Copyright 2006 American Scientic Publishers

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Printed in the United States of America

Journal of
Nanoscience and Nanotechnology
Vol. 6, 432444, 2006

Nucleation of Polystyrene Latex Particles

in the Presence of
-Methacryloxypropyltrimethoxysilane: Functionalized Silica Particles
Elodie Bourgeat-Lami,1
Mickaelle Insulaire,1 Stphane Reculusa,2 Adeline Perro,2
Serge Ravaine,2 and Etienne Duguet3
1

Laboratoire de Chimie et Procds de Polymrisation CNRS-CPE Lyon, Btiment 308 F,

43, boulevard du 11 novembre 1918, BP 2077, 69616 Villeurbanne Cedex, France
2
Centre de Recherche Paul Pascal CNRS, 115, Avenue du Dr Schweitzer, 33600 Pessac, France
3
Institut de Chimie de la Matire Condense de Bordeaux CNRS,
SCD
Universite
Bordeaux
(cid 87001294)
87, Avenue
du Dr Schweitzer,
336081Pessac
Cedex, France

IP : 147.210.61.244

RESEARCH ARTICLE

03 Feb
15:45:03
Silica/polystyrene nanocomposite Fri,
particles
with2006
different
morphologies were synthesized through
emulsion polymerization of styrene in the presence of silica particles previously modied by

-methacryloxypropyltrimethoxysilane (MPS). Grafting of the silane molecule was performed by
direct addition of MPS to the aqueous silica suspension in the presence of an anionic surfactant
under basic conditions. The MPS grafting density on the silica surface was determined using the
depletion method and plotted against the initial MPS concentration. The inuence of the MPS
grafting density, the silica particles size and concentration and the nature of the surfactant on
the polymerization kinetics and the particles morphology was investigated. When the polymerization was performed in the presence of an anionic surfactant, transmission electron microscopy
images showed the formation of polymer spheres around silica for MPS grafting densities lower than
typically 1 molem2 while the conversion versus time curves indicated a strong acceleration effect
under such conditions. In contrast, polymerizations performed in the presence of a larger amount of
MPS moieties or in the presence of a non ionic emulsier resulted in the formation of excentered
core-shell morphologies and lower polymerization rates. The paper identies the parameters that
allow to control particles morphology and polymerization kinetics and describes the mechanism of
formation of the nanocomposite colloids.
Keywords: Silica,
-Methacryloxypropyltrimethoxysilane, Nanocomposite Particles, Polystyrene,

Delivered
by Ingenta
Nucleation, Emulsion
Polymerization,
Particlesto:
Morphology.

1. INTRODUCTION
In the last few decades, the interest for hybrid particles that
combine organic and inorganic parts has increased considerably due to the potential benets of these nanoobjects in
multiple areas of material science.16
For example, Furusawa et al.7 described the synthesis
of silica/polystyrene core-shell particles in the presence
of hydropropyl cellulose (HPC) used as polymeric binder/
stabilizer. HPC provided hydrophobic loci that promoted
efcient capture of the growing polymer chains. When the
emulsion polymerization reaction was performed in the
presence of an anionic emulsier at concentrations higher
than its critical micellar concentration (cmc), particles with

Author to whom correspondence should be addressed.

432

J. Nanosci. Nanotechnol. 2006, Vol. 6, No. 2

a raspberry shape were obtained illustrating the determinant role of interfaces in the control of particles morphology. More recently, Armes et al.810 synthesized polymer/
silica nanocomposite particles through soapless emulsion
copolymerization of styrene and acrylic monomers using
4-vinyl pyridine (4-VP) as a basic comonomer. The presence of the 4-VP comonomer ensured strong interaction
of the vinyl polymers with the acidic silica surface resulting in the formation of nanocomposite colloids with a
currant-bun morphology characterized by silica beads
assembled into colloidal aggregates cemented together by
the polymer synthesized during the emulsion polymerization reaction. The small silica particles emerging from
the composite surface were shown to participate to the
colloidal stability of the particles. Following a related
1533-4880/2006/6/432/013

doi:10.1166/jnn.2006.021

Bourgeat-Lami et al.

Nucleation of Polystyrene Latexes on Functionalized Silica Particles

strategy, Luna-Xavier et al.1113 described the preparaacademic reports have been devoted to this system.2731
Moreover, very few efforts have been done up to now to
tion of poly(methyl methacrylate)/silica composite partidescribe the mechanism of formation of the nanocomposcles using an electrostatically-adsorbed cationic initiator to
ite particles. As a matter of fact, a better understanding is
promote polymerization at the surface of an anionic silneeded of where is nucleation occurring and how are these
ica sol, while Reculusa et al.1415 recently demonstrated
particles formed. In addition, no data have been provided
that the adsorption of a monomethylether mono methylso far on the kinetic aspects of the polymerization although
methacrylate poly(ethylene oxide) macromonomer allowed
previous works in the literature have demonstrated that
to control the assembly of polystyrene latex particles on the
polymerizations performed in the presence of mineral parsurface of silica particles through an in situ nucleation and
ticles may exhibit particular kinetic behaviors.3234
growth process. Either raspberry-like14 or dumbbell-like15
The aim of this paper is to give insights into the
morphologies were obtained with this technique depending
mechanism of formation of polymer/silica nanocomposite
on the size and concentration of the silica seed particles.
particles through emulsion polymerization using MPS as
In the 1990s, Espiard et al.1618 reported results on the
capping agent. Following a previous work,35 the grafting
encapsulation of silica particles through emulsion polyof MPS was performed directly in water and the emulsion
merization using
-methacryloxypropyl trimethoxysilane
polymerization reaction was carried out in the presence
(MPS) as capping agent. The role of MPS is to provide
of either an anionic or a non-ionic surfactant. In order to
reactive double bonds for covalent attachment of the growget a real control of the encapsulation process, we varied
ing polymer chains on the silica surface. Owing to the
the 1number
of inorganic seed particles by changing their
presence of the grafted polymer,SCD
the inorganic
surface
Universite Bordeaux
(cid 87001294)
size
or
their
mass
concentration. This work mainly focuses
turned out to be more hydrophobic and presented
loci
IP : 147.210.61.244
on the effect of the MPS grafting density, the silica parfor the adsorption of monomer molecules and
capture
of
Fri, 03 Feb 2006 15:45:03
ticles size and concentration, the amount and nature of
oligoradicals, which process enabled the formation of a
the surfactant on the polymerization kinetics and particles
polymer shell surrounding the silica particles. Following
1923
morphology.
this direction, Bourgeat-Lami and Lang
described in a

J. Nanosci. Nanotechnol. 6, 432444, 2006

2. EXPERIMENTAL DETAILS
2.1. Materials
Two kinds of silica suspensions were used: a colloidal
silica sol produced through the Stber process,36 and a
concentrated aqueous suspension of commercial silica particles (Klebosol 30N50, Clariant) with an average diameter
of 68 nm (as determined by dynamic light scattering) and
32 wt% solid content. The reagents for synthesis of the
Stber silica sol: absolute ethanol (Carlo Erba), ammonium hydroxide (25%, Laurylab) and tetraethyl orthosilIngenta
to: Fluka) were of analytical grade and used
icate (TEOS,
as supplied. Methacryloxy propyl trimethoxysilane (MPS,
Aldrich) was used as received. The monomer, styrene
(Aldrich) and the initiator, potassium persulfate (KPS,
MW = 27033 g mol1 , Acros Organics), were used without further purication. The anionic surfactant, sodium
dodecyl sulfate (SDS, MW = 28838 g mol1 , Acros
Organics) and the nonylphenol poly(oxyethylenic) nonionic surfactant (Remcopal NP30 , MW = 1540 g mol1 ,
a gift from CECA S.A, Paris) were of analytical grade
and used as received. Deionized water was puried by a
Milli-Q Academic system (Millipore Cooperation).
2.2. Synthetic Procedures
The suspension of silica particles in a mixture of ethanol
and water was prepared according to the procedure of
Stber et al.36 Typically, ethanol (665 g), water (89.7 g)
and concentrated ammonia (23.4 g) were introduced in a
433

RESEARCH ARTICLE

series of articles the encapsulation of MPS-grafted silica

beads using dispersion polymerization of styrene in aqueous alcoholic solutions. The authors rst demonstrated that
the use of MPS was a prerequisite condition for encapsulation to succeed.19 In the following articles,2022 they
have investigated in details the inuence of the size and
concentration of the silica beads on the shape and composition of the composite particles for a variety of monomers.
The average number of silica beads per polymer particle
was statistically determined from the transmission electron microscopy (TEM) images, and was found to vary
from one to several thousands with increasing the number of silica beads in the suspension medium.Delivered
While the by
particles containing only one silica bead had an irregular
contour, those loaded with a larger amount of silica
displayed a spherical shape. Regular core-shell morphologies were also obtained when using a poly(styrene-bethylene oxide) copolymer as steric stabilizer.23 In a recent
work, Reculusa et al. showed that daisy-shaped and multipod silica/polystyrene colloids were produced in emulsion polymerization when the grafting density of the MPS
silane molecule was sufciently low to promote formation of polymer nodules on the silica surface.25 Original morphologies were also achieved when the emulsion
polymerization reaction was performed in the presence of
methacryloxy propyl silane-functionalized clay colloids.26
Nanocomposite particles with an inverted core-shell
morphology (the clay platelets forming the shell of the
particles) were successfully produced by this approach.
Actually, a rapid survey of the literature on the use of
MPS in encapsulation reactions shows that only a few

RESEARCH ARTICLE

Nucleation of Polystyrene Latexes on Functionalized Silica Particles

Bourgeat-Lami et al.

reaction ask. Then, TEOS (41.8 g) was added quickly

out at the wavelength of 205 nm using predetermined calibration curves. The MPS grafting density, QMPS (mol
and the mixture was stirred at ambient temperature for
m2 ), was determined by titration of the supernatant soluseveral days. The alcoholic suspension was then centions using the depletion method according to:
trifuged (Beckman Coulter, Allegra 64R centrifuge) at
7,000 rpm for 10 minutes and redispersed into water with
C0 Ce V
106
(1)
QMPS mol m2  =
the help of a laboratory ultrasonic bath (Branson ultrasonic
Mw M Sspec
cleaner 5510).
The commercial aqueous Klebosol suspension was
where C0 (g L1 ) is the initial MPS concentration, Ce
diluted in absolute ethanol and centrifuged at 20,000 rpm
(g L1 ) is the MPS equilibrium concentration determined
for 10 minutes (Beckman Coulter, Allegra 64R centrifuge)
by UV analysis, V (l) designates the volume of solution,
in order to remove the small particles which are present in
M (g) is the mass of silica, Mw (g mol1 ) is the molar
the original suspension.
mass of MPS and Sspec . (m2 g1  is the specic surface
Grafting of the silane coupling agent was performed by
area of silica.
addition of the coupling agent to the aqueous silica sol
Sspec . was calculated using Eq. (2) assuming that the
containing 1 g L1 of the anionic surfactant. The mixtures
particles are non porous and spherical.
were prepared by introducing known amounts of MPS into
6000
100 mL of a 10 g L1 stock silica suspension. The dis(2)
Sspec m2 g1  =
 Dn
persions were stirred magnetically at ambient temperature
and allowed to equilibrate for 19 hours. They were next
where
 (g87001294)
cm3 ) is the density of silica and Dn (nm) is
SCD Universite Bordeaux
1 (cid
centrifuged and the supernatant solutions were analysed
its number average particle diameter.
IP : 147.210.61.244
by UV spectroscopy. The amount of grafted MPS was
grafting yield, which corresponds to the fraction of
Fri, 03 Feb 2006 The
15:45:03
determined by difference between the total amount and
MPS effectively attached to the silica surface, was deterthe free amount of MPS using a predetermined calibration
mined using the following formula:
curve established on silica-free suspensions of identical
(3)
Grafting yield% = 100QMPS /MPS
composition.
Emulsion polymerization reactions were carried out in
where QMPS (mol m2 ) is the MPS grafting density
batch at 70  C for up to 24 hours under nitrogen atmodetermined by UV analysis and [MPS] (mol m2 ) dessphere. The 300 mL glass reactor tted with a condenser
ignates the initial concentration of the silane molecule per
was charged with an aqueous dispersion containing known
unit surface of silica.
concentrations of grafted silica and surfactant. Degassing
The monomer to polymer conversions were determined
was carried out for 15 minutes under gentle stirring before
gravimetrically.
Typically, 37 g of the latex suspension
increasing the temperature up to 70  C. Then, the initiator
was placed in an aluminium dish and dried to constant
dissolved in 10 mL of de-ionized water and the monomer
weight at 80  C. The diameter, Dp, of the polymer latex
were added at once to start polymerization. Samples were
particles synthesized in the absence of silica was deterwithdrawn from the polymerization mixture at regular
mined by dynamic light scattering (DLS) using a Malvern
intervals of time and cooled down to stop polymerization
Autosizer Lo-C instrument with a detection angle of 90 .
before analysis.
The morphology
of the nanocomposite particles was
Delivered
to:
All the latexes produced were coded according
to the by Ingenta
characterized by transmission electron microscopy (TEM).
following nomenclature: A(N)X-K(S)Y-Z where A and N
Specimens for TEM were prepared by evaporating one
stand for Anionic or Non ionic surfactants, respectively, X
drop of dilute latex (103 /106 g cm3 ) on a 200 mesh
is the surfactant concentration in g L1 , K and S stand for
formvar-coated copper electron microscope grid. The grids
Klebosol and Stber silicas, respectively, Y (g L1 ) is the
were placed in the vacuum chamber of a Philips CM120
silica concentration and Z is the initial MPS concentration
electron microscope operating at 80 kV and observed
(mol m2 ). For example, A1-K10-10 designates a polyunder low illumination dose.
merization performed in the presence of 1 g L1 of SDS
The diameters of the polymer particles were measured
and 10 g L1 of the Klebosol silica particles grafted with
directly
from the electron micrographs. A minimum of 100
10 mol m2 of MPS while N 3 is an emulsion polymerparticles
were counted for each batch. The number averization of styrene carried out in the presence of 3 g L1
age diameter, Dn , was calculated using Eq. (4) where ni
of the non ionic surfactant in the absence of silica. The
designates the number of particles of diameter Di .
styrene and initiator concentrations were kept constant all


nD
along this work.
(4)
Dn =
i i
ni
2.3. Characterizations
UV analysis was performed using an UV/VIS spectrophotometer and quartz cells. The measurements were carried
434

The weight average diameter, Dw , was calculated from:

nD4
(5)
Dw =
i i 3
ni Di
J. Nanosci. Nanotechnol. 6, 432444, 2006

Bourgeat-Lami et al.

Nucleation of Polystyrene Latexes on Functionalized Silica Particles

and the polydispersity index (PDI) was given by:

PDI =

Dw
Dn

(6)

The particle number per unit volume of water (Np/L) was

calculated by the following equation:
Np
M/
1019
=
L
/6Dn 3 V

Table I. Number average diameters, weight average diameters and

polydispersity indexes of the silica sols used in the polymerization
experiments.

Dn
Dw
Dw /Dn

Klebosol 30N50

Stber silica

830
834
1005

2460
2476
1006

(7)

where M(g) is the total mass of solid, (g cm3 ) is the

density of the particles, Dn (nm) is the number average
particles diameter determined from the TEM micrographs,
and V (in liter) is the total volume of water.

(PDI = Dw /Dn ). PDI values lower than typically 1.05 indicate that the particles are monodisperse.
3.2. Grafting of the MPS Coupling Agent

J. Nanosci. Nanotechnol. 6, 432444, 2006

435

RESEARCH ARTICLE

A lot of work has been done in the literature on the grafting of organoalkoxysilanes onto several inorganic surfaces
3. RESULTS
for applications in chromatography, catalysis, etc. Classically, the grafting is performed in dried solvents and
3.1. Characterization of the Silica Sols
the water for hydrolysis is that contained on the mineral
17 87001294)
SCD
Universite
Bordeaux
1 (cid
The water may also be introduced in the reaction
surface.
Figure 1 shows TEM micrographs of the Stber and
IP
:
147.210.61.244
medium
and
removed further by distillation to promote
Klebosol silica suspensions, respectively. Both sets of parFri,
03
Feb
2006
15:45:03
condensation
reactions
as reported for instance by Philipse
ticles exhibit a spherical shape and a low size distribution.
37
et
al.
Silane
molecules
can also be conveniently grafted
The number and weight average diameters are indiin
mixtures
of
ethanol
and
water by direct addition of the
cated in Table I together with the polydispersity index
silane molecule to the alcosol as reported in previous studies from our group.1925 In the present work, the grafting
(a)
was done directly by simply adding the coupling agent to
a dilute aqueous suspension of the silica beads in the presence of surfactant. The role of the surfactant is to help
disperse the MPS molecules in water and also to reduce
the size of the polycondensates that are susceptible to be
formed in the surrounding aqueous solution.38
Because of the large surface area which commonly
occurs in colloidal systems, the amount of adsorption can
often be determined directly from the depletion of the
adjoining liquid phase, especially if strong interactions are
involved in the process. This technique is well developed
Delivered by Ingenta
to: for the determination of adsorbed surfacin the literature
tant concentrations and allows the establishment of adsorption isotherms. We decided to extrapolate this method
to the quantitative determination of the amount of MPS
(b)
on the silica surface without distinction on whether the
silane is simply adsorbed (as in surfactant systems) or truly
grafted. For simplicity, the MPS surface concentration will
be dened hereafter as the grafting density. The advantage of this technique compared to conventional titration
methods such as the estimation of the carbon content, is
the sensibility of UV analysis which allows accurate determination of very low residual concentrations in water solution. The technique thus appears particularly well suited
for low grafting densities determination which is actually
one of the objectives of this work.
Figure 2 shows the evolution of the MPS grafting density and the MPS grafting yield as a function of the
initial MPS concentration. The grafting density increases
Fig. 1. TEM micrographs of: (a) The commercial fractionated Klebosol
with increasing the silane content and reaches a plateau at
30N50 silica sol and (b) the Stber silica.

Nucleation of Polystyrene Latexes on Functionalized Silica Particles

Grafting density (moles/m)

Bourgeat-Lami et al.

Similar curves have been reported in the literature for

the emulsion polymerization of butyl acrylate using SDS
as surfactant39 or for styrene emulsion polymerization with
aerosol MA as surfactant.40 Considering that the cmc of
SDS in electrolyte free aqueous solution is 2 g L1 (i.e.,
6.93 mM), the different parts of the curves correspond
to the following regimes: surfactant concentration below,
around or above the cmc and can be explained as follows.
At low surfactant concentrations, homogeneous nucleation
predominates and the overall particle number is almost
independent on the SDS concentration. As surfactant concentration increases, there is a rise in particle number at
SDS concentration close to the cmc. This clearly illustrates that micelles are the main locus of particle formation
as suggested by the Smith-Ewart micellar theory.41 Well
above the cmc, micellar nucleation dominates and the particle number follows the [S]3/5 dependence on surfactant
concentration predicted by Smith-Ewart.

Grafting yield (%)

100

90
2.5

80
70

60
50

1.5

40
1

30
20

0.5

10
0

0
0

10

15

20

[MPS] (moles/m)

Fig. 2. MPS grafting density and grafting yield as a function of the

initial MPS concentration. The grafting was performed by direct addition
of MPS to a 10 g L1 aqueous silica particles suspension containing
1 g L1 SDS. The reaction was carried out at pH = 93 for 19 hours
SCD Universite Bordeaux
under magnetic stirring.

1 (cid 87001294)
IP : 147.210.61.244
3.4. Polymerizations Performed in the Presence of
Fri, 03 Feb 2006 15:45:03
MPS-Functionalized Silica Particles
high concentrations while, concurrently, the grafting yield

RESEARCH ARTICLE

decreases. It is worth noting that although the grafting was

performed under very different conditions, a similar curve
was reported by Bourgeat-Lami for the grafting of aerosil
silica with MPS in toluene.17
3.3. Polymerizations Performed in the Absence
of Silica Particles

Polystyrene latexes were prepared in batch through emulsion polymerization under conventional conditions using
either a non ionic or an anionic surfactant. The reactor was
charged with the surfactant, styrene monomer, KPS, and
water in the quantities shown in Table II.
Monodisperse spherical PS particles were produced
whatever the experimental conditions. The particles
diam- by
Delivered
eter and particles number determined by DLS are reported
in Table III together with the monomer conversion. The
polymer particle number is also plotted in Figure 3 as a
function of the surfactant concentration.
The curve of Figure 3 exhibits a sigmoidal shape with
three distinct slopes (1.5, 4.3, and 0.5, respectively).

(a) Effect of the MPS Grafting Density on Particles Morphology. As shown in previous works, grafting of the MPS
coupling agent is a prerequisite condition for successful formation of nanocomposite particles surrounded by
polymer.19 In order to investigate this parameter in more
depth, a set of experiments was performed using SDS as
surfactant and various MPS concentrations according to
the recipes given in Table IV. The actual amount of MPS
present on the silica surface was determined from the UV
isotherm shown in Figure 2 and is reported in Table IV. All
the polymerization were conducted under the same conditions, that is to say with 100 g L1 of styrene, 0.5 wt% of
KPS with respect to styrene, 1 gL1 of SDS and 10 gL1
of silica.
Figure to:
4 shows the conversion versus time curves for
Ingenta
polymerizations performed in the presence of silica particles containing an increasing amount of double bonds on
their surface. While the polymerization carried out with
un-grafted silica particles exhibits the same kinetic behavior as that of the reference experiment without silica (A1),
all the other experiments showed a higher polymerization

Table II. Recipes for studying the emulsion polymerization of styrene with various surfactant concentrations.
Latex code
Ingredient
Water (g)
SDS (g)
NP30 (g)
Styrene (g)
KPS (g)
[Surfactant] (mM)a
a

436

A0.5

A1

A1.5

A2

A3

A8

N3

100
005
/
10
005
173

100
01
/
10
005
347

100
015
/
10
005
520

100
02
/
10
005
693

100
03
/
10
005
1040

100
08
/
10
005
2774

100
/
03
10
005
195

Based on water. Temperature = 70  C.

J. Nanosci. Nanotechnol. 6, 432444, 2006

Bourgeat-Lami et al.

Nucleation of Polystyrene Latexes on Functionalized Silica Particles

Table III. Monomer conversion, particle size and particle number for a series of polymer latexes produced by emulsion
polymerization of styrene at 70  C using various concentrations of SDS and NP30 surfactants.
Latex code

Conversion (%)
Dp (nm) a
Np/Lb
a
b

A0.5

A1

A1.5

A2

A3

A8

N3

87
272
82 1015

97
199
23 1016

100
157
49 1016

100
99
2 1017

100
58
98 1017

100
50
16 1018

90
202
21 1016

Determined by DLS.
Determined from Eq. (7) by replacing Dn by Dp .

80
Slope=0.5

CMC

1.00E+19
1.00E+18

Slope=4.3
Slope =1.5

1.00E+17

Conversion (%)

Np / L
Un-grafted silica

60

QMPS =1.9 mol/m2

40

QMPS =0.95 mol/m2

QMPS =0.35 mol/m2

20
1.00E+16

0.001

0.01

1.00E+15
0.1

[SDS] (mol.L1)
Fig. 3. Particle number as a function of surfactant concentration for
styrene emulsion polymerization at 70  C with SDS as surfactant and
1.85 mM K2 S2 O8 initiator.

J. Nanosci. Nanotechnol. 6, 432444, 2006

0
0

10

Time (hours)
Fig. 4. Conversion versus time curves for polymerization of styrene
performed in the presence of silica particles with increasing amounts of
MPS on their surface. QMPS indicates the actual MPS grafting density as
determined by UV analysis using the depletion method.

437

RESEARCH ARTICLE

Table IV. Recipes for emulsion polymerizations of styrene in the

rate. It can be noticed that the lower the MPS grafting
presence of MPS-grafted silica particles and a constant surfactant
density, the higher the polymerization rate.
concentration.
Figure 5 shows TEM micrographs of PS/silica composLatex code
[MPS] (moles/m2 )
QMPS (moles/m2 )
ite particles produced for increasing MPS grafting densities. For the sake of clarity, micrographs were recorded
A1-K10-0
0
0
at low and high magnication to better visualize the parA1-K10-0.1
01
01
A1-K10-0.2
02
02
ticles shape. It can be seen from Figure 5 that only the
A1-K10-0.5
05
035
polymerization performed in the presence of un-grafted
SCD
Universite
Bordeaux
1 (cid 87001294) 1
A1-K10-1
065
silica particles gave rise to separate
populations
of silica
A1-K10-2
2
095
IP : 147.210.61.244
beads and polymer latexes with no apparent interactions
A1-K10-10
10
18
Fri,
03
Feb
2006
15:45:03
between them. For all the other experiments, the latex
[SiO2 ] = 10 g L1 , [SDS] = 1 g L1 , [Styrene] = 100 g L1 , KPS = 0.5 wt%
spheres showed more or less afnity for the silica surface.
relative to styrene.
For very low MPS grafting densities (typically below
0.5 moles m2 ), irregular daisy-shaped morphologies
the MPS grafting density and then increases for larger
were produced with only a few colloids surrounding the
MPS concentrations to reach a value which is close to that
silica spheres in an irregular fashion. It is worth noticing
measured in the absence of silica particles. The evolution
also the large size distribution of the polymer particles.
of the polystyrene particles diameter as a function of the
When the MPS grafting density increases and reaches a
MPS grafting density is shown in Figure 6.
2
value close to e.g., 1 mole m , most of the polymer
(b) Effect of the Silica Concentration. A series of experilatexes are located around the silica particles in more
ments
was performed with increasing silica concentrations
regular ower-like morphologies, each particles being surand
under
conditions giving rise to the formation of
rounded in average by eight polystyrene petals as deterowers
in
order
to give insights into the mechanism of
mined by the ratio of the number of polymer particles to
formation
of
this
original morphology. The size of the
the number of silica particles. With increasing further the
latexes
produced
was
again directly determined from the
MPS grafting density, core-shell particles were obtained as
TEM
micrographs.
Table
VI shows the number average
shown in Figure 5d.
particle
diameter
calculated
by measuring the diameter of
Delivered
by
Ingenta
to:
Table V summarizes the particle size and size distribution of the polystyrene latexes directly determined from
100
the TEM micrographs. It can be seen that the diameter of
the polystyrene latex particles decreases with increasing

Nucleation of Polystyrene Latexes on Functionalized Silica Particles

Bourgeat-Lami et al.
250

(a)
Silica

200

Dn (nm)

Polystyrene
150
100
50

(b)
0
0

0.5

1.5

QMPS (mol.m2)
Silica

Fig. 6. Polystyrene number average particles diameter as a function of

the MPS grafting density.
Polystyrene

Table VI. Number average particle diameters, weight average particle

diameters and polydispersity indexes of polystyrene latex particles produced in the presence of increasing concentrations of MPS-grafted silica
beads.

(c)

Silica

SCD Universite Bordeaux 1 (cid 87001294)1

Latex code
[SiO2 ](g L )
IP : 147.210.61.244
A1-K10-2
10
Fri, 03 Feb 2006
15:45:03
Polystyrene
Polystyrene

(d)

A1-K50-2
A1-K100-2

50
100

Dn

Dw

Dw /Dn

1130
604
486

1169
713
638

103
118
131

QMPS = 095 mol m2 . [SDS] = 1 g L1 .

Silica

80

Fig. 5. TEM images of silica/polystyrene composite particles obtained

for different MPS grafting densities. (a) Without MPS, (b) QMPS =
02 mol m2 , (c) QMPS = 095 mol m2 , and (d) QMPS =
19 mol m2 . The images were recorded at low (left) and high magnications (right). Scale bars: 500 nm (left) and 100 nm (right).

Conversion (%)

RESEARCH ARTICLE

100

60

Without silica
[SiO2]= 5gL1

40

[SiO2]=10gL1
[SiO ]=50gL1

2
20
more than one hundred particles as a function of the silica
Delivered by Ingenta to:
particles concentration.
It can be seen in Table VI that the diameter of the
0
1
2
4
5
6
7
9
0
3
8
10
polystyrene latexes decreases with increasing the silica
Time (hours)
concentration. The overall number of particles thus
increases.
Fig. 7. Conversion versus time curves for emulsion polymerizations

Table V. Number average particle diameters, weight average particle

diameters and polydispersity indexes of polystyrene latex particles synthesized in the presence of MPS-grafted silica particles with increasing
MPS grafting densities.
Latex code

QMPS
(mol m2 )

Conversion
(%)

Dn

Dw

Dw /Dn

A1-K10-0
A1-K10-0.1
A1-K10-0.2
A1-K10-0.5
A1-K10-1
A1-K10-2
A1-K10-10

0
01
02
035
065
095
19

100
96
95
86
962
996
985

1972
1295
1139
928
1105
1130
1905

2011
1434
1283
1136
1226
1169
1943

1.02
1.11
1.13
1.22
1.11
1.03
1.02

[SiO2 ] = 10 g L1 , [SDS] = 1 g L1 .

438

of styrene performed at 70  C in the absence of silica or with MPSgrafted silica of increasing concentrations. [Styrene] = 100 g L1 ,
[KPS] = 05 wt% relative to styrene, [SDS] = 1 g L1 , and QMPS =
095 mol m2 .

Table VII. Experimental conditions, number average particle diameters, weight average particle diameters and polydispersity indexes for
emulsion polymerization of styrene in the presence of various types of
silica particles.
Latex code

Silica

Dn

Dw

Dw /Dn

A1-K10-2
A1-S10-2

Klebosol
Stber

113.0
146.9

116.9
156.1

1.03
1.06

[SiO2 ] = 10 g L1 , [SDS] = 1 g L1 .

J. Nanosci. Nanotechnol. 6, 432444, 2006

Bourgeat-Lami et al.

Nucleation of Polystyrene Latexes on Functionalized Silica Particles

Table VIII. Experimental conditions, number average particle diameters, weight average particle diameters and polydispersity indexes of
emulsion polymerizations of styrene carried out in the presence of
increasing surfactant concentrations and various silica concentrations.

(a)

200 nm

100 nm

(b)

Latex code

[SiO2 ] (g L1 )

SDS (g L1 )

Dn

Dw

Dw /Dn

A1-K10-2
A2-K10-2
A3-K10-2
A2-K70-2

10
10
10
70

1
2
3
2

1130
833
593
512

1169
866
626
634

1.03
1.04
1.05
1.23

(a)

Delivered by Ingenta to:

(a)

(b)

(b)

Fig. 9. Effect of the surfactant concentration on the morphology of

the silica/polystyrene composite particles. (a) SDS = 1 g L1 and
(b) [SDS] = 3 g L1 . QMPS = 095 mol m2 . Scale bars: 400 nm.

Fig. 10. Effect of the nature of the surfactant on the morphology of the
silica/polystyrene composite particles. (a) SDS (1 g L1 ) and (b) NP30
(3 g L1 ). QMPS = 095 mol m2 .

J. Nanosci. Nanotechnol. 6, 432444, 2006

439

RESEARCH ARTICLE

again for the large silica particles although the diameters

of the polymer spheres are bigger than when smaller silica
particles are used as seeds (see Fig. 8 and Table VII).
(d) Effect of the surfactant concentration. As shown in
the previous section, the surfactant plays a key role in
1 m
200 nm
emulsion polymerization by determining the nal particle
number. Experiments were thus conducted under various
Fig. 8. Effect of the silica particles size on the morphology of the
silica/polystyrene composite particles. (a) Klebosol 30N50 (diameter =
surfactant concentration in order to clarify the role of the
83 nm) and (b) Stber silica (diameter = 267 nm). QMPS = 095 mol
surfactant
our system. As can be seen in Figure 9,
1 (cid in
87001294)
L1 . Universite Bordeaux
m2 . [SiO2  = 10 g L1 and [SDS] = 1 g SCD
increasing
the
surfactant concentration for a constant silIP : 147.210.61.244
ica
particle
concentration
resulted in the formation of free
03 Feb
Figure 7 shows the corresponding conversionFri,
versus
time 2006 15:45:03
latex particles that were grown separately from the silica
curves. We observe that the polymerization rate increases
surface. As will be discussed later, these particles presumwith increasing the silica concentration in agreement with
ably result from the presence of micelles that may compete
the increase in the overall particle number.
for capture of the growing radicals. However, increasing
(c) Effect of the silica particle size. In this series of
further the silica concentration enabled efcient capture
experiments, we varied the diameter of the silica partiof all the growing polymer even for concentrations above
cles while keeping a constant silica concentration. To do
the cmc illustrating the determinant role of the seed surthis, a silica suspension in alcohol was synthesized accordface in the nucleation mechanism. Table VIII shows the
ing to the so-called Stber method and next suspended
diameters and the polydispersity indexes of the resulting
into water by successive centrifugation/redispersion cycles.
latexes together with the experimental conditions used in
It was then grafted as mentioned above for the comthese experiments. It is worth noticing that the higher the
mercial aqueous silica suspension. The nal characterissilica concentration, the higher the proportion of polymer
tics of the composite latex suspensions are indicated in
that is located on its surface.
Table VII together with the experimental conditions used
(e) Effect of the Nature of Surfactant. By changing the
for polymerization. A ower-like morphology is achieved
nature of the surfactant, we expect again to signicantly

Nucleation of Polystyrene Latexes on Functionalized Silica Particles

Table IX. Experimental conditions, number average particle diameters,
weight average particle diameters and polydispersity indexes of emulsion
polymerizations of styrene carried out in the presence of SDS or NP30
and various Klebosol silica concentrations.
Latex code

[SiO2 ]
(g L1 )

SDS
(g L1 )

NP30
(g L1 )

Dn

Dw

Dw /Dn

A1-K10-2
N3-K10-2*
N3-K2-2

10
10
2

1
/
/

/
3
3

113.0
/
295.5

116.9
/
299.4

1.03
/
1.01

RESEARCH ARTICLE

QMPS = 08 mol m2 . *Flocculation after 1 hour of reaction (e.g., 10%

conversion).

Bourgeat-Lami et al.

separated from the silica surface. Silsesquioxane colloids

formation has already been reported to occur under similar
conditions.38 Therefore, the surfactant is absolutely necessary for an accurate determination of the grafting density
as the presence of these silsesquioxane particles renders
impossible any quantitative treatment. The low MPS grafting density observed under our experimental conditions
is thus presumably due to the presence of the surfactant
which may signicantly inuence the grafting reaction and
the MPS surface density. At last, it is worth pointing out
that the lower the MPS concentration, the higher the grafting efciency in agreement with previous studies on similar systems.17 45 46

inuence the nucleation mechanism and generate different

particles morphologies. Figure 10 shows the TEM images
of the composite particles obtained using either SDS or
4.2. Nanocomposite Particles Formation
NP30 as surfactants with silica concentrations of 10 g L1
and 2 g L1 , respectively (see Table IX). While SDS led
A number of mechanisms have been proposed in the literto the formation of owers, the polymerization carried out
ature for latex particle formation in emulsion polymerizawith the non ionic surfactant gave encapsulated silicas.
tion systems.47 It is commonly accepted that for monomers
SCD
Universite
Bordeaux
1 (cid
87001294)
It is worthwhile to notice that the core-shell particles of
of low
water
solubility like styrene and for polymerizaIP
:
147.210.61.244
Figure 10b have a lower size distribution than the polytions performed well above the cmc of the soap, nucleation
Fri,
Feb 2006
15:45:03
mer latexes of Figure 10a. In addition, it must
be03
emphamainly
occurs in surfactant micelles (so-called Smithsized that the polymerization carried out in the presence of
Ewart micellar nucleation theory), while below the cmc
10 g L1 of silica and 3 g L1 of NP30 gave an unstable
or for monomers of high water solubility, homogeneous
latex after around 1 hour of reaction. This is presumably to
nucleation is predominant (so-called HUFT theory based
be related to the specic nucleation mechanism involved
on the assumptions of Fitch and Tsai and those of Hansen
in this system as will be discussed later.
and Ugelstad). The HUFT theory assumes that polymer
chains grow until they reach a critical degree of polymerization, z, for which they undergo self-nucleation.48 49 The
4. DISCUSSION
freshly nucleated polymer particles are not stable unless
they are fully covered by surfactant and will undergo lim4.1. Grafting of MPS onto Silica
ited coagulation (limited because the coagulation stops
from Aqueous Suspensions
when the surface charge and potential has reached a level
It is generally admitted from previous studies in the literwhere the particles are stable). In the following, the term
ature that under dry conditions, the grafting of organosiprimary particle will be used to designate a precursor parlanes to mineral oxide surfaces requires high temperature
ticle formed by micellar entry or homogeneous nucleation
conditions (e.g., curing under vacuum or solvent reuxing)
and resulting from the growth of a single (or at most, a
Delivered by Ingenta
to: chains.
to promote condensation.
few) polymer
In the presence of water, the grafting involves a sigDetermining which nucleation mechanism predominates
nicantly different mechanism. The alkoxy groups of
in emulsion polymerization is not straightforward. Howthe organosilane rst quickly hydrolyze into silane triever, compared to conventional emulsion recipes, the
ols that can undergo self condensation.42 43 Therefore,
present system appears to be far more complicated. Thereit is assumed that aqueous silylation techniques lead to
fore, a fullled description of the mechanism of nucleation
the formation of localized polysiloxane networks on the
will not be attempted here and only a few directions will
nanoparticles surface instead of a monolayer coverage.44
be given in order to account for nanocomposite particles
However, despite the fact that the grafting was performed
formation and polymerization kinetics.
in an aqueous environment, our results show that the maxWhen bare silica particles are engaged in the polyimum surface coverage at saturation determined by UV
merization reaction, polymer spheres are grown separately
analysis (e.g., 2 mol m2 ) is of the same order of magfrom the silica surface while the conversion versus time
nitude as the value commonly accepted for a monomoleccurve is identical to that obtained without silica. Indeed, it
ular coverage (e.g., around 2.3 mol m2 ).17 It must
is well known that the encapsulation of inorganic particles
be recalled nevertheless that as the organo alkoxysilane
by polymers necessitates a preliminary surface modiis initially insoluble in water, a surfactant was introcation by molecular agents able to promote favorable
duced in the suspension medium for effective dispersion
interactions.4 5 Similar conclusions were already pointed
of the MPS molecule. Indeed, in the absence of surfactant,
out by Bourgeat-Lami and Lang19 and Reculusa et al.24 on
large silsesquioxane particles are formed that cannot be
similar systems.
440

J. Nanosci. Nanotechnol. 6, 432444, 2006

Bourgeat-Lami et al.

Nucleation of Polystyrene Latexes on Functionalized Silica Particles

conditions. In addition, if the MPS grafting density is sufciently high to account for the formation of a large num
Aqueous phase

SO4 + nM
propagation
ber of primary particles, the formation of new islands at
Micellar entry
the silica surface increases too and an homogeneous shell

Z-mer
CH3
O
Below cmc
is likely to be formed around silica. The shell may result
H2C =C -C-O(CH2)3-Si
O

Radical
O
O
from the collapsing of the growing polymer chains on
CH3
capture
O
the functionalized silica surface or from the coalescence
H2C =C -C-O(CH2)3-Si O
Propagation
+
O
O
of freshly nucleated neighboring primary particles, this
Coagulation
Surface
last issue being promoted by the close proximity of these
nucleation
precursor particles and the correspondingly low surface
High MPS
Low MPS
energy. For a too low MPS concentration, in contrast, the
grafting density
grafting density
polymer chains form segregated domains around the silica
particles as the high interfacial energy (due to the presence
of unreacted silanol groups), does not promote spreading
of the polymer chains on the surface nor interparticles coaFig. 11. Schematic illustration of the main features taking place during
lescence. A schematic picture of nanocomposite particles
the formation of the silica/polystyrene nanocomposite particles.
formation and growth is shown in Figure 11.
When considering the particle size or particle number
What is more interesting in this work is the mechvariation
the MPS grafting density (Fig. 6), some
Universite
Bordeaux 1 (cidversus
87001294)
anism of nanocomposite particlesSCD
formation
when MPS
interesting
features
were additionally evidenced that could
IP : obvi147.210.61.244
units are present on the silica surface. This system
help
us
support
or
refute
the above mechanism. The sysFri, 03
ously presents major differences in comparison
to Feb
con- 2006 15:45:03
tem obviously shows some variation in particles nucleation
ventional emulsion polymerization concerning in particular
as the overall number of polymer spheres is not constant
the nucleation step which can not be neglected contrary
in the different experiments that we have presented. The
to conventional seeded emulsion polymerization in which
polymerization kinetics is also strongly affected as it is
the nal particle number is determined by the number of
known that the rate of an emulsion polymerization is proseed particles, thus avoiding the complexities of nucleation
portional to the particle number. Therefore, the lower the
(provided, of course, that most of the surfactant is located
particles size, the higher the polymerization rate. When
on the seed surface and that there is not enough emulsier
the silica surface contains a large amount of double bonds,
in the water phase to form micelles).
the nal particle size (and therefore the nal particle numBy analogy with classical emulsion polymerization sysber) is very close to that obtained in the absence of silica
tems, nanocomposite particles formation can be described
particles. The silica seed particles seem to have no inuas follows (Fig. 11). The persulfate initiator starts to
ence on particles nucleation in this case. This may be due
decompose in the water phase giving rise to the formation
to the fact that for high MPS grafting densities, the silof radicals. These radicals will propagate with aqueous
ica seed particles are converted into a polymer latex in
phase monomers until they undergo one of the following
the early stages of polymerization and since their number
fates: (i) Aqueous phase termination or (ii) entry into a
is identical
Delivered
by
Ingenta
to:to that of the polymer particles formed in the
micelle or precipitation (depending on the surfactant conabsence
of
silica, there are no new particles created nor
centration), creating somehow a new particle. Aqueouscoagulation occurring under such conditions. For intermephase oligomers of all degree of polymerization can also
diate MPS concentrations, in contrast, latex spheres can
undergo frequent collision with the surface of the silica
be clearly identied on the seed surface. As they are all
seed particles, and have therefore a high probability to
located around silica, and since there is in average 8 polycopolymerize with the double bonds of silica, thus genmer petals per silica sphere, their size is much smaller than
erating chemisorbed polymer chains in the early stages
the one observed for unseeded experiments under identical
of polymerization. These discrete loci of adsorption are
conditions. These polymer latexes thus display a surface
preferred to adsorb further oligomers or radicals compared
area 5 times higher than that of the reference experiment
with the bare seed surface. As a result, these discrete loci
without silica. This result suggests that the silica particles
of adsorption become discrete loci of polymerization. Proare able to stabilize the growing polymer spheres and genvided that new polymer particles formation is not proerate a greater latex particle number than when SDS is
moted, polymerization will exclusively take place at the
used as surfactant alone. The number of polymer spheres
silica surface.
around each silica particle depends not only on the MPS
Let us now envisage what are the main factors that
grafting density but also on geometric considerations, as
will govern radical capture and (re)nucleation. First, it
increasing the silica particle size allows to introduce a
seems obvious that as the MPS grafting density increases,
larger number of polymer spheres around each individual
the probability of radical capture also increases so that
silica particle (see Fig. 8b). The silica seed particle ability
polymerization on the seed surface is promoted under such
Aqueous phase
termination

441

RESEARCH ARTICLE

J. Nanosci. Nanotechnol. 6, 432444, 2006

Above cmc

Nucleation of Polystyrene Latexes on Functionalized Silica Particles

Bourgeat-Lami et al.

RESEARCH ARTICLE

Np latex/ L

1E+19
to stabilize the growing latex sphere is not very surpris[SDS]=1g/L
[SDS]=2g/L
ing if one considers that the silica surface is negatively
charged and can thus ensure electrostatic stabilization of
1E+18
the latex spheres nucleated on top of it. This mechanism
is expected to be less effective however when the polymer
completely recovers the seed surface, as it is the case for
1E+17
high MPS grafting densities. In this situation, the overall particle number (and therefore the total surface area),
decreases to reach the value given by the reference exper1E+16
iment without silica. More surprising however is the fact
1E+14
1E+15
1E+16
1E+17
1E+18
Np SiO2 / L
that polymer spheres of small dimensions are formed for
very low MPS grafting densities even though they are not
Fig. 12. Evolution of the number of polymer particles as a function
all surrounding silica, most of them being present as free
of the silica particle number for a series of emulsion polymerization of
polymer latexes with no particular afnity for the minstyrene performed in the presence of various types and concentration of
eral surface. As before for higher MPS grafting densities,
silica particles. QMPS = 095 mol m2 .
these particles have been presumably nucleated on the silica surface in the earlier stages of polymerization. Howthe stability of the particles would be much less important
ever, contrary to the previous situation, they might have
when the contribution of micellar nucleation is not neglidesorbed later from the surface. Indeed,
it is known Bordeaux
that
SCD Universite
1 (cid
87001294)
gible,
(especially
in the batch reactions where the emulsisiloxane bonds can form and break reversibly depending
IP : 147.210.61.244
er concentration is close or largely above the cmc), the
on the experimental conditions and more precisely
onFeb
pH. 2006
Fri, 03
15:45:03
curves
of Figure 12 indicate on the contrary that even for
This scheme would be promoted by the nature of the interpolymerizations performed above the cmc, the number of
facial layer, the MPS units being irregularly distributed
polymer particles is mainly controlled by the number of
on the surface in the form of oligomeric regions which
silica particles introduced in the suspension medium.
would be highly sensitive to hydrolysis. It is clear that it
The results of the inuence of the silica concentration
is not possible to distinguish between a regular polysiloxon particles morphology are also quite instructive. It seems
ane lm from islands of poly(MPS) by the techniques
obvious from our data that the MPS grafting density is
described in this paper. However, the relatively low MPS
not the only parameter that promotes capture of the growgrafting density determined experimentally strongly suping radicals. Indeed, increasing the silica concentration
ports the hypothesis of a patchy-like conguration of the
enabled the exclusive formation of polymer spheres around
grafted MPS molecules. It is noteworthy to mention that
silica whereas renucleation occurred when the seed conthe formation of siloxane nanosized clusters has already
centration was too low. In other words, the larger the silica
been pointed out by several authors for the grafting of
particles number, the higher the amount of polymer on
MPS on silica surfaces.50 51 To determine whether the latex
their surface and the smaller the diameter of the nuclespheres were rst produced in solution (according to conated latex particles (compare for instance A2-K10-2 and
ventional nucleation mechanisms) and adsorbed further on
A2-K70-2 in Table VIII). Secondary nucleation in conthe seed surface or if they were directly nucleated
on the by Ingenta
Delivered
ventional to:
emulsion polymerization is most often related
seed surface is not straightforward. However, it is likely
to insufcient rates of capture. We can thus assume that
that primary particles may be present since the beginning
irrespective of the mechanism of particle formation, renuof the reaction in both places and continue to grow until
cleation will occur as long as there is not a sufcient numthey become mature and identiable particles. It should
ber of particles of sufcient size to capture all z-mers.
be noticed again that the formation of small particles for
Increasing the silica seed concentration allows creating a
low MPS grafting densities is supported by the kinetics
larger polymer surface area (as the growing latexes have a
data which indicate that the polymerization rate increases
smaller size) which enables to avoid renucleation as more
with decreasing the amount of MPS on the silica surface
soap is adsorbed on this freshly created surface and less is
(see Fig. 4).
available in the water phase to stabilize new particles.
The stabilizing role of the silica particles is clearly
Also of major interest was the investigation of the effect
illustrated in Figure 12 which shows the evolution of the
of the nature of the surfactant on the particles morphology.
polymer particle number as a function of the number of
While the polymerizations performed in the presence
silica particles. While for low silica particles number, the
of SDS and moderate MPS grafting densities always
number of polymer latexes is close to that of the referafforded ower-like morphologies, those performed with
ence experiments, this number increases with increasing
NP30 gave rise to a core-shell morphology. This is obvithe number of seed particles and reaches a value indepenously to be related to changes in interfacial properties
dent on the surfactant concentration. Although we would
(and thus in local monomer concentrations) due to the
expect that the contribution of the silica surface charges to
presence of adsorbed surfactant molecules. Indeed, it is

442

J. Nanosci. Nanotechnol. 6, 432444, 2006

Bourgeat-Lami et al.

Nucleation of Polystyrene Latexes on Functionalized Silica Particles

well known that non ionic emulsiers with ethylene oxide

7. K. Furusawa, Y. Kimura, and T. Tagawa, J. Colloid Interf. Sci. 109,
69 (1986).
units strongly adsorb onto silica in aqueous solution.52 The
8. C. Barthet, A. J. Hickey, D. B. Cairns, and S. P. Armes, Adv. Mater.
adsorbed surfactant molecules form a bilayer on the sur11, 408 (1999).
face which interfacial region is able to solubilize monomer
9. M. J. Percy, C. Barthet, J. C. Lobb, M. A. Khan, S. F. Lascelles,
molecules as micelles do in conventional emulsion
M. Vamvakaki, and S. P. Armes, Langmuir 16, 6913 (2000).
polymerization (so-called admicellization/adsolubilization
10. J. I. Amalvy, M. J. Percy, and S. P. Armes, Langmuir 17, 4770 (2001).
11. J. L. Luna-Xavier, E. Bourgeat-Lami, and A. Guyot, Colloid Polym.
behavior). The capture of the growing radical by this interSci. 279, 947 (2001).
facial region is thus promoted giving rise to polymer shell
12. J. L. Luna-Xavier, A. Guyot, and E. Bourgeat-Lami, J. Colloid Interf.
formation even for very low MPS grafting densities.
Sci. 250, 82 (2001).
In summary, all the experimental data presented in this
13. J. L. Luna-Xavier, A. Guyot, and E. Bourgeat-Lami, Polym. Int. 53,
article indicate that MPS-functionalized silica particles
609 (2004).
14. S. Reculusa, C. Poncet-Legrand, S. Ravaine, C. Mingotaud,
allows to nucleate polymer latex spheres on their surE. Duguet, and E. Bourgeat-Lami, Chem. Mater. 14, 2354 (2002).
face giving rise to the formation of original morphologies.
15. S. Reculusa, C. Poncet-Legrand, A. Perro, C. Mingotaud, E. Duguet,
The diameter and therefore the number of polymer latexes
E. Bourgeat-Lami, and S. Ravaine, Chem. Mater. in press.
formed around silica, depend on the MPS grafting density,
16. P. Espiard, A. Revillon, A. Guyot, and J. E. Mark, in Polymer
the seed particle number and the surfactant concentration.
Latexes: Preparation, Characterization and Applications, edited by
E. S. Daniels, T. Sudol, and M. El-Aasser, ACS Symposium Series
The question of whether or not a primary particle nucle492, Washington DC (1992), Ch. 24, pp. 387403.
ated on the surface of silica particles of very low MPS
17. E. Bourgeat-Lami, P. Espiard, and A. Guyot, Polymer 36, 4385
grafting densities can desorb and SCD
end up
in the aqueous
Universite
Bordeaux 1(1995).
(cid 87001294)
phase is hard to answer. However, the very high
18. P. Espiard and A. Guyot, Polymer 36, 4391 (1995).
IP : poly147.210.61.244
merization rate observed under such conditions
andFeb
the 2006
19. 15:45:03
E. Bourgeat-Lami and J. Lang, J. Colloid Interf. Sci. 197, 293
Fri, 03
(1998).
corresponding low polymer particles size support this
20. E. Bourgeat-Lami and J. Lang, J. Colloid Interf. Sci. 210, 281
assumption.

5. CONCLUSION

Acknowledgments: The authors thank Christian Novat

and Nicolas Tissier (LCPP, Villeurbanne) for their great
help in TEM analysis.

References and Notes

1.
2.
3.
4.
5.

C. H. M. Hofman-Caris, New J. Chem. 18, 1087 (1994).

A. D. Pomogalio, Russ. Chem. Rev. 69, 53 (2000).
G. Kickelbick, Prog. Polym. Sci. 28, 83 (2002).
E. Bourgeat-Lami, J. Nanosci. Nanotechnol. 2, 1 (2002).
E. Bourgeat-Lami, in Encyclopedia of Nanoscience and Nanotechnology, edited by H. S. Nalwa, American Scientic Publishers, Los
Angeles (2004), Vol. 8, p. 305.
6. V. Castelvetro and C. De Vita, Adv. Coll. Interf. Sci. 108109, 167
(2004).

J. Nanosci. Nanotechnol. 6, 432444, 2006

443

RESEARCH ARTICLE

Silica/polystyrene nanocomposite latexes were synthesized

through emulsion polymerization under batch conditions.
By varying the surface density of the reactive double bonds
or the nature of the surfactant, either ower-like or coreshell morphologies were obtained. All the results reported
in this article support the idea that the nucleation is taking
place through the capture of the growing radicals by the
silica particles. As the latter carry negative charges on their
surface, they are able to stabilize the growing latex spheres
which number (and therefore overall surface area) is much
larger than in the absence of silica. As the rate Delivered
in emulsion by
polymerization is proportional to the particle number, the
kinetics of polymerization was strongly accelerated under
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Received: 13 April 2005. Revised/Accepted: 12 July 2005.

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