Journal of Colloid and Interface Science 295 (2006) 457–463

www.elsevier.com/locate/jcis

Ceramic encapsulated latex composites

Ş. Uğur a , E. Pehlivan a , F. Tepehan a , Ö. Pekcan b,∗
a Department of Physics, Istanbul Technical University, 34469 Maslak, Istanbul, Turkey
b Department of Physics, Işık University, 34398 Maslak, Istanbul, Turkey

Received 29 April 2004

Available online 26 September 2005

Abstract
This work reports the encapsulation of latex particles in Al2 O3 –polystyrene (PS) composite films. These films were prepared from PS particles
in Al2 O3 dispersion at room temperature in various latex contents. Composite films were annealed at elevated temperatures in 10 min time
interval above the glass transition temperature (Tg ) of polystyrene. Transmitted photon intensities, Itr were monitored after each annealing step.
AFM micrographs were also used to observe the physical changes of the composite films during annealing. It was observed that latex particles
are encapsulated above a critical Al2 O3 content of 33 wt% which corresponds to the critical occupation probability of pc = 0.33 at which the
film obey the site-percolation model with a critical exponent of 0.45. Below pc , it was seen that complete latex film formation process took place,
where transparency of the film was increased by annealing.
 2005 Elsevier Inc. All rights reserved.

Keywords: Latex; Encapsulation; Percolation; Critical exponents

1. Introduction positing a solution or dispersion have been of interest in last

In last decade, there has been growing interest on produc-
ing new materials by filling polymers with inorganic natural
and/or synthetic compounds. These composite materials posses
high heat resistance, mechanical strength and impact resistance
or present weak electrical conductivity and low permeability
for gases like oxygen or water vapor. Since the inorganic par-
ticles display rather macroscopic dimensions and since there is
mostly no interaction between the two mixed components at
the interface between the two partners, the resulting composite
materials can be seen as filled polymers. In general processing
and structural development studies are coupled with investi-
gations of coating properties including optical, electrical and
mechanical properties [1–3]. Some efforts have been made to
construct microstructure and properties of coatings with com-
posite ceramic–polymer microstructures, where the emphasis
in composites in which a ceramic phase forms a connected
network in a polymer matrix. Processing and microstructure
development of ceramic and polymer coating prepared by de-
* Corresponding author.
E-mail address: pekcan@isikun.edu.tr (Ö. Pekcan).
0021-9797/$ – see front matter  2005 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcis.2005.08.053
few years [4,5]. Colloidal ceramics, sol–gel derived ceramics
and polymers have been studied as coating systems.
Nano-sized antimony-doped tin oxide particles and poly(n-
butyl methacrylate) lattices were combined to construct trans-
parent conductive coating and a reduction in the percolation
threshold was observed in the latex based matrix [6]. The reduc-
tion in the percolation threshold was attributed to the particle–
particle interactions that favored microphase separation during
film formation. Nano-sized carbon black particles were com-
bined with latex particles to produce the conductive polymeric
composites with segregated microstructures [7,8]. It was shown
that there is a drastic decrease in the electrical conductivity at
the percolation threshold which is very sensitive to the process-
ing conditions such as drying temperature, dispersant content
and latex particle characteristics. In the latex-based composites,
a segregated microstructure is formed, i.e. the carbon particles
segregate to the interstices and interfaces between coalescing
latex particles.
Film formation from soft (low-Tg ) and hard (high-Tg ) la-
tex dispersions can occur in several stages. In both cases,
the first stage corresponds to the wet initial stage. Evapora-
tion of solvent leads to second stage in which the particles
458 Ş. Uğur et al. / Journal of Colloid and Interface Science 295 (2006) 457–463
form a close packed array, here if the particles are soft they
are deformed to polyhedrons. Hard latex however stays unde-
formed at this stage. Annealing of soft particles causes diffu-
sion across particle–particle boundaries which leads to a ho-
mogeneous continuous material. In the annealing of hard latex
system, however, deformation of particles first leads to void clo-
sure [9–12] and then after the voids disappear diffusion across
particle–particle boundaries starts, i.e. the mechanical proper-
ties of hard latex films evolve during annealing; after all sol-
vent has evaporated and all voids have disappeared. Transmis-
sion electron microscopy (TEM) has been the most common
technique used to investigate the structure of the dried films
[13,14]. Pattern of hexagons, consistent with face centered cu-
bic packing, are usually observed in highly ordered films. When
these films are annealed, complete disappearance of structure is
sometimes observed, which is consistent with extensive poly-
mer interdiffusion. Freeze fracture TEM (FFTEM) has been
used to study the structure of dried latex films [15]. Small-
angle neutron scattering (SANS) has been used to study la-
tex film formation at molecular level. Extensive studies using
SANS have been performed by Sperling and co-workers [16]
on compression-molded polystyrene film. Direct-nonradiative
energy transfer (DET) method has been employed to investi-
gate the film formation process from dye-labeled hard [17] and
soft [18,19] polymeric particles. The steady state fluorescence
technique combined with DET has been used to examine heal-
ing and interdiffusion processes in the dye labeled poly(methyl
methacrylate) (PMMA) latex systems [20–22]. Recently UV–
visible technique was used to study film formation from PMMA
and polystyrene (PS) particles [23,24] where the transmitted
light intensity was monitored during film formation process.
In this work, the evolution of film formation from compos-
ites prepared with Al2 O3 ceramic and surfactant-free polysty-
rene (PS) latex, was studied. Nine different composites were
casted with different latex contents (27, 37, 47, 57, 67, 78,
87, 89 and 100 wt%). Then films were prepared by anneal-
ing composites above the glass transition temperature of PS for
10 min intervals at temperatures ranging from 100 to 280 ◦ C.
Transmitted photon intensity, Itr was monitored to study the
evolution of transparency. It was observed that Itr increased dra-
matically above a certain onset temperature, T0 called minimum
film formation temperature for the samples contained more than
67 wt% latex. Films with low latex content (less than 67 wt%)
show no variation in Itr upon annealing, i.e. microstructure of
these films present no change after annealing process has com-
pleted.
2. Theoretical considerations
2.1. Percolation model
Initially the percolation theory has been associated with a
paper of Broadbent and Hammersley which discussed the gen-
eral situation of a fluid spreading randomly through a medium
[25,26]. The most interesting feature of percolation phenom-
enon is the existence of a percolation threshold, pc below which
spreading process is confined to be a finite region. The spread
of a blight from tree to tree in an orchard was discussed by
Broadbent and Hammersley where the trees are planted on in-
tersection of a square lattice. The percolation threshold, pc for
this problem is around 0.6 for so called “site percolation” on
a square lattice. In other example is the seepage of water in
the cracks and fractures of a rock formation. A similar prob-
lem for practical interest is the spread of water displacing oil in
porous rocks, where neighboring pores are connected by small
capillary channels [27]. If no oil in the system injected water
into any given pore may only invade another pore through cap-
illary channels or “bonds.” The pores are “sites” connected to
the chosen centre of injection form what is called a “cluster.”
The largest cluster spans the lattice connecting the left and right
edges to the bottom edge, which is called “percolating cluster.”
The percolation probability, p∞ (p), is defined as the proba-
bility that water injected at a site, chosen at random, will wet
infinitely many pores. Here one should note that the probability
for having a pore at all the sites where water injection is at-
tempted is p. Extensive simulations and theoretical work have
shown that the percolation probability vanishes as a power-law
near pc :
p∞ (p) ≈ (p − pc )β , (1)
for p > pc , and p → pc . In a simple cubic lattice pc is found
to be 0.31 for site-percolation and 0.249 for bond percolation
models [28]. The exponent β for a simple cubic lattice is 0.45.
3. Experimental
3.1. Al2 O3 dispersion
2 ml aluminum-tri-sec-butoxide (Aldrich, 97%) was dis-
solved in 45 cm3 water at 70 ◦ C. The dispersion was stirred for
30 min. Small amount of acetic acid was continuously added as
catalyst, until the dispersion became transparent and stirred for
another 2 h. Oxide networks are formed upon hydrolytic con-
densation of alkoxide precursors.
3.2. PS latex
Pyrene labeled polystyrene particles were produced via sur-
factant free emulsion polymerization process. The polymeriza-
tion was carried out in a four-neck glass reactor equipped with
a glass paddle type agitation, condenser and nitrogen inlet. The
agitation rate was 300 RPM and the polymerization temperature
was controlled at 70 ◦ C. Water (100 ml) and styrene (5 g) were
first mixed in the polymerization reactor and when the temper-
ature was constant (at 70 ◦ C), potassium peroxodisulfate (KPS)
initiator (0.2 g) dissolved in small amount of water (2 ml) was
introduced in order to induce styrene polymerization. The poly-
merization was conduced during 18 h.
3.3. Composite films
Nine different films with 27, 37, 47, 57, 67, 78, 87, 89 and
100 wt% latex contents were prepared from the dispersion of
PS/Al2 O3 mixtures by placing the same number of drops on a
 Ş. Uğur et al. / Journal of Colloid and Interface Science 295 (2006) 457–463
Fig. 1. AFM images of composite films prepared with (a) 100, (b) 67, (c) 57 and (d) 37 wt% of PS latex before annealing.
glass plates with the size of 1.0 × 1.0 cm2 and allowing the wa-
ter to evaporate. The PS/Al2 O3 dispersion was stirred over night
to be sure that complete mixing was achieved. Then samples
were separately annealed above Tg of PS (105 ◦ C) for 10 min at
temperatures ranging from 100 to 300 ◦ C. The temperature was
maintained within ±2 ◦ C during annealing.
3.4. Photon transmission measurements
Photon transmission experiments were carried out using
model DU 530 Life Science UV–visible (UVV) spectrometer
from Beckman. The transmittances of the films were detected
between 300 and 400 nm. A glass plate was used as a standard
for all UVV experiments and measurements were carried out at
room temperature after each annealing processes.
3.5. Atomic force microscopy (AFM) measurements
Atomic force micrographs were taken with Shimadzu J3-
3PM-9500J3 scanning probe microscope. Figs. 1a, 1b, 1c
and 1d present the AFM micrographs of pure PS latex and
composite films prepared with 67, 57 and 37 wt% PS latex
before annealing, respectively. Here it has to be noted that the
latex film with no Al2 O3 in Fig. 1a present perfect order. Par-
459
ticles in Fig. 1d are seen to be much larger than the particles
in Figs. 1a–1c indicating that 37 wt% latex content particles
are highly encapsulated with Al2 O3 ceramic during mixing
and casting processes. However particles in films with 57 and
67 wt% PS are seen to be in the same size with the particles in
pure latex film. It is also seen in Figs. 1b–1d that encapsulation
of the latex particles by Al2 O3 destroys the order in the latex
system.
4. Results and discussion
Transmitted photon intensities from the films annealed at el-
evated temperatures are plotted in Figs. 2a, 2b, 2c, 2d, 2e and 2f
for the composites contain 37, 47, 57, 67, 89 and 100 wt% PS
latex, respectively. It is seen in Figs. 2a–2c that Itr presents no
variation in its intensity by predicting that microstructure of
these composites films shows almost no change. However an-
nealing of the films prepared with 67, 89 and 100 wt% latex
content, show a dramatic increase above a certain temperature
called the minimum film formation temperature, T0 . In fact
T0 moves slightly to the low temperature region by indicating,
early film formation process takes place as PS content increased
in these composites. Since higher Itr corresponds to higher clar-
ity of the composite, increase in Itr predicts that microstructure
460 Ş. Uğur et al. / Journal of Colloid and Interface Science 295 (2006) 457–463
Fig. 2. Plot of transmitted photon intensities, Itr versus annealing temperatures,
T from the composite film contain (a) 37, (b) 47, (c) 57, (d) 67, (e) 89 and
(f) 100 wt% PS latex.
Fig. 3. AFM images of composite films prepared with (a) 37 and (b) 57 wt% of PS latex before and after annealed at 280 ◦ C ((c) and (d)).
of these films change considerably by annealing them above
T0 , i.e. the transparency of these film evolve upon annealing.
Polystyrene starts to flow due to annealing and voids between
particles can be filled due to the viscous flow. However com-
posites prepared with 37, 47 and 57 wt% latex do not show this
behaviour, i.e. no viscous flow takes part and the voids cannot
be filled in these films upon annealing. Most probably encapsu-
lated latex particles can not be destroyed upon annealing. It is
also seen in Figs. 2d–2f that the maxima of Itr , (Itr )m increase
by increasing latex content in the composites and reaches its
highest value in pure latex film.
In order to support these findings AFM micrographs of the
composites prepared with 37 and 57 wt% latex are compared
in Figs. 3a, 3b and 3c, 3d before and after annealing at 280 ◦ C
for 10 min. It is seen in Figs. 3a and 3c that microstructure
of the composite film remain almost unchanged upon annealed
at 280 ◦ C, indicating that PS latex is highly encapsulated by
Al2 O3 which prevents PS particle from viscous flow even at
280 ◦ C temperature. Almost similar behaviour can be observed
when Fig. 3b is compared with Fig. 3d, i.e. if 57 wt% latex con-
tent composite annealed at 280 ◦ C film still keeps its original
microstructure form.
Figs. 4a, 4b and 4c, 4d compare the composite films pre-
pared with 67 and 89 wt% latex, before and after annealed at
280 ◦ C. It is seen that considerable change is occurred by an-
nealing the 67 wt% latex content film at 280 ◦ C (see Figs. 4a
and 4b), i.e. the microstructure of the composite film is changed
 Ş. Uğur et al. / Journal of Colloid and Interface Science 295 (2006) 457–463
Fig. 4. AFM images of composite films prepared with (a) 67 and (b) 89 wt% of PS latex before and after annealed at 280 ◦ C ((c) and (d)).
and the particle–particle interfaces are beginning to disappear
upon annealing. Figs. 4b and 4d compare the AFM micrographs
of 89 wt% latex content films before and after annealing where
it is seen that particle–particle boundaries are completely dis-
appeared after annealing process is completed. From here, both
Itr and AFM data suggest that 67 wt% latex content presents a
critical percentage, below which composite films are in encap-
sulated form and the replica of the particles can not be destroyed
upon annealing even at 280 ◦ C temperature.
In order to quantify the findings, presented in Figs. 2d–2f,
two types of treatment can be done for Eq. (1), at first it is as-
sumed that |p − pc |β can be taken proportional to |T − T0 |β
and then Eq. (1) becomes
Itr (T ) ≈ (T − T0 ) ,
β
(2)
where P∞ (p) is considered to be proportional to the transmitted
light intensity, Itr [29]. log Itr − log |T − T0 | plots are presented
in Figs. 5a, 5b and 5c for the composites prepared with 67, 89
and 100 wt% PS latex. The slope of the linear relation pro-
duce the critical exponent β for the composite film formation
process. β values and minimum film formation temperatures,
T0 are plotted against wt% of latex content in Figs. 6a and 6b,
respectively. It is interesting to note that the produced β value
461
corresponds to the β (= 0.45) value of a simple cubic lattice for
the film contain 67 wt% PS. For the second treatment we define
the following ratio
mAl2 O3
R= , (3)
mAl2 O3 + mPS
where mAl2 O3 and mPS present the weight of Al2 O3 and PS
in the composite film. If R is assumed to be the occupation
probability, p of Al2 O3 in the whole lattice then the percolation
threshold, pc becomes Rc and if once again P∞ (p) is consid-
ered to be proportional to the transmitted light intensity, Itr then
Eq. (1) can be written as [30]
Itr (R) ≈ (R − Rc )β . (4)
Equation (4) describes the percolation model for Al2 O3 dis-
tribution in PS matrix. When R reaches Rc , the largest clus-
ter of Al2 O3 appears by connecting the left and right edges
to the bottom edge of the PS matrix. It is seen in Table 1
that R with 33 and 22 posses β with 0.45 and 0.48 values.
These R values are equivalent to the pc for site-percolation
and bond-percolation models in simple cubic lattice where
β values are also satisfied. From here one may conclude
that the composite films with 67 and 78 wt% PS content
462 Ş. Uğur et al. / Journal of Colloid and Interface Science 295 (2006) 457–463

Fig. 6. Plots of (a) critical exponent, β and,1 (b) minimum film forming tem-
perature, T0 versus PS latex content.

Fig. 5. log Itr versus log(|T −T0 |) plots of composite films prepared with (a) 67,
(b) 89, (c) 100 wt% PS 1 latex content.

Table 1
Relation between ratio R and critical exponents β
Ra 33 22 16 11 0
βb 0.45 0.48 0.81 0.78 1.3
a R=m
Al2 O3 /(mAl2 O3 + mPS ), where mAl2 O3 is weight of Al2 O3 , mPS is
weight of PS.
b β—critical exponents, produced from Eq. (2).

obey percolation model, i.e. Al2 O3 percolate in the compos-
ite film during annealing above T0 . Composite films above
pc (R = 33) present Al2 O3 encapsulated replica of latexes.
However, composite films below pc (R = 22) show latex
film formation behaviours with a little effect of Al2 O3 . In
other word β values increase up to 1.3, indicating no perco-
lation takes place and complete film formation can be accom-
plished.
The produced β values and observed T0 values are plotted
versus PS latex content in Figs. 6a and 6b, respectively. It is
seen that as β exponent deviates from its percolation values as
T0 temperatures drop to lower values. In other words, if Al2 O3
stops to percolate in PS matrix, then latex film formation can
occur at low annealing temperatures.
Fig. 7. Plot of the maxima of transmitted light intensities, (Itr )max from Fig. 2
versus PS latex content.
On the other hand Fig. 7 presents the plots of the maximum
values of (Itr )max versus wt% latex content. It is interesting to
see that (Itr )max shows an increase starting from 67 wt% latex
content in composite film, predicting a percolation threshold
behaviour of Al2 O3 in polymer matrix. As we already know that
33 wt% Al2 O3 corresponds to the percolation threshold, pc for
the latex composite system, above which latex particles encap-
sulated with Al2 O3 ceramic. At pc , Al2 O3 percolates among
the latex film, below pc however latex film formation can be
completed with the residues of Al2 O3 barriers. This picture is
now depicted in Fig. 8 where the behavior of the composite film
below and above pc are presented which are supported by the
 Ş. Uğur et al. / Journal of Colloid and Interface Science 295 (2006) 457–463
Fig. 8. Cartoon presentation of (I) encapsulated (p < pc ) and (II) transparent
(p > pc ) composites. Is and Itr are the scattered and transmitted light intensi-
ties.
AFM pictures in Figs. 3 and 4. Here it is seen that when p > pc ,
encapsulated films shows no transparency to the light, however
if p < pc then composite film becomes transparent to the light
and (Itr )max increase dramatically.
In conclusion this work has shown that the presence of
Al2 O3 in PS matrix can affect the film formation processes. If
the presence of Al2 O3 is higher than the critical value, Rc the PS
latices are encapsulated by Al2 O3 . However, if the amount of
Al2 O3 lower than Rc , the classical latex film formation process
can take place.
References
[1] J. Sun, W.W. Gerberich, L.F. Francis, J. Polym. Sci. B Polym. Phys. 41
(2003) 1744.
463
[2] L.F. Francis, A.V. McCormick, D.M. Vaessen, J.A. Payne, J. Mater. Sci. 37
(2002) 4897.
[3] J.C. Grunlan, W.W. Gerberich, L.H. Francis, Polym. Eng. Sci. 41 (2001)
1947.
[4] D.M. Vaessen, F.A. Ngantung, M.L.B. Palacio, L.F. Francis, A.V. McCor-
mick, J. Appl. Polym. Sci. 84 (2002) 2784.
[5] D.M. Vaessen, A.V. McCormick, L.F. Francis, Polymer 43 (2002) 2267.
[6] Y.C. Wang, C. Anderson, Macromolecules 32 (1999) 6172.
[7] J.C. Grunlan, W.W. Gerberich, L.F. Francis, J. Appl. Polym. Sci. 80 (2001)
692.
[8] J.C. Grunlan, Y. Ma, M.A. Grunlan, W.W. Gerberich, L.F. Francis, Poly-
mer 42 (2001) 6913.
[9] P.R. Sperry, B.S. Synder, M.L. O’Dowd, P.M. Lesko, Langmuir 10 (1994)
2619.
[10] S. Mazur, in: N. Rosenweig (Ed.), Coalescence of Polymer Particles, in:
Polymer Powder Processing, Wiley, New York, 1995.
[11] J.K. Mackenzie, R. Shutlewort, Proc. Phys. Soc. 62 (1946) 838.
[12] J.W. Vanderhoff, Br. Polym. J. 2 (1970) 161.
[13] G. Kanig, H. Neff, Colloid Polym. Sci. 256 (1975) 1052.
[14] Y. Wang, A. Kats, D. Juhue, M.A. Winnik, R.R. Shivers, C.J. Dinsdale,
Langmuir 8 (1992) 1435.
[15] B.J. Roulstone, M.C. Wilkinson, J. Hearn, A.J. Wilson, Polym. Int. 24
(1991) 87.
[16] K.D. Kim, L.H. Sperling, A. Klein, Macromolecules 26 (1993) 4624.
[17] Ö. Pekcan, M.A. Winnik, M.D. Croucher, Macromolecules 23 (1990)
2673.
[18] Y. Wang, C.L. Zhao, M.A. Winnik, J. Chem. Phys. 95 (1991) 2143.
[19] Y. Wang, M.A. Winnik, Macromolecules 26 (1993) 1347.
[20] Ö. Pekcan, M. Canpolat, J. Appl. Polym. Sci. 59 (1996) 277.
[21] Ö. Pekcan, M. Canpolat, A. Göçmen, Polymer 34 (1993) 3319.
[22] M. Canpolat, Ö. Pekcan, J. Polym. Sci. Polym. Phys. Ed. 34 (1996) 691.
[23] E. Arda, V. Bulmuş, E. Pişkin, Ö. Pekcan, J. Colloid Interface Sci. 213
(1999) 160.
[24] Ö. Pekcan, E. Arda, Colloids Surf. A 153 (1999) 537.
[25] S.R. Broadbent, J.M. Hammersley, Proc. Cambridge Phil. Soc. 53 (1957)
629.
[26] H.L. Frisch, J.M. Hammersley, J. Soc. Industr. Math. 11 (1963) 894.
[27] M. Sahimi, Applications of Percolation Theory, Taylor and Francis, Lon-
don, 1994.
[28] D. Stauffer, Introduction to Percolation Theory, Taylor and Francis, Lon-
don, 1985.
[29] H. Özbek, S. Yıldız, Ö. Pekcan, Y. Hepuzer, Y. Yağcı, A.N. Berker, G.
Galli, E. Chiellini, Phase Trans. 76 (2003) 991.
[30] Ö. Pekcan, E. Arda, J. Colloid Interface Sci. 250 (2002) 471.