Journal of Colloid and Interface Science 281 (2005) 325–338

www.elsevier.com/locate/jcis

Assessing the effect of latex particle size and distribution on the

rheological and adhesive properties of model waterborne acrylic
pressure-sensitive adhesives films
Marcelo do Amaral a , Alexandra Roos b , José M. Asua a , Costantino Creton b,∗
a Institute of Polymer Materials (POLYMAT) and Grupo de Ingeniería Química, Facultad de Ciencias Químicas, University of the Basque Country,
Apdo. 1072, 20080 Donostia-San Sebastián, Spain
b Laboratoire de Physico-Chimie Structurale et Macromoléculaire, Ecole Supérieure de Physique et de Chimie Industrielles, 10 Rue Vauquelin,
75231 Paris, France
Received 14 April 2004; accepted 13 August 2004

Abstract
The adhesive and rheological properties of model acrylic pressure-sensitive adhesive (PSA) films prepared from high solid emulsions with
different particle sizes and distributions have been investigated with a customized probe tack apparatus. For each emulsion, the monomer
composition and gel content were kept constant but different average particle sizes and distributions were used. Adhesive films 100 µm thick
were then prepared from these emulsions and their rheological properties in the linear regime and adhesive properties were systematically
characterized. Surprisingly, both the rheological and adhesive properties were found to be very dependent on the initial latex particle size
distribution. A series of experiments were carried out to assess the adhesive properties of films made from blends of small- and large-
particle-size latexes. Using the probe tack test, a maximum in adhesion energy of the dry films was found for 60% of small particles in
the blend, a composition clearly different from that giving a minimum viscosity of the latex implying that optimizing for properties may
not be equivalent to optimizing for processing in these adhesive applications. Finally, the adhesive properties of two multimodal latexes
with different particle size distributions were investigated. Both gave significantly higher adhesion energies and clear evidence of a fibrillar
detachment process. This important result suggests that the spatial distribution of gel domains in the dry film and the molecular connectivity
between those gel domains also play an important role in controlling its adhesive properties.
 2004 Elsevier Inc. All rights reserved.

Keywords: Adhesion; Pressure-sensitive adhesive; Tack; Acrylic; Particle size distribution; Gel; Adhesive; Rheology

1. Introduction competitive cost [2]. Furthermore, acrylic PSAs, by virtue of

Acrylic polymers are widely used as pressure-sensitive
adhesives (PSAs). An ensemble of characteristics con-
tributed to making acrylic polymers one of the workhorses
of modern adhesive industry: They can be easily tailored to
control the polymer glass transition temperature, the mole-
cular architecture, and the crosslinking density; they have a
low plateau modulus [1]; and, equally important, they have a
* Corresponding author. Fax: +33-1-40-79-46-86.
E-mail address: costantino.creton@espci.fr (C. Creton).
0021-9797/$ – see front matter  2004 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcis.2004.08.142
their saturated backbone, have superior environmental sta-
bility and greater resistance to oxidation when compared
with rubber-based PSAs.
In recent years, great effort has been dedicated to fur-
ther understand the relationship between the molecular char-
acteristics of a PSA and its adhesive performance, and it
has been recognized that a subtle combination of molecu-
lar characteristics are needed to produce optimum perfor-
mance [3,4]. However, the vast majority of these studies
were generally undertaken with PSAs in which the base
polymer was produced by polymerization in solution, and
there have been relatively few systematic studies on the role
326 M. do Amaral et al. / Journal of Colloid and Interface Science 281 (2005) 325–338
of the molecular structure focusing on PSA prepared from
latexes despite their increasing commercial importance. The
underlying reason was the poor control of molecular charac-
teristics typically obtained with standard emulsion polymer-
ization techniques. However, advances in emulsion polymer-
ization processes now enable latex producers to tailor much
more finely the final properties of the polymer [5]. Given
these advances, systematic studies of the adhesive properties
of PSA obtained from such latexes are highly needed.
One of the important advances in emulsion polymeriza-
tion processes is the knowledge-based synthesis of latexes of
high solid content and low viscosity [6]. Latex particle size
distribution (PSD) is probably the most important variable in
designing low-viscosity concentrated aqueous polymer dis-
persions [7,8]. Results show that a broad PSD is favored
over a narrow PSD, and that the presence of large parti-
cles is highly recommended [9]. Therefore, when attempting
to produce highly concentrated latexes with low viscosity,
the PSD is an important process variable to be mastered.
Nevertheless, one should never forget that emulsion poly-
mers are sold for their final properties: The polymerization
process ought to be designed to produce, under optimum and
controlled conditions, products with the desired properties.
Consequently, it is essential also to assess the influence of
the latex PSD on the final adhesive properties of the dry ad-
hesive film, a field of research that, to the best of our knowl-
edge, has been neglected. In fact, most often, the empirical
idea that smaller particle size favors adhesive properties pre-
vails [10].
The probe tack test was used to quantify the influence
of the latex PSD of model acrylic PSAs. The study was di-
vided into two main parts. First, the adhesive properties of
two model PSA latexes of similar monomeric composition,
but different particle sizes were analyzed. Both latexes had
a rather narrow monomodal PSD. The same latexes were
used to compound blends with different PSDs. Next, the
adhesive properties of two high-solid-content low-viscosity
latexes were assessed. To check the hypothesis that the sole
or major variable in the study was the PSD of the latex the
rheological properties at small and large strain, gel content,
molecular weight distribution, and Tg of selected polymer
samples were characterized.
2. Background
The core component of all PSAs is a high-molecular-
weight polymer [11]. This is particularly true of acrylic PSA,
where a tackifying resin does not need to be added to obtain
PSA properties [2]. Hence, for both academia and industry,
there is great interest in investigating the relationship be-
tween the molecular structure of the polymer and the adhe-
sive properties of the PSA. Focusing on water-based acrylic
PSAs, there are a number of studies relating the polymer
structure and rheological properties to the adhesive perfor-
mance of the PSAs film [12–24].
While an exhaustive review is beyond the scope of this
article, it is nevertheless interesting to summarize the main
results. The first information on the role of the molecular
structure in the adhesive properties of PSAs was obtained
by Zosel [12] with the homopolymer 2-ethylhexyl acrylate
(2-EHA), PEHA, synthesized by emulsion polymerization.
Zosel [12,13] showed that to achieve a high fracture energy
during separation of the adhesive bond, the PSA had to form
bridging fibrils, and the author remarked that these bridging
fibrils could form only when the elastic modulus was be-
low a certain value. Further studies by Lakrout et al. [14],
also on adhesives prepared from PEHA latexes, showed that
the fibrils were actually walls between cavities, and finally
an extensive study from the same group showed that these
cavities expanded from defects at the interface between the
adhesive and the rigid surface [15].
These studies, all using the probe tack method, focused
on the mechanism of debonding from a rigid substrate and
defined the type of molecular structure and architecture
needed to obtain a good PSA. However, none really dis-
cussed the specificities of the formation of an adhesive film
from a latex.
A second category of studies, generally from more
chemistry-inclined groups, focused on the role played by
some of the additional synthesis parameters specific to emul-
sion polymerization techniques, such as the type and amount
of surfactant used in the reaction formulation [16–18], and
the composition profile of the latex particles (with two co-
monomers) [19–23]. These studies essentially showed that:
• The surfactants, and in particular the migration of the
surfactant molecules toward the interface, could have a
profound effect on adhesive properties [16,17].
• The composition profile of the particle (e.g., core–
shell particles) could also influence adhesive proper-
ties, although both studies [19,20] did not control post-
crosslinking, which is needed to optimize PSA prop-
erties in practice. In some cases, post-crosslinking of
the PSA would probably eclipse the minor effects of
the slight heterogeneity of composition of the polymer
chain.
Despite the common knowledge that the particle size of
a polymer aqueous dispersion can influence the final prop-
erties of thin films cast therefrom [10], little work has been
dedicated to systematically cover the influence of particle
size and PSD in adhesive properties [24]. Fabbroni et al. [25]
studied the adhesive and mechanical properties of hard–
soft nanocomposites. The nanocomposites were made from
blends of two different latexes, a latex of small particle size
(55 nm) and low Tg (soft), and another of large particle size
(268 nm) and high Tg (hard). It was observed that the pres-
ence of the rigid particles magnified the local strain that
must be applied to deform the film matrix of the adhesive.
It was shown that models commonly used to describe the
concentration dependence of the viscosity of well-dispersed
 M. do Amaral et al. / Journal of Colloid and Interface Science 281 (2005) 325–338
suspensions could be used to model the concentration depen-
dence of the stiffness of viscoelastic systems as well [26]. In
that case, the rigid particles dispersed in the film matrix were
considered to act like colloidal particles dispersed in a con-
tinuous medium.
Broadening the scope of application to fields other than
adhesives, it is possible to find some interesting studies that
tried to cover the gap between latex PSD and final proper-
ties [27–34]. Peters et al. [27,28] studied the effect of having
a latex for coating applications with a bimodal population of
particle sizes, on the film formation properties and on the fi-
nal properties of the dry film. Comparing with monomodal
systems, they observed that the minimum film formation
temperature (MFFT), drying rate, water adsorption, tensile
strength, and rheology measurements were all positively in-
fluenced by the multimodality characteristics of the latex.
That is, a latex with multimodal PSD had a higher dry-
ing rate, a lower MFFT, and a lower viscosity. However,
the study for coating high-speed runnability carried out by
Roper and Attal [29] showed poor results for a latex made
from a blend of 75 wt% large particles and 25 wt% small
particles. This blend composition, close to that for which
positive influences of latex bimodality on final properties
were found in the work of Peters et al. [27] and close to the
proportion that is known to minimize the viscosity at a given
solid content, gave a poor coat weight profile; i.e., the latex
could not be evenly spread on the substrate, causing severe
weeping in some experiments [29].
The influence of latex multimodality on the film for-
mation process and on final film properties has also been
studied [30–33]. The deformability of particles and the con-
tinuity of the dispersed phase were studied for combinations
of large hard particles and small soft particles and for combi-
nations of large soft particles and small hard particles. It was
observed that the critical volume fraction of small particles
required for continuity in a bimodal latex could be corre-
lated with the formation of a film with low void content [31].
Voids are generated by poor packing of monodisperse large
particles, and can influence the properties of the film, like
refractive index, as voids have a composition different from
that of the polymer. Geurts et al. [34] studied the effect of bi-
modality of the PSD on the MFFT of poly(n-butyl methacry-
late) latexes. They observed that the particle matrix became
more organized with less voids when particles of different
sizes were mixed. However, this did not necessarily change
the MFFT of the film.
3. Materials and methods
3.1. Materials
Technical-grade monomers 2-EHA (Quimidroga) and
methyl methacrylate (MMA) (Quimidroga), both with 10–
20 ppm of hydroquinone monomethyl ether (MEHQ) and
acrylic acid (AA) purity of 99% (Fluka), were used with-
327
out purification. The emulsifiers Dowfax 2A1 and Disponil
A3065, supplied by Dow Chemical and Cognis, respectively,
were used as supplied. Sodium persulfate (Fluka), ammo-
nium persulfate (Merck), NaHCO3 (Panreac), and hexade-
cane (Aldrich) were all used as received. Doubly deionized
water (DDI water) was used throughout the work.
3.2. Synthesis of model PSA latexes
Model acrylic PSAs were synthesized by free radical
polymerization in dispersed media. All latexes used were
based on a standard composition of 2-EHA, MMA, and AA,
88.2/9.8/2 wt%, respectively.
Polymerizations were carried out in a 500-mL jacketed
glass reactor equipped with reflux condenser, thermocou-
ple, stainless-steel stirrer at 250 rpm, nitrogen inlet (nitro-
gen flow at 10 ml/min), and three inlet tubes. The reactor
containing the initial charge was heated to the reaction tem-
perature. Then, for the semibatch polymerizations the semi-
continuous streams were added into the reactor. After the
addition period, the reactor was left for at least 2 h at the
polymerization temperature, and then it was cooled to room
temperature. No coagulum was found on the reactor walls or
on the surface of the stirrer. Solid contents were measured
by gravimetry and particle size distribution by capillary hy-
drodynamic fractionation (Matec 2000).
The large-particle-size model PSA latex was synthesized
by miniemulsion polymerization. The aqueous solution of
surfactant was mixed with the solution of monomers and
hexadecane by means of a magnetic stirrer for 10 min.
Immediately thereafter, the coarse dispersion was fed into
the Manton–Gaulin high-pressure homogenizer (Model Lab
60TBS, APV), whose first valve was set at 2000 psi, and the
second at 400 psi. Five cycles were used to homogenize the
dispersion. Then, the miniemulsion was fed into the reactor.
Both the small-particle-size model PSA latex and the two
latexes with broad PSDs were obtained by semicontinuous
emulsion polymerization, where the last two were prepared
by a seeded procedure. All details of the synthesis conditions
for large, small, MM, and MM2 latexes are given in Table 1.
Blends of the large and small model PSA latexes were
all prepared by calculating latexes on a weight basis of the
emulsion, so that S2L8 corresponds to 20 wt% small-particle
latex blended with 80 wt% large-particle latex.
3.3. Latex characterization
The glass transition temperature, Tg , of the large and
small model PSA latexes was determined by differential
scanning calorimetry (DSC) at a heating rate of 10 ◦ C/min.
A DSC 2920 Modulated differential scanning calorimeter
from TA Instruments was used.
Dynamic shear moduli were measured with a parallel
plate rheometer (RDA II, Rheometrics) at frequencies be-
tween 0.02 and 500 Hz and at temperatures varying be-
tween −80 and 150 ◦ C. Samples of selected model PSA
328 M. do Amaral et al. / Journal of Colloid and Interface Science 281 (2005) 325–338

Table 1
Formulations used for the synthesis of the model PSA latexes
Reaction Largea,b Small MM MM2
Initial charge DDI water: 230 g DDI water: 230 g DDI water: 30 g DDI water: 15 g
NaHCO3 : 0.37 g NaHCO3 : 0.37 g Large seed latex: 53 g Large seed latex: 50 g
Disponil A3065: 3.85 g Na2 S2 O8 : 1.25 g (solids content: 50%, (solids content: 50%,
Monomerc : 250.6 g Dowfax 2A1: 2.78 g particle size: 590 nm) particle size: 590 nm)
Hexadecane: 5 g Disponil A3065: 3.85 g Small seed latex: 13 g Small seed latex: 6.4 g (solids
(solids content: 50%, content: 50%, particle size: 34 nm)
particle size: 34 nm) Disponil A3065: 0.23 g

Additional streams Batch polymerization Feeding time: 120 min Feeding time: 240 min Feeding time: 240 min
initiator DDI water: 15.5 g DDI water: 20 g DDI water: 30 g DDI water: 30 g
(NH4 )2 S2 O8 : 1.25 g Na2 S2 O5 : 1.25 g (NH4 )2 S2 O8 : 2.9 g (NH4 )2 S2 O8 : 2.88 g
Na2 S2 O8 : 1.25 g

Neat monomer or Monomerc : 255 g DDI water: 77 g DDI water: 70 g

preemulsion Disponil A3065: 1.1 g Disponil A3065: 1.1 g
Dowfax 2A1: 4.9 g Dowfax 2A1: 4.8 g
NaHCO3 : 0.22 g NaHCO3 : 0.22 g
Monomerc : 292.5 g Monomerc : 299.4 g

Small seed latex d Small seed latex: 19.4 g (solids

content: 50%, particle size:
34 nm)

Temperature (◦ C) 50 80 70 70
Final total solid 50 50 64.2 67.7
content (%)
a The initial charge was homogenized before being added to the reactor.
b Miniemulsion polymerization.
c The same monomer composition was used in all polymerizations: 2-EHA/MMA/AA, 88.2/9.8/2 wt%.
d Three shot additions of equal volume at 60, 120, and 180 min.

films were obtained from dried latexes in the form of disks.

The dry polymer samples were deposited between the two
8-mm-diameter plates of the rheometer, and oscillatory shear
measurements were carried out. The samples were deformed
at a level of strain that did not exceed the linear viscoelastic
region of the material.

3.4. Probe tack experiment

The samples were made by depositing the corresponding

amount of latex on a standard microscope glass slide so as
to obtain a dry adhesive film of 100-µm thickness. The films
were formed from the latexes by water evaporation at 50 ◦ C
and further drying until constant weight at room tempera-
ture.
The probe tack experiments were done on a custom-
designed apparatus [15] adapted on a MTS 810 hydraulic
testing machine, schematically shown in Fig. 1. The sample Fig. 1. Overall schematics of the probe tack apparatus.
is fixed on the upper plate, which is connected to the load
cell. Parallelism between the sample and the probe is con-
trolled through micrometer screws. The probe is fixed on the video camera placed outside the testing chamber. To enhance
mobile lower shaft and its displacement is controlled with the definition of the images the sample was illuminated with
an LVDT transducer. The entire process of contact between a fiber optic light source. The displacement resolution of the
the probe and the film and the subsequent debonding were tack instrument is on the order of 1 µm, and the force reso-
followed from under the glass slide with a 45 ◦ mirror and a lution is approximately 0.2 N.
 M. do Amaral et al. / Journal of Colloid and Interface Science 281 (2005) 325–338
The tack test procedure consisted of first bringing the
probe into contact with the film at a constant speed of
30 µm/s. Next, the compressive force of 78.5 N (correspond-
ing to 1 MPa nominal contact pressure for 100% contact
area) was applied. The probe was left in contact with the ad-
hesive for 1 s. Finally, the probe was removed at a constant
speed, which was varied from 1 to 1000 µm/s. All exper-
iments were carried out at room temperature. During each
experiment, the force, the displacement of the crosshead,
and the elapsed time were simultaneously acquired. All tests
were filmed and tape-recorded with a black and white CCD
camera. Selected images were then digitized and analyzed.
Digital images were used to assess the maximum contact
area between the probe and the film in compression and to
compare the debonding stages of different adhesives.
The results of a tack test are a force displacement curve,
which can be transformed into a nominal stress-versus-
nominal strain curve by defining σ as F /A0 and ε as
(h − h0 )/ h0 , where A0 is the maximum area of contact
in compression and h0 is the initial layer thickness. Three
quantitative parameters can be extracted from the curve: the
peak stress σmax which is associated with the formation of
cavities in the adhesive layer [15,35]; the maximum exten-
sion εmax ; and the total work performed to detach the adhe-
sive layer from the surface, which can be obtained from the
integral under the stress–strain curve and is defined as Wadh .
The probe test is a very sensitive and reproducible test
which has been used successfully to characterize PSAs.
More details on interpretation of the debonding curves
and on the main deformation mechanisms can be found in
Refs. [36–38].
3.5. Tensile tests
Tensile tests were carried out to evaluate the properties
of selected model PSA films under large strains. For ten-
sile testing, 400- to 700-µm-thick films were prepared by
water evaporation at 50 ◦ C. The latex was deposited on an
anti-adherent film and placed in an oven with temperature
controlled at 50 ◦ C. The tensile measurements were per-
formed with an Instron 1222 tensile tester at room tempera-
ture. Samples of 15 mm in total length and 5 mm in width
were cut from the adhesive film. The tensile strength of the
samples was determined at fixed crosshead speeds, ranging
from 50 to 500 mm/min. Then, ultimate tensile strength
was defined as the maximum force applied (at the maxi-
mum stress) divided by the initial crosssectional area of the
sample. The elongation at break was calculated by divid-
ing the distance traveled by the crosshead until the sample
broke by the original length of the sample. The stress–strain
curves were recalculated into true tensile stress values by
taking into account the specimen dimensions, and all the
quantities presented relate to true values. All reported stress-
strain curves were reproduced from a series of six repli-
cate experiments, with variation within experiments of less
than 5%.
329
3.6. Gel content and molecular weight
Three samples were selected as representative examples
of the gel content of model PSA. The gel content of all sam-
ples was measured according to the method described by
Plessis [39]. A given mass of latex was dried on a substrate.
The substrate was placed inside a vessel with pure boiling
THF (Fluka) for 6 h. Afterward, the substrate was dried to
remove the solvent, and the amount of insoluble polymer
(gel content) was determined by the difference in weight of
the sample before and after solvent extraction.
The MWDs of the soluble fraction of model PSA latexes
large and small were determined by gel permeation chro-
matography (GPC) using a Waters 510 apparatus equipped
with two detectors: a refractometer and a viscometer (Vis-
cotek, Model 250). A series of three Styragel columns with
porosities of 102 , 104, and 106 Å (HR2, HR4, and HR6 from
Waters) was used. Filters were placed before the columns
to prevent gel damage to the columns. The temperature
was kept constant at 35 ◦ C on both detectors and column.
Distilled tetrahydrofuran was used as the solvent at a flow
rate of 1.0 mL/min. The molecular weight of the samples
was calculated using the universal calibration technique with
poly(styrene) standards.
4. Results
From the thermographs obtained in the characterization
of the large and small model PSAs, the Tg values observed
were −58 and −54 ◦ C, respectively. A slight difference in
the Tg values was observed. The large model PSA was poly-
merized in batch miniemulsion. The result indicated that
2-EHA units were largely incorporated at the end of the
polymerization, generating polymer chains richer in 2EHA,
which led to a slight reduction in the Tg of the polymer. In
batch polymerization, even if all droplets nucleated at the
same time, the less reactive monomer would still be prefer-
entially incorporated at the end of the process.
The gel contents of MM, MM2, small, and large PSAs
are given in Table 2. No chain transfer agent was used in
the polymerization formulations of model PSAs of large and
small particle sizes. As one can see, the gel content is nearly
the same for all four latexes, and in particular, the large and
small latexes have an identical gel content within experimen-
tal error.
The molecular weight distribution of the soluble fraction
is given in Fig.2, which shows that a slightly lower mole-
Table 2
Gel content of selected model acrylic PSAs
Sample Gel content (%)
MM 52.5
MM2 55.0
Small 56.5
Large 57
330 M. do Amaral et al. / Journal of Colloid and Interface Science 281 (2005) 325–338
Fig. 2. Molecular weight distribution of the small and large model PSAs.
Fig. 3. Particle size distribution of the small (!) and large (2) model PSA
latexes.
cular weight was obtained for the large model PSA. This
result was probably due to the fact that for such large parti-
cle size, the number average of radicals per polymer particle
was rather high, so that the system approached pseudobulk
conditions [40]. On the other hand, for the small model
PSA, which presented a higher molecular weight, the system
followed zero-one conditions [40], where a higher compart-
mentalization of the radicals enabled enhanced growth of the
polymer chains. For both model PSAs the final MWD ob-
tained is similar to those commonly obtained in emulsion
polymerization [39,41].
PSD characterization of the model PSA latexes used to
cast the adhesive films is illustrated in Fig. 3 and 4. PSDs of
the large and small model PSA latexes are given in Fig. 3,
whereas PSDs of MM and MM2 are represented in Fig. 4.
The final PSD reflected the process’ main characteristics,
where the large-monodisperse-particle-size latex was ob-
tained from a miniemulsion prepared with a nonionic sur-
factant and a large monomer droplet size [42]. A typical
Fig. 4. Particle size distribution of the MM2 (!) and MM (2) model PSA
latexes.
monodisperse small particle size was obtained by the con-
ventional semicontinuous emulsion polymerization process,
whereas bimodal and multimodal PSDs were obtained by
seeded semicontinuous emulsion polymerization employing
two seeds and multiple seeds, respectively.
We now turn to the rheological properties of our PSA
films once they are dry. The master curves of the linear
viscoelastic properties of the small, large, and S6L4 model
PSAs, obtained by applying the time–temperature superpo-
sition method, are given in Fig. 5. These curves were reduced
at a reference temperature of 20 ◦ C, corresponding to the
temperature at which the probe tests were performed.
Qualitatively [43], the linear viscoelastic properties of
commercial PSAs should lie within a window in the mod-
ulus-frequency domain. In essence, good PSA systems
should have a low modulus G at low frequencies (making
bonding favorable even on rough surfaces) and a higher-
modulus in the high-frequency range (causing the initiation
of failure to occur at higher stresses), as well a reasonably
high value of tan δ to dissipate energy on debonding. All
model PSA latexes used in this study fall in the right vis-
coelastic window as defined by Chang [43]. Furthermore,
the linear viscoelastic properties of the adhesive films ob-
tained from the dry latexes are quite similar to those reported
previously for PSA acrylic latexes [15].
However, direct comparison of G , G , and tan δ for
the two adhesives and the blend shows, within this window,
significant differences. In particular, the adhesive prepared
from large particles has a distinctly higher modulus and is
less dissipative than the adhesive prepared from small parti-
cles. However, the overall gel content is the same for both
latexes and the sol fraction is of lower molecular weight
for the large-particle latex (Fig. 2), a result that would lead
to a slightly lower value of G for the same polymer syn-
thesized in solution. Given that the monomer composition
is the same and so is the glass transition temperature, this
discrepancy suggests that the interfaces between particles
may play an important role here in determining the lin-
ear viscoelastic properties of the dry film. While it is well
known that controlling the degree of interdiffusion across
interfaces is crucial to the mechanical properties of poly-
mer blends [44,45] and for the case where interdiffusion
competes with crosslinking [46,47], this is an unexpected
 M. do Amaral et al. / Journal of Colloid and Interface Science 281 (2005) 325–338
(a)
(b)
(c)
Fig. 5. Rheological properties of the large (1), small (!), and S6L4 (Q)
latexes in the linear viscoelastic regime at a reference temperature of 20 ◦ C:
(a) G ; (b) G , (c) tan δ.
result for our experimental system. The Tg values of both
latexes are well below ambient temperature and interdiffu-
sion of polymer chains across the interfaces should be fast
and complete. Recent experiments on particles containing
a significant amount of gel fraction have shown, however,
that only the mobile chains can diffuse across the interface,
while the gel remains essentially immobile [48]. The origi-
nal structure of the latex, i.e., the particle size, would then
be retained and it is conceivable that the interfaces, enriched
331
(a)
(b)
Fig. 6. Representative probe tack curves for a debonding rate of 10 µm/s
for the PSA prepared from small and large particle sizes and blends thereof.
in the low-molecular-weight soluble species, would play an
important role in determining the linear viscoelastic prop-
erties. The magnitude of the effect is, however, spectacular
and would deserve further study. The blend S6L4 has proper-
ties almost exactly intermediate between those of its compo-
nents, which does not suggest any specific synergistic effect
but remains consistent with a simple picture of dissipative
interfaces.
If one seeks to define an approximate strain rate for tack
tests that would allow a comparison with rheological data, a
reasonable method consists of defining the equivalent strain
rate as Vdeb / h0 , where Vdeb is the probe velocity during
debonding and h0 is the initial thickness of the film [15].
With this definition, the tack tests were performed at 20 ◦ C
at a strain rate corresponding to a pulsation ω ranging from
0.1 to 10 rad/s. Based on the results of Fig. 5, one would
clearly expect to see differences in tack behavior between
these three latexes.
Fig. 6 shows the probe tack curve of selected but repre-
sentative experiments with the small and large model PSAs,
as well as with blends thereof. The debonding rate of the
probe tack tests shown in Fig. 6 was 10 µm/s, but simi-
lar results were observed at other debonding rates (100 and
1000 µm/s), qualitatively confirming the results from Fig. 6.
332 M. do Amaral et al. / Journal of Colloid and Interface Science 281 (2005) 325–338

Fig. 7. Representative probe tack curves for a debonding rate of 100 µm/s and corresponding images for the small and large model PSAs.

Unlike the results obtained in Fig. 5, for linear viscoelas-

tic properties, for blends comprising more then 20 wt%
small particles, the probe tack curve showed greater values
of εmax and Wadh than the curves for pure large and small
model PSAs. At the three different debonding rates, similar
values of the curve peak were obtained, irrespective of the
model PSA assessed. Clearly a synergistic effect has arisen
here that cannot be attributed to the linear viscoelastic prop-
erties in an obvious way. A question that immediately arises,
given the differences observed in the probe tack curves, con-
cerns the micromechanism of adhesive failure. As pointed
out previously, imaging the probe tack tests helps to eluci-
date this point. From the video recorded during the tests, key
images were digitized. To ease the comparison, only pho- Fig. 8. Average values of the maximum stress σmax measured in the probe
tographs corresponding to the test with the large and small tack curves as a function of the blend compositions of model PSAs. Probe
model PSAs are shown in Fig. 7. velocity: (") 10, (2) 100, (Q) 1000 µm/s.
Despite differences in the probe tack curves, the pictures
are rather similar, implying a similar micromechanism of ad- The average values of the main quantitative parameters
hesive failure initiated by a cavitation process and followed that can be extracted from the probe tack tests are illustrated
by controlled lateral growth of the cavities at the interface in Figs. 8–10. The error bars in the figures represent the stan-
between the probe and the film. An identical debonding dard deviations obtained. These figures show the results for
mechanism was observed for all tack experiments with our three debonding rates. Regardless of particle size, the val-
model adhesives. Therefore, the measured values of force ues of σmax , εmax , and Wadh increased with debonding rate.
and displacement can be quantitatively compared between This effect is well documented and is due to the viscoelastic
different films produced from different latexes [15,35,49]. behavior of the adhesive film [15,49].
 M. do Amaral et al. / Journal of Colloid and Interface Science 281 (2005) 325–338
Fig. 9. Average values of the maximum strain εmax measured in the probe
tack curves as a function of the blend composition for model PSAs. Probe
velocity: (") 10, (2) 100, (Q) 1000 µm/s.
Fig. 10. Average values of the energy of adhesion Wadh measured with the
probe tack curves as a function of the blend compositions of model PSAs.
Probe velocity: (") 10, (2) 100, (Q)1000 µm/s.
At the highest debonding rate, almost the same value of
σmax was obtained in all experiments, as shown in Fig. 8.
However, at the two lower debonding rates, a definite trend
can be seen, with a slightly higher value of σmax for the
S6L4 blend and a lower value for the small model PSA. Al-
though earlier publications [15] related the value of σmax to
the expansion of cavities, controlled by the elastic compo-
nent of modulus G , this simplistic picture was refined by
subsequent experiments showing that the size of the inter-
facial defects from which cavities expand can have a clear
influence on the value of σmax [50,51]. In our case, however,
there is no reason to think that the defect size at the interface
is different for the different blends, and a good correlation
between G and σmax is expected.
This correlation with G in small-strain viscoelasticity,
shown in Fig. 5, is verified for the large and small latexes,
but the S6L4 blend has the highest value of σmax while hav-
ing a modulus intermediate between those of the small and
the large PSAs. In principle, it is possible that a bimodal
PSD could have led to more uniform spatial distribution of
material in the dry films and, hence, to a reduction of the de-
333
fect size at the interface during contact with the probe, but
at this stage this remains a speculation and deserves further
investigation.
On the other hand, both εmax and Wadh (Figs. 9 and 10, re-
spectively) showed very marked variation among the model
PSAs assessed. In the debonding regime where failure oc-
curs by progressive propagation of interfacial cracks as is
the case here, the value of εmax is directly related to adhe-
sion energy [35,52] and this is obvious by comparing Figs. 9
and 10.
Except for the model PSA S2L8, which gave results inter-
mediate between those of the large and small model PSAs,
synergy was observed for other compositions of the small
and large model PSAs. Interestingly, behavior at all tested
debonding rates was consistent. For blends consisting of
40 wt% or more small particles, adhesive properties were
superior to the adhesive properties of the parent particles.
Moreover, adhesive properties showed a maximum in both
adhesion energy and maximum strain as a function of the la-
tex PSD used to cast the adhesive film. Blends with 80 wt%
small particles also showed synergy, but the results were in-
ferior to the optimum of properties detected at a composition
of 60 wt% small particles. The results suggest that for a fixed
copolymer composition, it would be possible to influence the
adhesive properties by changing the PSD of the latex.
It is, however, important to point out that the most effec-
tive synergy between the large and small model PSAs was
observed for a composition different from the composition
known to minimize the viscosity at high volume fraction.
Therefore, according to these results, to maximize adhesive
properties it may be necessary to drift from the PSD that
leads to the lowest viscosity [8,9].
4.1. Probe tack results of multimodal model PSAs
Given the results obtained for the large, small, and blends
of large and small model PSAs in probe tests, the next step
was to test the properties of two PSA latexes of high solid
content and low viscosity, whose major difference is the
PSD. The model PSA MM has a bimodal PSD, whereas the
model PSA MM2 presents a PSD with several distinct parti-
cle modes, as represented in Fig. 4. To check the influence of
solid content, which in turn influences drying time, the MM
sample was diluted to 50 wt% solid content. Tests with MM
diluted to 50 wt% solid content were termed MM50.
Images from the probe tack experiments (not shown) with
the high-solid-content latexes showed a pattern similar to
that observed for the blends of large and small particles. Ta-
ble 3 summarizes the main results (εmax , σmax , and Wadh ) for
the adhesives tested at 10 µm/s. It is interesting to remark
that the drying rate, evaluated by comparison of MM with
MM50, did not seem to influence much the average results.
The probe test results of the diluted samples, MM50, were
close to those for the sample applied “as is.” The comparison
was of course made for films of similar dry thickness.
334 M. do Amaral et al. / Journal of Colloid and Interface Science 281 (2005) 325–338

Table 3
Comparative main results obtained from the tack testa
Model σmax , εmax , Wadh , energy
PSA maximum maximum of adhesion
stress (MPa) strain (J/m2 )
MM 0.42 ± 0.13 4.4 ± 0.2 90.7 ± 3.2
MM50 0.42 ± 0.04 4.7 ± 1.4 106.4 ± 45
MM2 0.34 ± 0.01 7.1 ± 0.6 125.1 ± 3.4
Small 0.25 ± 0.02 2.1 ± 0.9 25.0 ± 10.4
Large 0.33 ± 0.07 1.0 ± 0.15 16.4 ± 2.5
S2L8 0.33 ± 0.07 1.6 ± 0.45 25.7 ± 10.1
S6L4 0.39 ± 0.08 3.8 ± 0.7 64.0 ± 11.8
a Debonding rate 10 µm/s.

(a)
It is interesting to compare in Table 3 the results for
MM and MM2 and the results for the model PSA latexes.
While the maximum stress values were only slightly higher
for the MM latexes, the εmax and Wadh values were signif-
icantly higher than those obtained for the model bimodal
PSA. Even composition S6L4, which gave the highest ad-
hesion for 50 wt% latexes, was found to give results clearly
inferior to those for MM and MM2, the high-solid-content
multimodal model PSA latexes.
Similar to the case of large and small model PSAs and
their blends, the probe test results for the multimodal model
PSA showed a marked dependence on the PSD of the latex
used to cast the adhesive film. The difference in PSD was
apparent in the values of εmax and Wadh , but not in the val-
ues of σmax , which were rather similar. On the other hand, (b)
the large difference in εmax observed may be due to differ-
ences in the adhesive interactions with the surface or in the
dissipative properties of the latexes.
To investigate whether the different results were influ-
enced by interfacial interactions between the adhesive and
the adherent, a series of probe tests were carried out with
a modified probe. The modified probe was spin-coated with
a thin layer of poly(ethylene–propylene) random copolymer
(Excelor 703 G2 provided by ExxonMobil Chemical). Some
model PSAs were selected for the experiments and Fig. 11
shows the stress–strain curves of the same PSA on both
surfaces for the small, large, and S5L5 films at 100 µm/s.
Clearly and regardless of the type of latex, the probe tack
curves on EP surfaces show lower values of σmax and much (c)
lower values of deformation before detachment. In all cases
the detachment is adhesive and the mechanism is analogous Fig. 11. Representative probe tack curves for a debonding rate of 100 µm/s
for the PSA prepared from small particles, large particles, and a 50/50 blend
to that observed in Fig. 7, except for two aspects: the number
on both steel and an EP surface.
of cavities actually formed is much smaller, and their propa-
gation rate is much faster. This is typical of what occurs on
low-energy surfaces and has been described in previous pub- the main difference between the stainless steel probe and
lications [53–55]. Table 4 shows the main results obtained the EP-coated probe is the lower level of adhesion, which
from the probe tests carried out at a debonding velocity of is evident from both the lower value of σmax and the much
10 µm/s. lower value of εmax . This lower level of adhesion trans-
Unlike the results obtained against the stainless-steel sur- lates into a lower strain at debonding (values of εmax are
face, the probe tack curves obtained with a probe coated all less than 2 at Vdeb = 100 µm/s as opposed to the steel
with a thin layer of a low-adhesion surface showed, except surface, where 2 < εmax < 8 at the same debonding rate). In
for the small model PSA, no marked influence of PSD of terms of debonding mechanisms, this means that the cavi-
the model PSA latexes. In general, it should be noted that ties have propagated at the interface rather rapidly and under
 M. do Amaral et al. / Journal of Colloid and Interface Science 281 (2005) 325–338 335

Table 4
Comparative main results obtained from the tack test using a probe coated
with poly(ethylene–propylene)a
Model σmax , εmax , Wadh , energy
PSA maximum maximum of adhesion
stress (MPa) strain (J/m2 )
MM 0.16 ± 0.03 0.49 ± 0.01 4.6 ± 0.8 Fig. 12. Schematic representation of the two competing mechanisms during
MM2 0.17 ± 0.01 0.49 ± 0.01 3.4 ± 0.7 the debonding process.
Small 0.19 ± 0.01 0.72 ± 0.07 7.6 ± 0.4
Large 0.17 ± 0.01 0.47 ± 0.01 3.2 ± 0.1
S4L6 0.19 ± 0.01 0.39 ± 0.02 4.5 ± 0.1 • For high Gc /G , the initial mechanism of failure is cav-
S5L5 0.16 ± 0.01 0.52 ± 0.13 3.8 ± 1.8 itation and fibrillation. The maximum extension of the
a Debonding rate 10 µm/s. fibrils is not controlled by the surface, but rather by
the rheological properties of the adhesive in elonga-
tion. This mechanism is never observed for these adhe-
low stresses. The distinctly lower measured values of σmax sives, but it is classic for PSAs for permanent applica-
relative to steel surfaces (for all latexes) are characteristic tions [35].
of a debonding controlled by the critical energy release rate • For very low values of Gc /G , failure occurs by crack
Gc rather than by the defect size or elastic modulus of the propagation without any preexisting cavitation in the
adhesive. Characteristically, the higher value of σmax in this bulk [53,54]. This mechanism is observed only when
configuration is measured for the small latex, which has the the adhesion is very weak and is observed here with the
lowest modulus G (see Fig. 5) but is the most dissipative. probes coated with EP.
Normally such an interfacial mechanism magnifies the ef- • For intermediate values of Gc /G , the initial failure
fects of interfacial interactions and reduces the bulk dissipa- mechanism can still be cavitation; however, the maxi-
tive effects. mum extension of the fibrils is controlled by the surface
The fact that the PSD does not have a significant effect of the adhesive [35]. This is the mechanism observed for
on EP surfaces suggests that the effects seen on steel were our model latexes on steel surfaces.
not due to interfacial phenomena, but rather to differences in
the local dissipative mechanisms induced by the growth of a A more detailed analysis of the debonding mechanism for
cavity along the interface between the film and the steel, and the three cases reveals that lateral propagation of the existing
that these differences might be due to the different film struc- cracks is faster for the low-Gc situation [54]. If lateral prop-
tures resulting from and influenced by the latex PSD [30,31]. agation is fast enough, it prevents any growth of cavities in
the bulk of the adhesive and, therefore, formation of elon-
gated bridging fibrils. As a consequence, adjoining cracks
coalesce, and the adhesive film debonds from the probe at
5. Discussion
relatively low levels of deformation [54].
Fig. 5 shows that the small model PSA has the highest
The results obtained from the rheological tests at small tan δ value among the model PSAs assessed. A higher value
strains (Fig. 5) help us to understand the differences ob- of tan δ indicates that the small model PSA is the most dissi-
served in the probe tests. During the debonding process two pative adhesive at small strains. In the probe tests done with
main mechanisms compete with each other: the propagation the probe coated with poly(ethylene–propylene), the initia-
of cavities along the interface as cracks (normal to the ten- tion of debonding occurred at a similar stress, and the final
sile direction) and the bulk expansion of the same cavities detachment occurred at a rather low value of strain for all the
parallel to the tensile direction. This competition determines model PSAs. The higher Wadh observed for the small model
to a large extent the final properties of the adhesive. The two PSA, due to slower lateral growth of the cavities under the
mechanisms are illustrated in Fig. 12. same applied stress, can be attributed to the more dissipative
Interfacial propagation is limited by the interfacial criti- properties of the polymer [54].
cal energy release rate, Gc which characterizes the amount For the experiments performed on steel surfaces, on the
of energy dissipated by a propagating crack at the interface other hand, the interpretation of adhesive properties in terms
between the PSA and the surface [54]. It depends mainly of rheology is more complicated. Recent experiments on ad-
on the adherent’s surface and on the dissipative properties hesives based on styrenic block copolymers [52] have shown
of the adhesive. Bulk expansion is limited chiefly [56,57] that the large-strain part of the tack curve (ε > 2) cannot be
by the elastic properties of the adhesive, i.e., by its elas- accurately predicted by linear viscoelastic properties alone
tic modulus, G . Fixing the experimental geometry, the key but the nonlinear elastic properties of the adhesive films
parameter controlling the behavior of the adhesive is the ra- must also be characterized. As an example, probe test curves
tio of the energy release rate to the elastic modulus, Gc /G . of the S6L4 and MM2 blends are shown in Fig. 13. Al-
Three different cases can be observed [38]: though both latexes have a blend of small and large particles
336 M. do Amaral et al. / Journal of Colloid and Interface Science 281 (2005) 325–338
Fig. 13. Representative probe tack curves obtained for Vdeb = 10 µm/s for
the S6L4 and of the MM2 model PSA.
Fig. 14. True stress as a function of extension λ for experiments performed
at two different crosshead velocities in uniaxial elongation for the MM
(dashed line) and MM2 (full line) multimodal PSA.
leading to rather similar values of G and G intermediate
between those of the small and large PSAs, the shapes of
the probe tests at Vdeb = 10 µm/s are markedly different at
large strains with the MM2 film, showing almost a plateau
in stress. This difference strongly suggests differences in the
nonlinear elastic properties of the two model PSAs, which
can be assessed with tensile tests.
Unfortunately, due to the drying process it was difficult
to obtain reproducible films of the desired thickness from
all the PSA latexes, and only exploratory experiments with
the multimodal latexes could be performed. The tensile test
results in Fig. 14 show that the nonlinear elastic properties
of the films cast from MM and MM2 are markedly different.
Two important observations illustrating potential differences
between PSAs produced from different latexes can be made:
the nonlinear elastic properties of the MM film are much
more strain rate dependent, and, at high strain rate, the MM
film shows a more pronounced strain hardening behavior
(upturn in stress at high strain), than the MM2 film.
These results could help to elucidate the differences in
performance of model PSAs. It is important to remember
that large-strain properties cannot be predicted easily from
small-strain viscoelastic data in the linear regime, at least
not from the absolute values of G and G . The MM2 model
PSA showed consistently better adhesive properties than the
MM model PSA. Because the drying rate did not seem to
influence the results much (as observed in the comparison
between adhesive films obtained from MM and from MM
diluted to 50 wt%, MM50), the key difference between MM
and MM2 was the PSD, considering that both model PSAs
had a similar molecular weight distribution and gel content.
It is now interesting to try to speculate on the reasons
leading to the differences in adhesion properties observed as
a function of latex PSD. The homogeneity of the adhesive
film, in combination with the chemical structure of the bulk
polymer, determines the ultimate film properties [58]. Al-
though the role played by the latex PSD in the film formation
process is not fully understood, many authors have investi-
gated it. Eckersley and Rudin [58] found, for example, that
as their latex dried, it was transformed from a colloidal dis-
persion into a continuous polymer film having mechanical
integrity. However, other types of films always retain, to a
certain extent, the memory of the particles from which they
were made [17]. In principle, for films prepared from parti-
cles of low Tg , polymer particles should deform and coalesce
due to the forces acting during the drying process and [59–
61], no noticeable voids should be observed in the adhesive
film [34].
The morphology of the final adhesive film may also influ-
ence the final adhesion properties, and it is intimately related
to the mechanism of drying and film formation. Recently,
Mallégol et al. [62], in their study of surfactant distribu-
tion in waterborne PSA, proposed that water-soluble species
would be carried to the surface with the water during drying
and build up around the particles. When the water evapo-
rated, these species would be deposited between particles,
where they would be highly effective in preventing any par-
ticle coalescence. However, working with two model PSAs
of different PSDs, the authors did not find a noticeable influ-
ence of particle packing on the migration of water-soluble
species to the film surface during drying.
The microstructure of the polymer (its chemical compo-
sition distribution (CCD), gel content, and MW) is influ-
enced by the polymerization process. Gel content is sim-
ilar for small (conventional emulsion polymerization) and
large (miniemulsion polymerization) PSAs, showing the in-
fluence of chain transfer to polymer in polymerizations with
acrylates. The different MWs observed in the samples show
the influence of the number average of radicals inside the
particles. Different CCDs can be obtained because of the
difference in reactivity of the two monomers. The batch
miniemulsion process led to the formation a microstructure
richer in blocky units of 2EHA, whereas the semicontinu-
ous polymerization ran under starved conditions could avoid
the accumulation of 2EHA. Investigation of the effect of the
CCD on adhesive properties [18], showed only a slight effect
on the performance of the adhesives.
During the drying process, particles approach each other.
Once contact is established free molecular chain ends and
 M. do Amaral et al. / Journal of Colloid and Interface Science 281 (2005) 325–338
low-molecular-weight polymer chains start to diffuse [54].
The highly branched molecules of ultrahigh molecular
weight that constitute the gel fraction, on the other hand,
probably do not diffuse at all, remaining in their original par-
ticle [48]. As a consequence, despite the similar gel content
observed in the model PSA, a different spatial organiza-
tion of the gel domains would be observed as a function
of the PSD. Therefore, films originating from latexes with
multimodal PSDs would probably have rather multimodal
distributions of gel domains.
By analogy with studies carried out with PSAs based on
styrenic block copolymers [52,63], the spatial organization
of gel domains may not influence much the rheological prop-
erties of the film in the small-deformation regime. Neverthe-
less, at large strains the connectivity between gel domains
may become crucial in controlling nonlinear elastic prop-
erties. The differences in adhesive properties observed as a
function of the PSD could be related, to a certain extent, to
the resultant distribution of gel domains in the adhesive film.
6. Summary and outlook
Probe test results for adhesive films prepared from latexes
with varying PSDs showed marked differences in adhesive
properties, which could possibly be related to particle size
and PSD of the model emulsion PSA. To make the compari-
son meaningful, the same copolymer composition was used
in all polymerizations resulting in the same gel fraction and
a very similar molecular weight distribution of the sol frac-
tion.
For the first series of experiments, using small and large
particle size latexes and blends of both latexes, marked dif-
ferences in adhesive properties were detected as a function
of PSD. The blends of small and large model PSAs had a
synergistic effect, and optimum adhesive properties could be
attained for a proportion of small particles close to 60 wt%.
Interestingly, this proportion differs from the proportion of
small particles known to minimize the viscosity of a highly
concentrated aqueous polymer dispersion. An optimum bal-
ance of both characteristics is likely to be found in the range
40–60 wt% small particles. A lower proportion of small par-
ticles, minimizes viscosity, but was found to give poorer
adhesive properties. A higher proportion of small particles
would unnecessarily increase viscosity, since it was found
that this point did not give better adhesive properties than
the point using 60 wt% small particles.
The probe test performed on adhesive films prepared
from multimodal latexes also showed an influence of PSD
on adhesive properties. The drying rate did not seem to influ-
ence much the adhesion properties of model PSA films. For
those adhesive films, analysis of large-strain deformation
showed a significant difference between MM (high-solid-
content, bimodal model PSA latex) and MM2 (high-solid-
content, multimodal model PSA latex). It is speculated that
latexes with different PSDs would probably lead to films
337
with different spatial organizations of gel domains and dif-
ferent molecular connectivities between those same gel do-
mains. These differences would probably influence the prop-
erties of the adhesive at large strains, and be the reason for
the observed difference in probe test results.
Finally, it is important to point out that these results have
a practical relevance. The PSD of a latex has important influ-
ence on the viscosity of high-solid-content aqueous polymer
dispersions. The final PSD of a latex is, to a large extent,
the result of the interplay of key process variables of the
emulsion polymerization process. Therefore, our results im-
ply that it is possible to design the process and formulation
of a high-solid-content PSA emulsion that would maximize
adhesive properties and would minimize viscosity, without
changing the core characteristics of the polymer (like gel
content, molecular weight distribution, and particle mor-
phology), which are due mainly to choice of monomer and
feeding strategy.
Acknowledgment
Dr. M. do Amaral acknowledges the financial support
from Surface Specialties—UCB.
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