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Journal of Macromolecular
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Pure and Applied Chemistry

MS#4/23
TITLE: PICKERING EMULSION POLYMERIZATION KINETICS OF STYRENE:
COMPARISON OF BARE AND SURFACE MODIFIED SIO2 NANOPARTICLES
AUTHORS: B. FOUCONNIER,1 A. ROMN-GUERRERO,2 AND F. LPEZ-SERRANO3*

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Running head: Pickering emulsion polymerization kinetics: SiO2 effect

Pickering emulsion polymerization kinetics of styrene: Comparison of
bare and surface modified SiO2 nanoparticles
B. Fouconnier,1 A. Romn-Guerrero,2 and F. Lpez-Serrano3*
1

Facultad de Ciencias Qumicas. Universidad Veracruzana. Av. Universidad Km 7.5, Col. Santa Isabel,
C. P. 96535 Coatzacoalcos, Veracruz. Mxico

Departamento de Biotecnologa, Universidad Autnoma Metropolitana-Iztapalapa, San Rafael Atlixco No.

186, Col. Vicentina, C.P. 09340 Mxico, D.F. Mxico

Departamento de Ingeniera Qumica. Facultad de Qumica. Universidad Nacional Autnoma de Mxico.

Ciudad Universitaria, D. F. 04510. Mxico

Abstract
A step towards the understanding of some mechanistic events occurring in the styrene
Pickering emulsion, using a SiO2 dispersion, is presented. Polymerizations at 80C with
different levels of a water soluble initiator were performed. The emulsion polymer content
was ca. 15% with conversions close to 90%. With conversion and particle size
measurements, the particle density was estimated for bare and surface modified SiO 2
particles. Then, the average number of radicals per particle was inferred, yielding a pseudobulk type polymerization. It was found that bare SiO2 nanoparticles do not participate in the
nucleation mechanism; however, they, along with the initiator, promote an enhanced
oligomer coagulation. On the other hand, the hexadecyltrimethylammonium bromide
modified SiO2 nanoparticles do participate in the nucleation and coagulation mechanisms,
yielding more stable and smaller poorly-covered polymer particles. This approach allowed
untangling some events such as: particle nucleation, radical entry to particles, particle
density, coagulation and vitreous and Trommsdorff effects.
Key words: Pickering, emulsion polymerization, kinetics, styrene, SiO2, mechanisms
*Corresponding author e-mail: lopezserrano@unam.mx

1. Introduction
The synthesis of inorganic/organic hybrid materials with specific properties represents an
academic and industrial topic of growing interest since the past decade (1, 2). Combining
the individual properties of inorganic particles and the polymer matrix, extraordinary
synergy in chemical and physical properties are conferred to the nanocomposites (3, 4)
which make them very attractive for a broad range of applications such as: chemical
sensors, electro-optics, drug delivery, enzyme immobilization, molecular recognition,
energy storage, and catalysis (5-8).
Recently, new developments of fabrication routes for nanocomposite materials have
promoted the use of finely divided solids as stabilizers instead of surfactants (9-11). Solid
nanoparticles can act as emulsifiers and stabilize droplets due to their adsorption at wateroil interface. These surfactant-free dispersed systems are the so-called Pickering emulsions,
which differ from conventional emulsions due to their high stability against coalescence
(12-14). For these reasons, Pickering emulsions are used for the synthesis of core-shell
nanocomposite

particles.

Their

preparation

can

be

very simple,

sophisticated

instrumentation is not required, commercial solid dispersions or solutions can be used

without further treatments, and the produced latex is surfactant-free (15-19).
Ongoing research in designing inorganic/organic hybrid materials does not solely
focus on promoting the compatibility between the inorganic particles and the polymer but
also on the understanding of the mechanisms of latex particle nucleation, including the
effect of inorganic particles on the absorption of radicals and coagulation of the composite
polymer particles (20). The conventional emulsion polymerization process (CEP) can be
described by three possible mechanisms: micellar nucleation, homogeneous coagulative
5

nucleation and droplet nucleation (17, 21, 22). Droplet nucleation is only predominant in
miniemulsion polymerization (20, 21) or in emulsion polymerization when a hydrophobic
initiator is used (23-25).
Despite the fact that the inorganic particles play a key role in stabilizing latex
particles, they also directly affect the kinetics of the polymerization reaction. Colard et al.
(26) reported that the inorganic particles have a pronounced effect on the number, size and
distribution of armored polymer particles. On the other hand, Sheibat-Othman et al. (27)
and Colver et al. (28) investigated the kinetic of polymerization in soap-free emulsions
using laponite clays and silica particles as stabilizers respectively, and showed that the
concentration of inorganic particles had negligible effect on latex particle size. Teixeira et
al. (29) showed that the use of increasing amounts of laponite clay, to prepare armored
soft polymer latexes, leads to smaller average size particles, but inflicts a longer
nucleation period. Therefore, the particle size and distributions are broader. It is also
noteworthy that the latex particles do not need to be fully covered to be stable. Namely, less
than 50 percent coverage can be sufficient to get colloidal stability (27). Additionally, the
presence of inorganic particles onto the polymer surface may reduce the polymerization
rate, because they can act as a barrier to the diffusion of the oligoradicals (30).
Mainly concentration, wettability and electrostatic charge of the inorganic particles
govern the reaction rate, conversion, size and shape of the polymer particles. However,
additional parameters have to be considered, such as the impeller speed and type, and
initiator concentration, among others. Sheibat-Othman et al. (30) reported that at low
stirring rate, the kinetics are diffusion controlled, depending on the monomer
hydrophilicity, and that the reaction can accelerate if radical termination is reduced, due to
a Trommsdorff effect. On the contrary, at high stirring rate, the monomer droplets are
6

smaller, the monomer diffusion through the aqueous phase is favored, but coagulation of
armored particles occurs, leading to an increase in particle diameter. Alternatively,
coagulation depends on the presence of the inorganic particles, onto the polymer surface,
which can provide colloidal stability. Furthermore, at high stirring, the oligomeric diffusion
in the water phase is promoted (31). Also, Arai et al. (32) reported that a polymerization
rate decrease was due to a reduced gel effect motivated by an increase in monomer
concentration inside the particles, induced by enhanced monomer transfer when increasing
agitator speed. Conversely, the average number of radicals per particle increases with the
particle size and consequently, the overall reaction rate and conversion are increased when
the gel effect is promoted. Teixeira et al. (29) reported the occurrence of a catastrophic
coagulation phenomenon for Pickering emulsion polymerizations, carried out at low
concentration of particles and laponite clay discs. Sheibat-Othman et al. (27) also studied
polymerization of styrene with laponite clay platelets. They found that the number of
polymer particles was independent of the laponite clay discs concentration. This indicated
an efficient nucleation process, due to an enhanced capture of radicals, provided by the
presence of the surface modified laponite platelets onto the polymer particle surface.
Although many works deal with the polymerization in Pickering emulsions, the
mechanisms are not fully understood and to the best of our knowledge, the proposed
mechanisms are mostly schematically described.
The present work is dedicated to evidence the mechanisms of Styrene (St)
polymerization at 80C, in a heterogeneous process, in the presence of negatively charged
silica nanoparticles, using ammonium persulfate (APS) as initiator, at different
concentrations. For that purpose, the interactions between the bare silica nanoparticles
(bSP) and the growing oligomers were initially investigated. Then, the silica nanoparticles
7

were superficially modified (mSP), using hexadecyltrimethylammonium bromide (CTAB),

a cationic surfactant, to improve affinity with the oligomers. Also, the concentration of this
modified silica was evaluated. In all events, conversion, polymerization rate, nucleation
process, average number of radicals per particle, absorption of radicals and particle
coagulation, were analyzed.
2. Materials and methods
Styrene

99%

or

greater

purity

was

washed

to

remove

the

inhibitor

and

hexadecyltrimethylammonium bromide (CTAB) (SigmaAldrich Quimica), sodium

chloride (NaCl, 98% purity) and ammonium persulfate (APS, 98% purity) (J. T. Baker,
S.A. de C.V.) were used as received. Bindzil 830, the colloidal dispersion of silica
nanoparticles (SiO2; 30% w/w; Bindzil 830 (d = 10 nm, pH = 10.5, specific surface area =
305 m2/g and bulk density = 1.2 g/cm3), was kindly provided by Silicatos y Derivados, S.A.
de C.V. Deionized water (W) was used in all the experiments.
2.1 Preparation of the emulsions
In the case of modified silica particles (mSP), the dispersion was prepared by putting in a
volumetric flask the requisite amounts of Bindzil, CTAB and NaCl in water in order to
obtain the composition given in Table 1 (33). This dispersion was then mixed during 5 h
and sonicated in an ultrasonic bath (Branson 5510), during 15 min before its use for the
emulsion formulation. The amounts charged for the bSP experiments are presented in Table
2.
Coarse emulsions with dispersed phase mass fraction of 0.15 were obtained by
dripping the requisite amount of St (previously washed with a 10 wt% NaOH aqueous
solution) onto a dispersion of silica-CTAB-NaCl containing 2.1 wt% of silica particles and
mixed with the help of an Ultra-Turrax T25 (IKA-WERKE Works Inc., Wilmington, NC,
8

USA) at 20,000 rpm for 10 min., as shown in Table 2.

2.2 Particle synthesis
The batch polymerization reactions were carried out at 80C in a 0.5 L double-walled
reactor, equipped with an external circulating heating bath (PolyScience), a condenser and a
three-bladed metal overhead turbine stirrer fitted from the four-necked reactor vessel
running at 250 rpm. In experiments using the non-modified silica particles (bSP) solely,
water, silica colloid dispersion (Bindzil 830) and St were introduced into the reactor and
stirred. Then the suspension was heated to 80C and purged with nitrogen during 15 min.
When the suspension reached a stable temperature of 80C, the polymerization was
initiated by the addition of APS, previously dissolved in few ml of water, in the reaction
medium at different concentrations (i.e.: 0.5, 1 and 2 wt% relative to St). In the
polymerizations, using mSP, the protocol was similar. St/W emulsions were introduced in
the reactor and heated to 80C and degassed with nitrogen. When the dispersed systems
reached 80C, the emulsion polymerization was initiated by adding APS at the same
concentrations as in the bSP experiments.
All reactions were monitored by withdrawing samples at regular time intervals to
determine the solid content and the polystyrene nanoparticle size (Dp). In emulsion
polymerizations, the solid contents were both determined by gravimetry and Raman
spectroscopy, but solely with gravimetry in processes involving bSP due to inhomogeneity
of the suspension and immediate separation of the organic phase from the water phase,
especially at the beginning of the reaction, which led to imprecision in the intensity of the
absorbance peaks.

2.3 Particle Characterization

The average polystyrene nanoparticle size was determined by dynamic light scattering at
25C, using a Zetasizer Nano-ZS2000 (Malvern Instruments Ltd., Malvern, Worcestershire,
UK) with a refractive index of 1.330.
3. Balance equations
To describe the Pickering emulsion polymerization it is assumed that this process proceeds
basically as the traditional emulsion polymerization, with some subtle differences. Here,
because not enough emulsifier is present to provide micelles as polymerization nuclei, it
will be assumed that the following equation still prevails:
(1)
here, x is the fractional conversion, kp the propagation rate constant (mol L-1 s-1), Mp the
monomer concentration inside the particles (mol L-1), n the average number of radicals per
particle, Np the particle density (L-1), M0 (mole) denotes the moles of monomer charged to
the reactor and Nav is Avogadros number (mol-1).
3.1 Monomer mass balance
To perform the monomer balance, the following simplifying assumptions are applied: (i)
monomer solubility in the water phase is negligible for consumption via polymerization,
(ii) monomer swelling in polymer particles is similar to the one achieved in conventional
emulsion polymerization, (iii) all polymer particles have a very similar size, and (iv) the
polymerization is isothermal, implying that kp is constant.
The monomer mass balance is:
(2)

10

m0, mp, ms, md are the monomer charged to the reactor, converted to polymer, swelling the
polymer particles and located in droplets, respectively.
Eq. 2 can be rewritten as:
(3)
where,
+Vp),

is the volume fraction of monomer swelling the polymer particles (

=Vm/(Vm

is the density and V is the volume, the subscripts m and p refer to monomer and

polymer, respectively.
The total particle volume p (L) can be obtained assuming volume additivity as:
(4)
When the monomer droplets disappear (see Eq. 2), the mass of monomer inside the
particles (ms) becomes:
(5)
The monomer concentration inside the particles is given by:
(6)
here, Mw is the monomer molecular weight.
The number of polymer particles (Np) is given by the total polymer mass (mp) divided by
the mass of one particle (m1p), yielding:
(7)
here, Dp is the particle diameter. The reader should be aware that in Eq. 7, Np is
undetermined when the particle diameter is close to zero and will yield very high values at
small particle diameters.
3.2 Inferring n
11

One of the objectives is to gather as much information as possible. Eq. 1 can be rewritten as
follows (34):
(8)
here, ne is the estimated number of radicals. As can be seen in Eq. 8, all the terms in the
RHS are known. The conversion derivative (Eq. 9) is obtained using an auxiliary function
to fit (smooth) the conversion experimental data (

using the following 5-parameter

empirical function:
,

(9)

where kxis (i = 1-5) are fitting parameters. The particle diameter (dpe) is obtained fitting the
particle diameter experimental data with a rational 3-parameter expression as follows:
(10)
where kdis (i = 1-3) are fitting parameters. Thus, a continuous description for the particle
density (Npe), is obtained substituting xe and dpe into Eq. (7). As will be presented later,
smoothing the disperse data allows a better (and continuous) data trajectories and trends
description. Table 3 lists the parameters used for the calculations.
4. Results and Discussion
In surfactant-free polymerization processes or when the emulsifier is below its CMC, the
homogeneous coagulative nucleation is the dominating mechanism, as the micellar
nucleation mechanism is excluded. Therefore, the mechanisms of emulsion polymerization
can be roughly described as follows: monomer partially dissolves in the water phase and
reacts with radicals, issued from the hydrophilic initiator decomposition, depending mainly
on temperature and pH, to form oligomers which grow until reaching a critical length due
to their insolubility (2-3 monomer units for styrene) (37). Then, the oligomers agglomerate
12

to reduce the interfacial area and form mature latex particles. These particles, stabilized by
the adsorption of the inorganic nanoparticles, could grow via swelling, due to monomer
diffusion through the aqueous phase. The swelling process continues until the monomer
droplets vanish and the latex particles formed are sub-micron sized.
4.1 Bare SiO2 particles (bSP)
To test the capability of bare or unmodified SiO2 particles (bSP) in the Pickering emulsion
polymerization, preliminary experiments were performed to obtain a stable recipe using
styrene (15% wt.) and different amounts of colloidal SiO2 (Bindzil 830).
The recipe for this experiment is shown in Table 2. The results are presented in
Figure 1, where the conversion against time and its derivative against conversion (inset) are
shown. As expected, the polymerization rate increases with APS concentration.
An interesting feature is depicted in Figure 1 inset, where one could see a similarity
with the conventional emulsion polymerization (CEP), showing a long interval I, a steadystate regime (Interval II) and a pronounced gel effect that hinders Interval III.
Figure 2 depicts the experimental particle diameter (Dp) against smoothed x1/3. This
presentation was selected because, as seen in Eq. (7), Dp will be linear against x1/3 if Np is
constant. Here, as APS is increased, a larger particle diameter is observed. Figure 3 shows
the experimental particle density (Np) against conversion. Figure 4 shows the inferred
average number of radicals per particle against conversion. The continuous lines in all
figures are obtained with the smoothing functions for conversion (Eq. 9) and particle
diameter (Eq. 10).
To address the effect of the SiO2 content, a blank (without SiO2) was run with 1%
APS content. In Figure 1 it appears that at the same initiator content, the reaction is slower
in the blank. Figure 2 shows that the particle size (Dp) is similar, or perhaps a little larger,
13

than the experiment performed with SiO2. The particle density number (Np), as seen in
Figure 3, shows a growing tendency but is lower than the corresponding experiment with
SiO2.
Regarding Figure 2, one would expect that the higher the APS content the larger the
nucleation rate, because more oligomers could be formed as APS increases. The opposite
behavior occurs, probably a higher nucleation rate occurs the higher the APS content, but
coagulation increases when the SiO2 colloidal particles are not capable of stabilizing the
growing particles and the reduction helps to achieve colloidal stability. Interestingly
enough, a smaller particle size could lead to a higher Np and one should expect a higher
polymerization rate. However, the opposite behavior is observed, as seen in Figure 1.
Figure 3 confirms this fact, and a lower particle number appears as APS is increased.
Figures 2 and 3 contradict what is presented in Figure 1. Due to this fact, the average
number of radicals was inferred (ne) as presented in a previous section. This calculation
allowed understanding the behavior of Figure 1, which shows that the higher the APS
content is, the faster the reaction rate.
Figure 4 shows that from 0.5 to 2 % APS content, a 7-fold increase in ne appears
going from 45 to ca. 380 radicals per particle (at the highest point), respectively. In this
figure also, the average radicals per particle number (ne) for the blank is lower (ca. 75) than
the corresponding experiment (ca. 110). This explains the behavior of a slower reaction in
the blank. It must be pointed out that this high amount of initiator content is sufficient to
impart stability to the emulsion due to the presence of SO2- groups, from the initiator,
surrounding the latex particles.
In the non-modified polymerization processes (bSP), when the initiator is added, the
primary radicals, issued from initiator decomposition, react with the monomer dissolved in
14

the aqueous phase and give rise to the formation of growing oligomers, which become
insoluble and aggregate, to form mature polymer particles. As can be observed in Figure 1
inset, the conversion derivative curves increase until approximately 15% conversion. This
period presents a similarity to interval I in the CEP for these polymerization processes.
Next, constant-rate interval succeeds (similar to interval II in CEP), and then (ca. 50%
conversion) the Trommsdorff effect appears. If a very short nucleation period occurs, this
would yield a fast occurrence of a stable and constant number of growing latex particles.
Therefore, a plot of Dp vs. x1/3 should show a linear behavior (see Eq. 7). This is the case for
all the experiments carried including the blank up to x1/3 = 0.70 (x = 0.34). Therefore, it can
be assumed that these polymerization processes are characterized by a short nucleation
period, where a stable and constant number of mature particles are produced. After 34%
conversion, the experiments containing 2% and the blank, keep a linear tendency; the other
two (0.5 and 1 % APS) show further nucleation, looking at a horizontal behavior, meaning
that Np is proportional to x. This event is confirmed by Figure 3, where Np increases very
rapidly (at very small conversions, between 5 and 10%). Afterwards, a constant particle
density remains for the 2% APS and the blank (1% APS), because in the other experiments
nucleation is occurring, being more noticeable in the 0.5 % APS content. Finally, the
production of polymer starts decreasing (Fig. 1) due to monomer depletion inside the
particles and also probably due to a vitreous effect (34). With a decrease in kp, caused by
approaching the glass transition temperature (Tg) of the reacting mixture, recall that the
reaction temperature (80C) is below the Tg of polystyrene (ca. 100C). Notice that when
estimating ne (Eq. 8), the propagation rate constant was assumed not to vary. By comparing
all experiments, it can be seen that the coagulative process is affected by the concentration
of initiator. Indeed, the coagulative process is enhanced at high concentration of initiator,
15

which can also be observed in Figure 4, by analyzing the number of radicals in polymer
particles. Even in the pseudo-steady-state, the average number of radicals per particle is
well above the 0-1 approach, implying a pseudo-bulk system. If we assume that during the
oligomer coagulation mechanism, each one conserves its identity (39), the higher the
concentration of initiator, the higher the number of radicals per particle.
This nucleation period is, as stated above, caused by the APS concentration and the
bSP can stabilize the particles, especially at high APS concentration. Nevertheless, these
bPS help the stabilization mechanism, as seen when the experiment (at 1% APS) is
compared with the blank. As reported by Zhou et al. (40), the coagulation of oligomers onto
the surface of silica does not occur because the electrostatic repulsions between the silica
particles and dissolved KPS. Consequently, the oligomers become insoluble in the aqueous
phase and precipitate to reduce their interfacial area. The resulting polymer particles further
grow and their surface charge density then decreases. Zhou et al. (40) and Colver et al. (28)
mentioned that when collision occurs, the nanoparticles adhere to the growing polymer
particle surface, providing extra electrostatic charge repulsions between growing polymer
particles and thus impeding the system coagulation.
The experimental results allow stating that silica particles are not involved in the
nucleation step, but it is expected that they promote the coagulative process, especially at
high APS concentration. This effect is observed in Figure 2, where the latex particle
diameter grows as the concentration of APS increases. Also, the coagulation is enhanced at
high APS concentration. Nonetheless, the bSP presence is beneficial for the polymerization
process because the latex particle diameter of the blank (1 wt% APS) is larger than the
particles obtained at 1 wt% APS, when bSP were used. It has been reported (28) that during
the growing step (interval II of the emulsion polymerization processes), the interfacial area
16

between latex particles and the aqueous phase increases. Therefore, the particles need to be
stabilized with enough charge or by other agents, to impede coagulation. In this part of the
study, the negative hydrophilic silica particles do not have any affinity with the growing
latex particles. Therefore, the stability effect promoted by hetero-coagulation between silica
and latex particles can be excluded. We propose that the bSP, as well as the APS in
solution, act like a salting-out-effect, promoting oligomeric coagulation. Actually, if we
consider that the length of an oligomer is composed by 2-3 monomer units (36) and it is
about 5 long, then, a silica particle (10 nm) is about 20 times larger than an oligomer.
The experiments containing 0.5 % and 1 % APS will have 50% and 70% fewer
oligomers, when compared with the 2% APS experiment, even though this reduction in
oligomeric concentration is not important, the salting-out-effect caused by the bSP, in
relation with the APS concentration, is very pronounced as seen in Figure 1, when
comparing the conversion evolution, as well as the average radical concentration, inside the
particles pictured in Figure 4.
Additionally, the ratio

, where R is the gyration radius of an oligomer and D the

diameter of a silica particle, is about 0.06, this signifies that during the nucleation period
silica particles can be considered the big particles with respect to oligomers (41). Therefore,
at low initiator concentration, the production of oligomers is slow and the oligomers are
relatively well dispersed in the aqueous phase. Thus, coagulation inevitably occurs because
the oligomers need to reduce their interfacial area and charge density to be stable. Then, it
can be considered that the big silica particles provide an additional barrier to the system due
to electrostatic repulsions charges and their size. At low APS concentration, fewer
oligomers need to participate in the coagulation event to form a mature polymer particle.
Regarding the entry to particles coefficients

(min-1), if we assume that we can obtain an

17

approximate value, if = dn/dt at time equal to zero, the corresponding values are: 0.05,
0.16 and 1.7 (min-1) for the 0.5, 1.0 and 2.0 APS wt.%, respectively. For the blank, was
0.1 min-1. If we compare the values for the 1% APS for the bSP and the blank, it is evident
that SiO2 promotes the entry of radicals.
4.2 Modified SiO2 particles (mSP)
Previous works have used stability coadjuvants such as PEGMA (30) and EGDMA (42), to
improve the Pickering process. In this work, after some previous experimental trials, the
addition of small amounts of CTAB (310-3 M below the CMC = 810-3 M (43)) and NaCl
were tested to perform this task (44, 45). Table 2 shows the recipe employed in these
experimental runs.
Figure 5 shows the corresponding conversion kinetics and it can be seen that the
physical modification can substantially improve the rate of polymerization and reduce the
particle diameter. Fig. 5 shows as before, that the higher the APS content the faster the
polymerization. In this graph, the experiment in which no physical modification (bSP) was
performed for 1% APS is also presented (open circles). Comparing the bSP (open circles)
with the mPS (solid circles), both with 1% APS, it can be seen that the time to reach
maximum conversion can be reduced approximately by half, going from 180 min (open
circles) to ca. 100 min. (solid circles) when the physical modification is performed.
The inset in Figure 5 presents the conversion derivative against conversion, a faster
approach to a steady-state plateau is reached almost immediately, and a gel effect is also
observed starting at about 45% conversion.
Figure 6 presents Dp against x1/3 where the particle diameter is reduced as the APS is
increased, as expected, as opposed to what happened in the bSP case (see Figure 2). Also,
the particle diameter is less sensitive to initiator concentration. In this case, the small
18

addition of CTAB helped to improve the particle stabilization. This is also confirmed
comparing the experiment at 1 % APS (open circles) observing that the particle diameter is
reduced from 550 to less than 300 nm. A horizontal behavior means that Np is linear with
conversion (Eq. 7).
Figure 7 confirms that particle stabilization was achieved because the higher the
APS content, the higher the nucleation rate. Two nucleation periods are observed: one very
fast, up to less than 10% conversion, and a second one, linear with conversion, up to the
end of the experiment. The higher the APS content the higher the slope in the second
nucleation period. For the 1% APS content in the untreated SiO2 case, the particle number
is almost an order of magnitude smaller, as compared with the mSP at the same APS
content.
Figure 8 presents the inferred ne against conversion. Here, it is evident that the
average number of radicals is drastically reduced when compared with the bSP. Here, a
pseudo-bulk system is also detected. The entry to particles coefficients, calculated as stated
above, yield: 0.22, 0.24 and 2.14 (min-1) for the 0.5, 1.0 and 2.0 APS wt %, respectively.
These are much higher than the ones obtained in the bSP. Comparing the values for the 1%
APS for the bSP (0.16 min-1) and the mSP (0.24 min-1), it is evident that the modification of
SiO2 promotes the entry of radicals in a more controlled fashion.
The main differences observed between the kinetics using bSP and mSP
polymerization processes lies in the presence of silica-CTAB aggregates. Therefore, it is
clear that both systems play a crucial role in the nucleation process and on the latex
particles growth, even though, as pointed out above, the bSP do not participate in the
nucleation process. Actually, the CTA+ cations interact electrostatically with the SiO
anions on the solid nanoparticles surfaces, and therefore adsorb onto the silica surface, and
19

the emulsifier tails are projected towards the aqueous phase. At this low CTAB
concentration, there is only formation of hydrophobic patches onto the silica and
consequently, particles agglomerate due to their reduced superficial charge (44) and the
existence of hydrophobic interactions between particles CTA+ tails. Zhou at al. (39) argued
that the silica-aggregates form hydrophobic sites, which can serve as micelles and, due to
partial solubilization of monomer molecules in water, they can fit inside the aggregates as
shown in scheme 1.a. Once the initiator is injected, it decomposes in the aqueous phase and
forms oligomers which will react with the monomers located inside the pseudo-micelles
(aggregates in hydrophobic zones, Scheme 1.a). The resulting nuclei can grow, via
diffusion of monomer from the aqueous phase, due to swelling of these incipient polymer
nuclei. Therefore, the oligomers coagulation occurs because they need to reduce their
interfacial area and give rise to the formation of mature particles. The initial nucleationcoagulation process is drastically reduced due to the presence of silica-CTAB
nanoparticles, surrounding the growing polymer particles, providing them stability. This
nucleation period is similar to the CEP processes, represented by the interval I, where
primary nucleation occurs, yielding the formation of mature polymer particles (Scheme
1.c). On the other hand, in Figure 6, Dp vs. x1/3 is fairly constant for all experiments
involving CTAB-modified silica particles (mSP), this signifies that Np is almost
proportional to conversion x (Scheme 1.d). This is confirmed in Figure 7, where the slope
of the Np vs. x curves drastically increases at the beginning of the reaction to continue
rising, although more slowly. These results indicate that the polymerization process
involves two nucleation periods. A first one (corresponding to CEP interval I), ceasing at
approximately 5-10% conversion (Scheme 1.c), followed by another slower period
(Scheme 1.d). A large nucleation process period was observed by Sheibat-Othman et al.
20

(30) with the polymerization of styrene using laponite clay platelets. They reported that an
increase in particle number with time reveals the occurrence of secondary nucleation. The
fact that there is a continuous generation of particles means that the pseudo-micelles could
store monomer and/or the formed particles surrounded by mSP swell less than in a CEP,
yielding a longer interval II where monomer droplets exist at higher conversions (Scheme
1.d). Here, the higher the concentration of initiator, the smaller the latex particles, as
expected. These events can solely be ascribed to the presence of the silica-CTAB
aggregates.
Indeed, the amount of silica-CTAB particles used for preparing the emulsion is in
excess to fully cover the monomer/water interface (ca. 3-5 m), addressed at the end of this
section. The formation of two types of aggregates (small and large) was mainly caused by
sonication. It is expected that the smallest aggregates are located in the monomer/water
interface, impeding droplet coalescence (28). At the beginning of the reaction, the larger
ones are dispersed in the aqueous phase forming a 3-D network. Consequently, as a large
amount of aggregates continue to be dispersed in the aqueous phase, the silica-CTAB
particles are exclusively available for nucleation.
A bridge will be formed between the growing oligomers and the CTAB-ends
pointed towards the aqueous phase (29). These agglomerated oligomers will keep growing
via swelling and two outcomes can occur: (i) coagulation between/among oligomers and/or
(ii) oligomers can hide from the aqueous phase, migrating towards the hydrophobic areas,
inside the pseudo-micelles (39), to achieve stability. Thus, as polymerization proceeds, the
increasing polymer/water interface is initially stabilized by the CTAB-modified silica
particles. During the reaction, the growing latex particles are poorly covered by negative
silica-CTAB particles because they contain SO2- groups, and both particles repel each
21

other. Finally, the aggregates are destroyed as the latex particles grow inside them (Scheme
1.c and 1.d) and the colloidal latex dispersion is stable due to electrostatic repulsions
between latex particles and silica-CTAB particles (Scheme 1.e).
Finally, as the mSP participate in the nucleation process and stabilize the polymer
particles, the amount of mSP in the aqueous media should have a direct impact on the
polymerization kinetics and the latex particle size. Consequently, the quantity of mSP used
in the original recipe (2.1 wt.%) was reduced to 75 and 50%, to verify that the mSP were
used in excess and how the mSP concentration affects the nucleation process and the
polymer particle stabilization. Figure 9 shows that using 75% of the initial solution yields a
better result regarding the rate of polymerizations and particle size (Figure 10).
In Figure 11, it can be observed that all experiments present two nucleation periods, one
very fast (around 10% conversion) and a second one, linear with conversion, up to the end
of the polymerization process. Therefore, a high and stable number of particles was
produced in the first polymerization step, followed by a continuous nucleation period until
monomer supply depletion. The particle density goes from higher to lower as: 75% > 100%
> 50%. This indicates that better polymer particle stability was provided at 75%;
consequently, the coagulative process was reduced (also revealed by a small-inferred n as
shown in Figure 12). Accordingly, there is an optimum concentration of mSP, which helps
to obtain a faster polymerization rate and smaller polymer particle size, which is in
agreement with the work of Teixeira et al. (29) where they reported that the particles act in
the nucleation process.
5. Conclusions
The effect of initiator (ammonium persulfate) content on bare and modified -with
hexadecyltrimethylammonium bromide- SiO2 nanoparticles, was studied in the styrene
22

Pickering emulsion polymerization. An anomalous behavior occurs when SiO2 are not
surface modified, yielding a chaotic nucleation. The more initiator used, the greater the
particle diameter obtained, contrary to what is expected. The bare SiO2 particles participate
in the nucleation process, providing a salting-out-effect and acting as a barrier to the
oligomers formed accelerating the reaction, as compared with a blank (i.e., without SiO2)
emulsion polymerization. The fastest reaction rate at high initiator content is explained
by a higher radical number inside the particles. Particle nucleation occurs along the reaction
in the experiments which have low initiator concentrations. When SiO2 particles are surface
modified, with a small amount of hexadecyltrimethylammonium bromide (below the
critical micelle concentration), a higher polymerization rate and a more controlled process
are obtained. In this latter case, particle nucleation occurs along the reaction. Two
nucleation rate periods exist when the modified SiO2 particles are present. The modified
SiO2 nanoparticles participate in the growing polymer particles nucleation and stabilization
mechanisms, providing affinity with silica nanoparticles due the presence of CTAB tails
onto the silica particles, therefore leading to the formation of smaller particles in
comparison with bare SiO2 nanoparticles experiments. It was found that the modified SiO2
nanoparticles promote the entry of radicals in a more controlled fashion. Regarding the
average number of radicals per particle, in all studied systems a pseudo-bulk system was
detected. To prove that an excess of mSP was used, the amount was reduced by 50%
without significantly altering the rate mechanisms.
Funding
This work was financially supported by: DGAPA-PAPIIT project IN113215, CONACyT
grant CB-2014-240160, PRODEP project UV-PTC-227, PROFOCIE project 30MSU0940B

23

and UNAM-UV interchange program. We thank Prof. E. J. Vernon-Carter (UAM-I) for the
Dynamic Light Scattering equipment utilization.
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27

Glossary of Tables and Figures

Table 1: Composition of aqueous dispersion for the modified silica particles (mSP).
Table 2. Emulsion polymerization reaction composition for bare silica particles (bSP) and
CTAB-modified silica particles (mSP).
Table 3. Parameters used for the average radical number per particle (ne) estimation.

Fig. 1. Experimental conversion against time data for bSP (Triangles: 2%, circles: 1% and
squares 0.5 % APS; open diamonds: 1 % APS without SiO2). Continuous lines correspond
to the fitting conversion (Eq. 9).

Inset: Smoothed time-conversion-derivative against

smoothed conversion (Eq. 9).

Fig. 2. Experimental particle diameter (Dp) against smoothed x1/3 for the bSP (Triangles:
2%, circles: 1% and squares 0.5 % APS; open diamonds: 1 % APS without SiO2).
Continuous lines correspond to the fitted diameter and conversion (Eqs 10 and 9).
Fig. 3. Experimental particle density (Np) against smoothed conversion for the bSP
(Triangles: 2%, circles: 1% and squares 0.5 % APS; open diamonds: 1 % APS without
SiO2). Continuous lines correspond to estimating Np applying Eq. 7 using the smoothed
conversion and diameter (Eqs 9 and 10).
Fig. 4. Continuous lines correspond to the inferred average radicals per particle number
(ne) against conversion using Eq. 8 with the smoothed conversion derivative (Eq. 9) and Eq.
7 for the bSP.
Fig. 5. Experimental conversion against time data for the surface modified SiO2 (mSP)
(Triangles: 2%, circles: 1% and squares 0.5 % APS; open circles: 1 % APS without
CTAB). Continuous lines correspond to the fitting conversion (Eq. 9). Inset: Smoothed
time-conversion-derivative against smoothed conversion (Eq. 9).
28

Fig. 6. Experimental particle diameter (Dp) against smoothed x1/3 for the mSP (Triangles:
2%, circles: 1% and squares 0.5 % APS; open circles: 1 % APS without CTAB).
Continuous lines correspond to the fitted diameter and conversion (Eqs 9 and 10).
Fig. 7. Experimental particle density (Np) against smoothed conversion for the mSP
(Triangles: 2%, circles: 1% and squares 0.5 % APS; open circles: 1 % APS without
CTAB). Continuous lines correspond to estimating Np applying Eq. 7 using the smoothed
conversion and diameter (Eqs 9 and 10).
Fig. 8. Continuous lines correspond to the inferred average radicals per particle number
(ne) against conversion using Eq. 8 with the smoothed conversion derivative (Eq. 9) and Eq.
7, for the mSP.
Fig. 9. Experimental conversion against time data for the physically modified SiO2. Circles:
100 % mSP; squares: 75% mSP and diamionds: 50% mSP. Continuous lines correspond to
the fitting conversion with (9). Inset: Smoothed time-conversion-derivative against
smoothed conversion.
Fig. 10. Experimental particle diameter (Dp) against smoothed x1/3, circles: 100 % mSP;
squares: 75% mSP and diamionds: 50% mSP. Continuous lines correspond to the fitted
diameter (Eq. 10) and conversion (Eq. 9).
Fig. 11. Experimental particle density (Np) against smoothed conversion (circles: 100 %
mSP; squares: 75% mSP and diamionds: 50% mSP). Continuous lines correspond to
estimating Np applying Eq. 7 using the smoothed conversion and diameter (Eqs 9 and 10).
Fig. 12. Continuous lines correspond to the inferred average radicals per particle number
(ne) against conversionusing Eq. 8 with the smoothed conversion derivative (Eq. 9) and Eq.
7.

29

Scheme 1. Schematic representation (not to scale) of the styrene polymerization process in

emulsion stabilized by mSP particles. a) Emulsion before injecting APS, b) Initiation of the
polymerization process, c) First nucleation step similar to interval I in the CEP, d) Second
interval step, e) Latex particle poorly covered by mSP nanoparticles.

30

Tables:
Table 1. Composition of aqueous dispersion for the modified silica particles (mSP).

Bindzil 830

mSP dispersion

-1

CTAB (g.L )

300

-1

CTAB:SiO2

wt% of

ratio

silica

0.013

NaCl (g.L )

1.2

0.5

Table 2. Emulsion polymerization reaction composition for bare silica particles (bSP) and
CTAB-modified silica particles (mSP).

SiO2-CTABStyrene

Water

wt.% of Silica
Bindzil 830

NaCl Dispersion
(g)

(g)

in the water
(g)

(g)

phase

bSP

75

395

---

30

2.1

mSP

75

325

100

---

2.1

Table 3. Parameters used for the average radical number per particle (ne) estimation.
Parameter

Value

Reference

924-0.918 (T-273.15)

(35)

1,084.8-0.605(T-273.15)

(35)

Mpmax (mol L-1)

5.5

(36)

Mw (g mol-1)

104.15

kp (L mol-1s-1)

4.27107Exp (-32500/RT)

m (g

L-1)

(g L-1)

(38)

31

Figures:

Fig. 1. Experimental conversion against time data for bSP (Triangles: 2%, circles: 1% and
squares 0.5 % APS; open diamonds: 1 % APS without SiO2). Continuous lines correspond
to the fitting conversion (Eq. 9).

Inset: Smoothed time-conversion-derivative against

smoothed conversion (Eq. 9).

32

Fig. 2. Experimental particle diameter (Dp) against smoothed x1/3 for the bSP (Triangles:
2%, circles: 1% and squares 0.5 % APS; open diamonds: 1 % APS without SiO2).
Continuous lines correspond to the fitted diameter and conversion (Eqs 10 and 9).

33

Fig. 3. Experimental particle density (Np) against smoothed conversion for the bSP
(Triangles: 2%, circles: 1% and squares 0.5 % APS; open diamonds: 1 % APS without
SiO2). Continuous lines correspond to estimating Np applying Eq. 7 using the smoothed
conversion and diameter (Eqs 9 and 10).

34

Fig. 4. Continuous lines correspond to the inferred average radicals per particle number
(ne) against conversion using Eq. 8 with the smoothed conversion derivative (Eq. 9) and Eq.
7 for the bSP.

35

Fig. 5. Experimental conversion against time data for the surface modified SiO2 (mSP)
(Triangles: 2%, circles: 1% and squares 0.5 % APS; open circles: 1 % APS without
CTAB). Continuous lines correspond to the fitting conversion (Eq. 9). Inset: Smoothed
time-conversion-derivative against smoothed conversion (Eq. 9).

36

Fig. 6. Experimental particle diameter (Dp) against smoothed x1/3 for the mSP (Triangles:
2%, circles: 1% and squares 0.5 % APS; open circles: 1 % APS without CTAB).
Continuous lines correspond to the fitted diameter and conversion (Eqs 9 and 10).

37

Fig. 7. Experimental particle density (Np) against smoothed conversion for the mSP
(Triangles: 2%, circles: 1% and squares 0.5 % APS; open circles: 1 % APS without
CTAB). Continuous lines correspond to estimating Np applying Eq. 7 using the smoothed
conversion and diameter (Eqs 9 and 10).

38

Fig. 8. Continuous lines correspond to the inferred average radicals per particle number
(ne) against conversion using Eq. 8 with the smoothed conversion derivative (Eq. 9) and Eq.
7, for the mSP.

39

Fig. 9. Experimental conversion against time data for the physically modified SiO2. Circles:
100 % mSP; squares: 75% mSP and diamionds: 50% mSP. Continuous lines correspond to
the fitting conversion with (9). Inset: Smoothed time-conversion-derivative against
smoothed conversion.

40

Fig. 10. Experimental particle diameter (Dp) against smoothed x1/3, circles: 100 % mSP;
squares: 75% mSP and diamionds: 50% mSP. Continuous lines correspond to the fitted
diameter (Eq. 10) and conversion (Eq. 9).

41

Fig. 11. Experimental particle density (Np) against smoothed conversion (circles: 100 %
mSP; squares: 75% mSP and diamionds: 50% mSP). Continuous lines correspond to
estimating Np applying Eq. 7 using the smoothed conversion and diameter (Eqs 9 and 10).

42

Fig. 12. Continuous lines correspond to the inferred average radicals per particle number
(ne) against conversionusing Eq. 8 with the smoothed conversion derivative (Eq. 9) and Eq.
7.

43

Scheme 1. Schematic representation (not to scale) of the styrene polymerization process in

emulsion stabilized by mSP particles. a) Emulsion before injecting APS, b) Initiation of the
polymerization process, c) First nucleation step similar to interval I in the CEP, d) Second
interval step, e) Latex particle poorly covered by mSP nanoparticles.

44