ED
X r0 − R
= (22) B0 ϕP3 ρP
Xmax r0 − Rmin =
E0 DM r02 CA (r0 , 0)[ϕP ρP − CB (r0 , 0)MU ]
X/Xmax is also the reaction conversion of monomer B
BD
at reaction time t. = (25)
ED
2.2. Special models C0 ϕP2 CD
= = (26)
E0 DM CA (r0 , 0) ED
Several special models can be derived by simpli-
D0 ϕP2 r0 DD
fying the above general model. =− = (27)
E0 DM CA (r0 , 0) ED
2.2.1. Interfacial polymerization under It should be noted that Eqs. (7), (14)–(16) can be inde-
nonsteady-state boundary conditions pendently derived from Eqs. (4) and (6) based on the
Under nonsteady-state boundary conditions, the assumptions specified in this section and the general
following special models can be obtained. assumptions made in Section 2.1.1.
 J. Ji et al. / Journal of Membrane Science 192 (2001) 55–70 61

2.2.2. Interfacial polymerization under the condition ϕP (r0 − R) ϕP X

t= =
of constant concentration of monomer B in the kI CA (r0 , 0)CB (r0 , 0) kI CA (r0 , 0)CB (r0 , 0)
capsule core (32)
If the amount of monomer B converted to the poly-
mer is much less than that left in the capsule core, then Mathematically, this result is the same as the solid
the concentration of B in the capsule core is essen- spherical model developed by Neogi and Allan [21,22]
tially constant. Under this condition, the second term for the controlled release of pesticides by decomposi-
on the left hand side of Eq. (6) is negligible compared tion of the polymeric carrier. As such it is the reverse of
to the first term, thus CB (R, t) ≈ CB (r0 , 0). This the encapsulation. It is important to note that Eq. (32)
condition is approximately satisfied in the early stage is mathematically identical to Eq. (25) that we ob-
of the polymerization, even under nonsteady-state tained previously for a flat sheet model [11]. It should
boundary conditions. be emphasized that in this work Eq. (32) is obtained as
Although the thickness of the capsule wall formed a special case of a more general model derived above.
by interfacial reaction changes with time, this case
is often referred to as the steady-state model in the 2.2.2.3. Diffusion-controlled interfacial polymeriza-
literature [20]. tion. If the reaction rate is much larger than the
diffusion rate, i.e. k I
D M , then the reaction term on
2.2.2.1. Reaction- and diffusion-controlled interfacial the right hand side of Eq. (30) is negligible compared
polymerization. Assuming that both reaction and to the diffusion, thus Eq. (30) reduces to
monomer diffusion are rate controlling steps, Eq. (4)
still holds, but Eq. (2) is changed to ϕP2 (r0 − R)2 ϕP2 X 2
t= = (33)
dR kI 2DM CA (r0 , 0) 2DM CA (r0 , 0)
− = CA (R, t)CB (r0 , 0) (28)
dt ϕP Mathematically, Eq. (33) is the same as Eq. (26) that
Combining Eq. (4) with Eq. (28) gives the growth rate we obtained previously for a flat sheet model [11].
of the capsule wall as Eq. (33) is also similar to the model reported by Evans
[20] for the corrosion of a metal. Evans showed that
dR DM kI CA (r0 , 0)CB (r0 , 0) the model was consistent with experimental data on
− = (29)
dt DM ϕP + ϕP2 kI CB (r0 , 0)(r0 − R) the oxidation of copper. Eq. (33) is also essentially the
same as reported by Janssen and te Nijenhuis [7–9] for
Integration of Eq. (29) gives the polycondensation of terephthaloyl dichloride with
ϕP2 (r0 − R)2 ϕP (r0 − R) diethylenetriamine at the interface of an oil-in-water
t= + (30) emulsion. It should be noted that, in this work, Eq. (33)
2DM CA (r0 , 0) kI CB (r0 , 0)CA (r0 , 0)
is obtained as a special case of a more general model
The first term on the right hand side of Eq. (30) is derived above.
the time needed for monomer diffusion from the outer Although the above special models were derived
surface of the capsule wall to the reaction zone, and by simplifying the general model, it is important to
the second term is the reaction time. This can be seen point out that these special models can also be derived
clearly from the following two special models. independently from the general assumptions discussed
earlier and the assumptions specified in this section.
2.2.2.2. Reaction-controlled interfacial polymeriza- The spherical model under the nonsteady-state
tion. If the diffusion rate of monomer A is much boundary conditions developed in this work is dif-
faster than the reaction rate, i.e. D M
k I , Eq. (29) ferent from the flat sheet model developed earlier
reduces to due to the material balance associated with different
dR kI CA (r0 , 0)CB (r0 , 0) geometry. The spherical model under the steady-state
=− (31) boundary conditions is mathematically identical to
dt ϕP
the flat sheet model, as no material balance is required
and Eq. (30) reduces to for the steady-state models.
62 J. Ji et al. / Journal of Membrane Science 192 (2001) 55–70

3. Results and discussion t, approaches infinity, the capsule wall approaches

In this section, the validity of the model is first
qualitatively assessed by examining the model under
several limited conditions, then the model is quanti-
tatively assessed (1) by comparing with the experi-
mental data reported in the literature [7–9], and (2)
by systematically varying a variety of factors that
influence interfacial polymerization.
3.1. Qualitative assessment of the general model
the maximum thickness, thus R approaches Rmin . The
right hand side of Eq. (16) approaches infinity, and the
growth rate given by Eq. (14) approaches zero, and as
expected, Eq. (7) gives C B (R, ∞) = 0.
Similar analyses can be applied to the special mod-
els to give the same conclusions as discussed above.
The above analysis clearly indicates that the model is
physically reasonable. The general model, Eq. (16),
provides an analytical solution for the formation of the
capsule wall.

The validity of the models developed above can be
qualitatively assessed in terms of the physical meaning
of the models at certain limits.
The general model, given by Eq. (16) along with
Eqs. (7), (14), (15) and (22), correctly reduces to the
expected values at various points in the time domain.
At t = 0, Eq. (16) gives R = r0 , i.e. X = r0 − R = 0,
the thickness of the capsule wall is zero. Based on
Eq. (14), at t = 0, the maximum growth rate of the
capsule wall is proportional to the initial monomer
concentration. At t = 0 and R = r0 , both Eqs. (7)
and (15) correctly reduce to the initial concentration
of B and A, respectively. When polymerization time,
3.2. Comparison of the general model with the
published experimental data
In order to verify the validity of the general model,
a modified Marquart non-linear parameter estimation
routine, UWHAUS [23] was used to fit the general
model, Eq. (16), to the experimental data reported
by Janssen and te Nijenhuis [9] for the capsule wall
thickness versus the polymerization time. The results
obtained are presented in Fig. 2.
In Janssen and te Nijenhuis’ work, the cap-
sule wall was formed by interfacial polymeriza-
tion of terephthaloyl dichloride (TDC) contained in

Fig. 2. Comparison of the general model with the experimental data reported by Janssen and te Nijenhuis [9]. The solid line is produced
by the general model using Eq. (16) and the parameters in Tables 1 and 2.
 J. Ji et al. / Journal of Membrane Science 192 (2001) 55–70
Table 1
Variables used in fitting the model to experimental data
CA (r0 , 0) = 1.0 kmol/m3
CB (r0 , 0) = 0.233 kmol/m3
k = 1.0 × 10−3 m4 /(kmol s)
KA = 1.0
MA = MDETA = 103.17 kg/kmol
MB = MTDC = 203.02 kg/kmol
MZ = MHCl = 36.45 kg/kmol
ρ P = 1200 kg/m3
ϕ P = 0.78
dispersed dimethylphthalate droplets with diethyl-
enetriamine (DETA) in a continuous aqueous phase.
Thus, monomer B corresponds to TDC, and monomer
A to DETA in the general model discussed above.
The general model can be correlated to the interfacial
polymerization of TDC with DETA as follows:
TDC + γ DETA → Polymer + HCl (34)
The effect of HCl produced from the condensation re-
action is negligible due to the presence of 1 kmol/m3
of NaOH in the system used by Janssen and te Nijen-
huis [9]. The reaction ratio, γ , is in a range between
2/3 and 1, i.e. 2/3 ≤ γ ≤ 1. If γ = 1, a linear
polymer is formed. If 2/3 < γ < 1, a crosslinked
network is formed. Therefore, in attempting to fit the
general model with the experimental data reported by
Janssen and te Nijenhuis [9], the apparent reaction
rate constant kI , in Eq. (2) was replaced with kI γ , and
the apparent diffusion coefficient, DP , in Eq. (3) was
replaced with DP /γ [7]. The exact numerical value of
γ was not given by Janssen and te Nijenhuis [7–9].
All parameters except K, k and ϕ P in Table 1 were
taken from the work by Janssen and te Nijenhuis [7–9].
The average polymer volume, ϕ P , in the capsule wall
was measured from SEM’s of the capsule wall shown
in [7] using Sigma Scan graphic analyzer [24]. No
numerical value of ϕ P was given in [7–9] although it
was used by the authors. In Janssen and te Nijenhuis’
work [9], two methods were used to calculate polymer
fraction, ϕ P , in the capsule wall. In the first method,
the water flux was assumed to be a constant, thus the
polymer fraction, ϕ P , in the capsule wall is propor-
tional to the reaction time. In the second method, the
water flux was assumed to be proportional to the flux
of the DETA monomer, resulting in ϕ P being indepen-
dent of reaction time. Janssen and te Nijenhuis [7–9]
63
Table 2
The results of data fitting with 95% confidence intervals
Diffusion coefficient (1.00 ± 0.15) × 10−12 m2 /s
Number of degrees of freedom 9
reported that both methods were equally effective. As
a result, the second method was used in the current
work because of its simplicity.
The partition coefficient, K, of DETA between the
aqueous phase and capsule wall was assumed to be
one. Based on Janssen and te Nijenhuis’ work [7–9],
the rate constant, kr , of the polymerization of TDC
with DETA is in the order of 104 –106 m3 s/kmol, thus
the rate of interfacial polymerization of TDC and
DETA is controlled by monomer (DETA) diffusion.
For the data fitting purpose, the actual value of kI
in Eq. (2) is not critical in this work because it is a
diffusion-controlled process.
Therefore, a single parameter fitting of Eq. (16) to
the experimental data was conducted using a modified
Marquart non-linear parameter estimation routine,
UWHAUS [23]. The solid points in Fig. 2 are the
experimental data reported by Janssen and te Nijen-
huis [9]. The solid line was produced by the general
model using Eq. (16) and parameters in Tables 1
and 2. The capsule wall thickness linearly increases
with the square root of reaction time as shown in
Fig. 2. The data fitting gives a diffusion coefficient of
(1.00 ± 0.15) × 10−12 m2 /s as shown in Table 2. This
value is reasonable, because it is very close to the
reported diffusion coefficient of 1,6-hexanediamine in
polyamide, 8.0 × 10−12 m2 /s [25]. The above results
clearly demonstrated that the general model devel-
oped in this work is consistent with experimental data
reported by Janssen and te Nijenhuis [7–9] with the
capsule wall thickness linearly increasing with the
square root of reaction time. It is important to point
out that the special model derived above for diffusion
controlled interfacial polymerization, Eq. (33), can
also describe the data in Fig. 2.
3.3. Effect of water diffusion on the
thickness and porosity of the capsule wall
The general model developed in this work allows
the formation of a porous capsule wall by considering
the simultaneous diffusion of water and monomer A.
64 J. Ji et al. / Journal of Membrane Science 192 (2001) 55–70
Table 3
The relationship between the polymer volume fraction, ϕ P , in
the capsule wall and the molar ratio, β, of water to the amine
monomer transported together
β ϕP
0 1.0
2 0.87
4 0.78
8 0.64
16 0.47
The relationship between the polymer volume frac-
tion, ϕ P , in the capsule wall and the molar ratio of
water to diethyltriamine flux, β, given by Eq. (5),
is presented in Table 3. A detail discussion on this
relationship was given in our previous work [11]. As
expected, the amount of water transported increases,
corresponding to increasing β, the polymer volume
fraction, ϕ P , decreases. If no water is transported with
diamine monomer, a dense capsule wall is formed
because ϕ P = 1 when β = 0. This result is consistent
with the experimental results reported by Morgan and
Kwoleck [16]. They could not make a dense reverse
osmosis membrane by liquid–liquid interfacial poly-
merization of hexamethylenediamine in water and
Fig. 3. The effect of polymer fraction in the capsule wall and polymerization time on the thickness of the capsule wall. The curves are
produced using Eq. (16) and the parameters in Tables 1 and 2.
sebacoyl chloride in an organic solution, because the
presence of water resulted in a porous membrane.
A typical impact of the polymer volume fraction
on the thickness of capsule wall is displayed in Fig. 3.
At a given polymerization time, the thickness of cap-
sule wall increases with decreasing volume fraction
of the polymer in the capsule wall. These simulations
indicate the importance of water transport from the
aqueous phase into the forming capsule wall on the
porosity and thickness of the capsule wall. It also pro-
vides an important guideline to control the porosity
and the thickness of the capsule wall. For example,
the diffusion of water should be eliminated or min-
imized to obtain a dense capsule wall (membrane),
and maximized to obtain a very porous capsule wall.
3.4. Kinetic behavior of capsule wall formation by
interfacial polymerization
Having established the model and approximated a
set of parameters, then the effects of different factors
on the kinetics of interfacial polymerization and on the
formation of capsule wall can be studied. In particular,
those parameters which are difficult to measure exper-
imentally are of interest. In this section, the general
 J. Ji et al. / Journal of Membrane Science 192 (2001) 55–70
Fig. 4. The effect of polymerization time on the thickness and the growth rate of the capsule wall. The curves are produced using Eqs. (16)
and (14) and the parameters in Tables 1 and 2.
model developed for encapsulation by reaction- and
diffusion-controlled interfacial polymerization under
nonsteady-state boundary conditions, and the param-
eters in Tables 1 and 2, except where noted otherwise,
are used in the following simulation.
The relationship between the growth rate of the
thickness of the capsule wall with polymerization
time is displayed in Fig. 4. The growth rate decreases
rapidly with time in the early stage of polymerization,
then gradually approaches zero. In contrast, the cap-
sule wall thickness increases dramatically with time
at the beginning, then slowly approaches the maxi-
mum value with time, even when the reaction time
approaches infinity. For the case shown in Fig. 4, the
polymerization is completed in about 0.8 h, however,
the wall thickness exceeds 50% of the maximum
wall thickness in less than 25% of the reaction time.
As would be expected the early stage of polymer-
ization plays a more important part in the formation
of capsule wall than the later stages of the reaction.
Prolonging the polymerization time is not effective in
attempting to increase the capsule wall thickness.
The impact of monomer B concentration on the
capsule formation is shown in Fig. 5. The capsule
wall thickness is calculated by Eq. (16). Regardless
of initial B concentration, the capsule wall thickness
65
increases with polymerization time. However, at a
higher initial concentration of B, the capsule wall
grows faster and approaches a higher maximum wall
thickness, but takes a longer time to reach the same
reduced thickness, X/Xmax . These simulations indi-
cate that the use of a higher initial B concentration
can significantly increase the growth rate of the cap-
sule wall and shorten the time required for a certain
wall thickness, thereby increasing the efficiency of
the encapsulation process.
The effect of the initial concentration of monomer
A on interfacial polymerization and capsule formation
are illustrated in Fig. 6. As can be seen from Fig. 6,
the capsule wall thickness increases more rapidly and
approaches the maximum value at shorter times when
the concentration of A, CA (r0 , 0), is increased. How-
ever, the maximum thickness of the capsule wall is
independent of the initial A concentration. The maxi-
mum thickness of the capsule wall is solely determined
by the initial B concentration, Eqs. (21) and (22).
The rate constant for the polymerization is an impor-
tant parameter with respect to the kinetics of capsule
wall formation by interfacial polymerization [13–19].
Experimentally it is difficult to study the effect of
change in rate constant without making other changes
in the system. The effect of the reaction rate constant
66 J. Ji et al. / Journal of Membrane Science 192 (2001) 55–70

Fig. 5. The effect of monomer B concentration and polymerization time on the thickness of the capsule wall. The curves are produced
using Eq. (16) and the parameters in Tables 1 and 2.

Fig. 6. The effect of monomer A concentration and polymerization time on the thickness of capsule wall. The curves are produced using
Eq. (16) and the parameters in Tables 1 and 2.
 J. Ji et al. / Journal of Membrane Science 192 (2001) 55–70 67

Fig. 7. The effect of the apparent reaction rate constant, k, and polymerization time on the concentration profile of monomer A in the
reaction zone. The curves are produced using Eq. (15) and the parameters in Tables 1 and 2.

Fig. 8. The effect of the apparent reaction rate constant, k, and polymerization time on the concentration profile of monomer B in the
reaction zone. The curves are produced using Eq. (7) and the parameters in Tables 1 and 2.
68 J. Ji et al. / Journal of Membrane Science 192 (2001) 55–70
Fig. 9. The effect of the apparent reaction rate constant, k, and polymerization time on the thickness of the capsule wall. The curves are
produced using Eq. (16) and the parameters in Tables 1 and 2.
and polymerization time on the concentrations of A
and B in the reaction zone, CA (R, t) (Eq. (15)) and
CB (R, t) (Eq. (7)), are displayed in Figs. 7 and 8,
respectively. Three types of interfacial polymeriza-
tion can be distinguished from Fig. 7 in terms of the
rate-controlling step.
When the apparent reaction rate constant is small
(1 × 10−8 m4 /(kmol s)), no significant change in
both CA (R, t) and CB (R, t) is observed after 0.7 h
reaction from Figs. 7 and 8, respectively. This is
a typical reaction-controlled interfacial polymeriza-
tion. In this case, the diffusion of A has no effect
on the capsule wall formation, because the driving
force (concentration gradient) for diffusion of A
is zero. The wall thickness increases linearly with
time as shown in Fig. 9. It should be noted that
the same result can be obtained using the special
model, Eq. (32), for reaction-controlled interfacial
polymerization.
When the reaction rate constant is large, 1 ×
10−3 m4 /(kmol s), the diffusion of A is the rate con-
trolling step. As soon as the polymerization starts,
the concentration CA (R, t) falls to zero, and CB (R, t)
also quickly approaches zero with time. As a result,
the capsule wall thickness rapidly approaches the
maximum value (Fig. 9). In general, the interfacial
polymerization of a diamine with a diacid chloride to
form polyamide belongs to this type [7–9,12–19].
For cases involving intermediate reaction rate con-
stants, (e.g. 1 × 10−6 m4 /(kmol s)), the driving force
for diffusion (C A (r0 , 0)−C A (R, t)), is initially small.
As time proceeds, the driving force increases, indicat-
ing the importance of diffusion on the growth rate of
capsule wall, and finally decreases as the dicarbonyl
chloride is consumed and polymerization is controlled
by the reaction kinetics. Thus, for this case both reac-
tion and diffusion are important for the formation of
capsule wall. The wall thickness gradually increases
with time and eventually approaches the maximum
value, Fig. 9.
Diffusion coefficient of monomer A has a simi-
lar impact on the kinetics of capsule wall formation
as discussed above for reaction rate constant. Three
types of encapsulation process can be found, namely:
(1) reaction controlled, (2) diffusion controlled, and
(3) both reaction and diffusion controlled processes.
4. Conclusion
A general model for the encapsulation by both
diffusion- and reaction-controlled interfacial polymeri-
 J. Ji et al. / Journal of Membrane Science 192 (2001) 55–70
zation under nonsteady-state boundary conditions
has been developed, which is consistent with the
experimental data published in the literature [7–9].
The general model developed can be reduced to the
following special models under given conditions:
1. nonsteady-state boundary conditions;
• reaction-controlled interfacial polymerization,
• diffusion-controlled interfacial polymerization,
2. constant concentration of monomer B in the
capsule core;
• both diffusion- and reaction-controlled interfa-
cial polymerization,
• reaction-controlled interfacial polymerization,
• diffusion-controlled interfacial polymerization.
The analytical solutions to the second model of
case 2 agreed with the spherical model developed
by Neogi and Allan for the controlled release of
pesticides by decomposition of the polymeric car-
rier [21,22]. And the analytical solutions to the third
model of case 2 agreed with the flat sheet models
published earlier [7–9,11]. Therefore, the general
model developed in this work is not only supported
by the experimental data [7–9] but also by its special
models being mathematically identical to the mod-
els published in the literature [7–9,11,21,22]. All the
models developed above are simple, have easy to use
analytical solutions, have clear physical meaning, and
predict results that would be expected for the encap-
sulation by interfacial polymerization. This work has
significantly extended the existing theories of capsule
wall formation by interfacial polymerizations.
The effects of the reaction rate constant and the dif-
fusion coefficient on capsule wall formation have been
systematically studied. Both the reaction rate constant
and the diffusion coefficient strongly affect the cap-
sule wall growth rate. Three cases of interfacial poly-
merizations have been predicted by the model in terms
of the rate controlling step: (1) diffusion-controlled,
(2) reaction-controlled, and (3) both diffusion- and
reaction-controlled. Monomer concentration has an
important effect on the capsule wall formed. Increas-
ing the concentration of monomer B increases not
only the growth rate but also the maximum thickness
of the capsule wall. However, increasing the con-
centration of monomer A only increases the growth
69
rate of the capsule wall, but not the maximum thick-
ness. The higher the concentration of B, the shorter
the polymerization time needed to obtain a certain
capsule wall thickness. However, with a higher con-
centration of B longer reaction time is required to
reach the same reaction conversion of B expressed by
the reduced thickness, X/Xmax , of the capsule wall.
The thickness of the capsule wall rapidly increases
with time during the early stage of polymerization,
then levels off with time as the polymerization pro-
ceeds, while the growth rate of the capsule wall
decreases with polymerization time. After the initial
rapid growth, the capsule wall thickness does not
increase much. Thus, lengthening the polymeriza-
tion time in an attempt to increase the capsule wall
thickness would be ineffective.
Diffusion of water, associated with the monomer A,
during the capsule wall formation has an important im-
pact on the physical structure of capsule wall formed
by interfacial polymerization. A porous capsule wall is
formed when water diffuses together with monomer A
towards reaction zone. Elimination of water diffusion
during capsule wall formation gives a dense capsule
wall free of micro voids.
Although the models discussed above are devel-
oped for encapsulation by interfacial polymerization,
they are mathematically suitable for any kind of in-
terfacial reactions which satisfy the assumptions used
to develop the models. The models developed provide
an important guide for the effective control of the
capsule wall thickness and porosity.
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