Progress in Organic Coatings 35 (1999) 171–181

Control of rheology of water-borne paints using associative thickeners

A.J. Reuvers
Akzo Nobel Central Research, Department of Physical Chemistry and Mathematics, P.O. Box 9300, 6800 SB Arnhem, The Netherlands

Received 15 July 1998; received in revised form 15 December 1998; accepted 3 March 1999

Abstract

Water-borne decorative topcoats generally show inferior leveling and open time compared to solvent-based paints. Basically, this
behavior is caused by the divergent viscosity–solid content relationship for dispersions and emulsions and by the relatively high evapora-
tion rate of water. Employment of associative thickeners may improve leveling and open time of latex paints only if they introduce a
substantial amount of ‘network viscosity,’ characterized by a short relaxation time and little dependence on solid content. This network
viscosity enables one to formulate a paint with sufficient high-shear viscosity at a particle-packing density far below the value where low-
shear viscosity starts to diverge. Addition of an associative thickener not only affects rheology, but also the interaction between latex
particles: Associative HEUR thickeners may induce undesired phase separation by strong bridging between the latex particles. The
influence of HEUR thickeners on latex particle interaction has been studied by turbidity measurements. The experimental results could
qualitatively be interpreted very well by two-particle interaction potentials computed using the Self-Consistent-Field theory of Scheutjens
and Fleer. It is demonstrated how viscosity, created by the addition of an associative thickener to a highly concentrated latex, can be split up
into a polymer network viscosity and a contribution to (relative) dispersion viscosity. According to these analyses, reduction of the
molecular weight of tri-block HEUR thickeners yields an increase of the favorable network viscosity and a reduction of the unfavorable
dispersion viscosity. However, reduction of the molecular weight of the HEUR thickener is limited by the introduction of undesired phase
separation (bridging flocculation) below a certain molecular weight.  1999 Elsevier Science S.A. All rights reserved.

Keywords: Rheology; Dispersions; Associative thickener; Latex paint

1. Introduction
Water-borne decorative topcoats generally show inferior
application properties compared to solvent-based paints.
Application properties like leveling out of brush or roller
marks, open time, wet-edge time and filling capacity need to
be improved in order to make (semi-) gloss water-borne
paints competitive with solvent-based products. Here, we
define the open time of a paint as the period of time during
which the painter can make corrections in the freshly
applied wet paint without leaving extra brush marks at the
corrected spots. The wet-edge time on the other hand, repre-
sents the period of time that lapping of a freshly painted area
does not leave any marks at the edges of the area painted
previously. The filling capacity of a paint is inversely pro-
portional to the amount of topcoat layers needed to prevent
telegraphing of roughness of the primer layer to the surface
of the topcoat.
In this paper the fundamental causes for inferior leveling
behavior, open time and filling capacity of latex paints will
be elucidated. Subsequently, the influence of associative
thickeners on these application properties will be discussed
on the basis of rheology and turbidity measurements per-
formed on well-defined latices thickened with hydrophobi-
cally end-capped polyethylene glycol’s varying in
molecular weight.
2. Experimental
2.1. The binder latices
Three latices with almost identical chemical composition
but different particle radius have been prepared through
semi-batch emulsion polymerization. The monomer compo-
sition for the latices is given by: MMA/BuA/MAA = 54/
40/6 (weight ratio). APS has been used as an initiator. The
latices A and B have been stabilized with the anionic sur-

0300-9440/99/$ - see front matter  1999 Elsevier Science S.A. All rights reserved.
PII: S03 00-9440(99)000 14-4
172 A.J. Reuvers / Progress in Organic Coatings 35 (1999) 171–181

factant SDBS (C12H25 C6H4SO3Na) with an equal concen-
tration of surfactant per latex particle surface. Latex C has
been stabilized with a mixture of SDS and Triton X-165.
The latices have been neutralized with a 1 M NaOH solution
up to pH values of 6.5 and 9.0, respectively.
2.2. Synthesis of the HEUR thickeners
to avoid detection of multiply scattered light, the ratio of
the wavelength of the light, l, and the latex particle radius,
a, have been chosen as high as possible (l/a = 6.6 for all
examined latices). The turbidity measurements have been
performed at room temperature using a two-beam UV-VIS
Perkin Elmer spectrophotometer and flat sample cells with
a thickness of 0.02 cm.

Hydrophobically end-capped PEO thickeners (usually

denoted by ‘HEUR’ = Hydrophobically Modified Ethoxy-
lated Urethane) have been synthesized by the reaction of
polyethylene glycol with an excess of alkyl monoisocya-
nate. The purified reaction products are dried under vacuum
at 40°C. In order to prevent degradation the thickeners are
stored at −20°C. The HEUR thickeners obtained (Cn –
NCO–(PEO)–NCO–Cn) are denoted by Cn –mK, where n
represents the number of carbon groups of the hydrophobic
end-caps and m represents the molecular weight average of
the PEO spacer in kilogram per mol.
2.3. Rheology measurements
All rheology measurements have been performed at
20°C, using a Bohlin Controlled Stress Rheometer and a
cone/plate measuring geometry with a cone angle of 1°
and a cone diameter of either 4.0 or 5.5 cm.
2.4. Turbidity measurements
Turbidity measurements have been carried out with con-
centrated (thickened) latices in order to elucidate optically
the influence of added thickener on the interaction between
latex particles. Since the absorption of light by the latex may
be neglected, the turbidity, t, of a (thickened) latex is:
t = − ln(It =I0 )=L = − ln(T =Twater )=L,
where T represents the intensity of the transmitted light
through a cell containing latex, Twater represents the inten-
sity of the transmitted light through a cell containing water
and L represents the path length (= cell thickness). In order
Table 1
Latex characteristics
3. Rheology of unthickened latices
In this section an outline will be given of the character-
istic rheology of dispersions of Brownian particles. In Sec-
tion 4 it will be shown how this rheology is reflected in the
application properties of latex paints.
For a dispersion containing spherical-shaped particles,
dispersed in a Newtonian liquid with viscosity hl, the visc-
osity as a function of the shear stress, h(j), is described by
[1]:
h(j) = hl × hd (j) (2)
where hd(j) is a number representing the relative dispersion
viscosity which is determined by:
1. the volume fraction particles F;
2. the particle radius, a;
3. the polydispersity of the particle size distribution;
4. the interaction between the colloidal particles as
described by the two-particle interaction potential.
The influence of the two-particle interaction potential on
the rheology of dispersions will be discussed in the next
subsection.
3.1. Dispersion rheology as affected by the physico-
chemical interaction between particles
(1)
Generally, dispersed particles experience long range
( = soft) repulsive forces through the presence of surface
charge and/or attractive van der Waals forces. The latices
described in Table 1 contain negative surface charge origi-

Latex A Latex B Latex C

a
Surfactant 0.6% SDBS 0.3% SDBS 0.2% SDS, 0.2% Triton X-165

pH 9.0; 0.14 mol/l NaCl

Particle radiusb (nm) 45 84 158
Swelling factor, Sc 1.87 1.80 1.69

pH 6.5; 0.07 mol/l NaCl

Particle radius (nm) 39 78 137
Swelling factor, S 1.22 1.17 1.10
a
Wt% surfactant based on monomer weight.
b
Particle radius measured with QELS at pH 6.5; particle radius at pH 9.0 has been calculated from the increase of the particle volume upon neutralization to
pH 9.0.
c
Determination of the swelling factor is described in Section 3.1.
 A.J. Reuvers / Progress in Organic Coatings 35 (1999) 171–181
Fig. 1. Low-shear viscosity of latex A (39.5 wt% solids, pH 6.5) vs.
concentrated NaCl added; the inserted graphs represent the two-particle
interaction potential U as a function of the inter-particle distance h.
nating from the initiator, from the anionic surfactant and,
mainly, from neutralized weak acid MAA groups. There-
fore, the latex particles experience a physico-chemical inter-
action dominated by long-range electrostatic repulsion. This
repulsive interaction can be described by a two-particle
interaction potential, U, as a function of the inter-particle
distance h, as shown in the left top graph inserted in Fig. 1.
The range over which the electrostatic interaction acts, is
reduced by the addition of electrolyte (NaCl). Beyond a
critical NaCl concentration the (short range) van der
Waals attraction starts to dominate the two-particle interac-
tion (see Fig. 1). Ultimately, at very high salt concentrations
the attraction well in the particle–particle interaction poten-
tial becomes so deep, that Brownian motion of the particles
is insufficient to escape and phase separation (flocculation)
takes place.
Fig. 1 reflects the development of the low-shear viscosity
of latex A as a function of the concentration NaCl added.
hd(j → 0) turns out to be minimized at a NaCl concentra-
tion of about 0.07 mol/l water. At this minimum the parti-
cles experience a so-called ‘hard-sphere’ interaction [2];
‘hard-sphere’ particles do not repel or attract each other
until they actually make contact and further approach is
strictly impossible.
All further measurements have been performed on latices
in which a hard-sphere particle interaction had been created
by the addition of a proper amount of NaCl. At pH 6.5, a
minimum low-shear viscosity was attained at a concentra-
tion NaCl of 0.07 mol/l water. At pH 9.0, a minimum low-
shear viscosity was attained at 0.14 mol/l NaCl. The intro-
duction of a hard-sphere particle interaction in the latices
enabled us to elucidate the pure influence of water-soluble
thickeners on the interaction between latex particles.
Furthermore, in this case the volume fraction particles of
a latex can be determined by employing the unique relation-
ship between hd(j → 0) and F for monodisperse hard-
sphere particles which has been determined previously
[3]. For the examined latices, both at pH 6.5 and pH 9.0,
the weight fraction particles c was determined at which the
173
relative low-shear viscosity value equals 12.0. For hard-
sphere dispersions this value is known to be achieved at a
volume fraction F of 0.453. Subsequently, the swelling fac-
tor S to be used for the calculation of F for latices with a
known weight fraction particle c was determined, employ-
ing the following equation:
F = S =[1 + r(c − 1 − 1)] (3)
where r represents the density of the polymer (r = 1.1 g/
cm3). The swellin at decreasing particle size the contribu-
tion of this surface layer to the total volume of particles
increases and, thus, S increases. At pH 9.0 apparently con-
siderable swelling occurs. This must be ascribed to water
being absorbed within the bulk of the particles upon neu-
tralization of MAA.
3.2. Rheology of unthickened latices characterized by a
hard-sphere particle interaction
Monodisperse spheres experiencing a hard-sphere parti-
cle interaction represent the most ideal kind of dispersion.
For this type of dispersion, hd is described by the following
relationship [4]:
hd = F(F, ja3 =kT) (4)
For j → 0, hd becomes independent of the particle radius
a (see Fig. 2(a)); hd(j → 0) is only affected by the volume
fraction particles.
Fully monodisperse hard-sphere latices start to crystallize
above a critical volume fraction Fc = 0.494 [5–7]. Beyond
Fc the latex shows thixotropic behavior and no longer exhi-
bits a Newtonian low-shear viscosity. Already at a modest
deviation from monodispersity, crystallization occurs
beyond a higher critical volume fraction. This is the case
for latex C. The degree of monodispersity of the other two
latices was insufficient to yield any crystallization at all;
they exhibited a Newtonian low-shear viscosity within the
whole examined concentration range. Fig. 2(b) presents the
relative viscosity vs. the reduced shear stress for the same
latices.
Fig. 3 displays the relationship between hd(j → 0) and
F for our (approximately) monodisperse hard-sphere latices.
Latex A shows a slightly deviating behavior which is most
likely to be caused by its polydispersity in particle size. For
latices B and C the relationship between hd (j → 0) and F,
for F . 0.40, is described by the following empirical
equation:
hd (ja3 =kT → 0) = 0:53 × (1 − F=0:61) − 2 3
:
(5)
Upon normalization of j through multiplication with a fac-
tor a3/kT (see Fig. 2(b)), the viscosity profiles become
independent of the particle radius, as expected for mono-
disperse hard-sphere latices [4]. Beyond F . 0.3, a shear-
thinning region appears, characterized by an inflection
point in a log(hd) versus log (ja3/kT) diagram at a critical
reduced shear stress jca3/kT = 0.4. Shear thickening is
174 A.J. Reuvers / Progress in Organic Coatings 35 (1999) 171–181
Fig. 2. (a) Viscosity h vs. shear stress for latex A (45 nm), B (84 nm) and C
(158 nm) at two volume fraction particles; pH = 9.0; [NaCl] = 0.14 mol/
l. (b) Relative viscosity hd vs. reduced shear stress ja3/kT for the same
latices as described under Fig. 2(a).
observed beyond a reduced shear stress of about 4. At
F = 0.57 the scaling law of Krieger [4] is not obeyed
exactly. This is probably caused by slight deviations from
a hard-sphere particle interaction and/or from a monodis-
perse particle size distribution.
3.3. Why inferior leveling behavior and open time for
water-borne coatings
In Fig. 3 the viscosity–concentration relationship for un-
swollen monodisperse hard-sphere latices has been com-
pared with that of an alkyd solution. While the logarithm
of the low-shear viscosity of the alkyd solution increases
linearly with concentration (at least within this concentra-
tion range of interest), the low-shear viscosity of the hard-
sphere latices hardly increases at low concentration and,
subsequently, starts to diverge very rapidly upon approach-
ing a concentration of 61 vol% particles. This divergent
behavior is caused by the approach of the maximal packing
density of particles, where the particles become immobile.
In case of soft repulsive or attractive interaction between the
latex particles, divergent behavior occurs at even lower
volume fraction particles.
From this rheological behavior it can be explained why
latex paints have to be formulated with a water-soluble
thickener. In order to apply a paint (by brush or roller) at
sufficient film thickness, the viscosity at a shear rate of
104 s − 1 must be at least 0.2 Pas. Without a thickener, this
level of high-shear viscosity is only reached at volume frac-
tion particles very close to the maximum packing value,
where leveling out of brush or roller marks is opposed by
a very high low-shear viscosity (see Fig. 3). Therefore, the
volume fraction particles in the latex paint must remain
limited in order to obtain leveling and open time, and a
water-soluble thickener has to be added in order to obtain
sufficient high-shear viscosity.
Let us now consider the low-shear viscosity measured as
a function of drying time and compare the behavior of a
‘state of the art’ latex paint with that of an alkyd paint. In
Fig. 4 it can be seen that the low-shear viscosity, h0, of the
latex paint at t = 0 is already considerably higher than
h0(t = 0) of the alkyd paint, despite its lower viscosity at
a shear rate of 104 s − 1 (latex paint: 0.2 Pas; alkyd paint: 0.5
Pas). This is caused by the undesired pseudoplasticity intro-
duced by the addition of the HASE thickener; before addi-
tion of the thickener a Newtonian paint is obtained, yet with
insufficient high-shear viscosity.
Fig. 4 also demonstrates the undesired rapid increase of
the low-shear viscosity characteristic for latex paints and
responsible for a short open time. Firstly, this is caused by
the relatively high evaporation rate of water as compared
with the solvent of the alkyd paint. Secondly, this is caused
by the swelling of the latex particles with water and co-
solvent and through adsorption of thickener on the latex
particle surface; through that the effective particle density
at t = 0 is already very close to 61% (the volume fraction
corresponding with a divergent low-shear viscosity as
depicted in Fig. 3), despite the relatively low solid content
of the latex paint (35–40 vol% solids against 50–55 vol%
solids for the alkyd paint).
In Section 5 it will be shown how the application proper-
ties we are aiming for are affected by the interaction
between latex particles and water-soluble HEUR thickeners.
Fig. 3. Relative low-shear viscosity vs. volume fraction binder for un-
swollen monodisperse hard-sphere dispersions and for an alkyd solution.
 A.J. Reuvers / Progress in Organic Coatings 35 (1999) 171–181
Fig. 4. Low-shear viscosity vs. drying time for a latex and an alkyd paint.
4. Rheology of HEUR solutions in water
Fig. 5 reflects the specific low-shear viscosity of HEUR
solutions in water as affected by the length of both the
hydrophobic end-cap and the PEO spacer. (The specific
viscosity is defined as (h/hwater) − 1).
Hydrophobic end-capping of PEO turns out to yield a
viscosity increase beyond a critical wt% HEUR; this critical
concentration apparently reduces at decreasing PEO spacer
length and increasing hydrophobe length and is probably
related to the Critical Micelle Concentration (CMC) of
Fig. 5. Specific low-shear viscosity of HEUR solutions in water at 20°C, as
affected by the length of the hydrophobic end-cap at a PEO spacer length
of 12 000 and 35 000 g/mol.
175
these polymer surfactants. Beyond the CMC a space-filling
dynamic network of bridged micelles is created [8–10],
inducing a ‘network viscosity’ hn proportional to the aver-
age number density of polymer coils being active in this
network. This number density increases at increasing hydro-
phobe length. The relaxation time of hn(j) is determined by
the lifetime of the associations within the micelles; both
increase at increasing length of the hydrophobic end-caps.
hn(j) obtained for HEUR solutions in water can be strongly
affected by the addition of surfactants [9,10] or co-solvents
[11].
5. Rheology and stability of latices thickened with
HEUR
5.1. Introduction
HEUR thickeners adsorb on the latex particle surface if
the hydrophobic end-caps are sufficiently large and if the
surface of the particles is sufficiently apolar [12,13]. The
lifetime of these (HEUR hydrophobe–particle) associations
is commonly very short (, , 1 s), but new associations
arise continuously. So far HEUR thickeners behave similar
to ordinary non-ionic surfactants. Since, however, the
HEUR thickeners contain two hydrophobes per molecule
they can also form bridges between neighboring particles.
Although every individual bridge has a very short lifetime,
yet all the time the latex comprises a space-filling network
of polymer coils connected by the latex particles if the
volume of fraction particles is sufficiently high. Such a net-
work induces a level of low-shear viscosity proportional to
the number density of springs. This number density
decreases at decreasing strength of the (hydrophobe parti-
cle) associations; at the same time the shear rate increases
beyond which the network thickening diminishes, which is
favorable for obtaining thickening at high-shear rates with-
out introduction of pseudoplasticity (Fig. 6).
Thus, bridging between particles of added HEUR induces
a network viscosity, denoted by hn(j). This mechanism of
thickening is very favorable in a latex paint, since sufficient
high-shear viscosity can be obtained at volume fraction
particles far below the highest packing density, resulting
in an extension of the open time. However, the adsorption
on, and bridging between, particles of added HEUR influ-
ences the latex rheology also by affecting the interaction
between the latex particles:
Adsorption of HEUR may result in an increase of the
effective volume fraction particles which reinforces the
undesired dispersion rheology of the paint, character-
ized by the divergent viscosity–concentration relation-
ship
Bridging of HEUR between latex particles induces an
attraction force between particles which may result in
undesired low-shear pseudoplasticity and, in the
176 A.J. Reuvers / Progress in Organic Coatings 35 (1999) 171–181

and xSW = 0,
where S and W represent the particle surfaces and water,
respectively. The excess free energy per surface area Aint/
kTL is calculated after ensemble averaging. the Full equi-
librium is assumed. Calculated interaction curves are
shown in Fig. 7.
Before addition of HEUR the plates (or particles) are
assumed to experience hard-sphere interaction. At a volume
fraction HEUR of 0.001, a repulsive interaction appears at
small particle separations because of steric interaction
between adsorbed HEUR molecules; at a somewhat larger
Fig. 6. Microstructure of a latex thickened with HEUR. distance attractive interaction is induced because of brid-
ging of HEUR molecules between the particles.
At increasing concentration of HEUR the range over
extreme situation, undesired phase separation [14,15]
which the repulsive force acts increases continuously; the
well in the interaction curve, however, firstly becomes dee-
Both the latex particle interaction and the rheology
per but reduces beyond a HEUR concentration of 0.01.
obtained are strongly affected by the strength of the
According to these calculations a critical bulk concentration
HEUR hydrophobe–particle associations. The latter,
affected by both the length of the hydrophobic end-caps of HEUR exists, inducing a maximal attractive force
between the particles. Beyond a certain depth of the mini-
and the polarity of the particle surface, will be kept constant
mum, the Brownian energy of the particles will be insuffi-
in this investigation. In this paper, we investigate the latex
cient for the particles to escape from the potential well and
particle interaction and the rheology obtained as affected
bridging flocculation (phase separation) may occur.
by: (a) the spacer length and the concentration of the
From these calculations the influence of HEUR on the
HEUR thickener; (b) the size of the latex particles.
interaction between latex particles can be understood qua-
Section 5.2 will focus on the influence of HEUR thick-
litatively. This knowledge will be used in the next para-
ener added on the latex particle interaction and spatial dis-
tribution, both theoretically and experimentally. In Section graphs to interpret turbidity and rheology measurements
on thickened latices.
5.3 the rheology of a thickened latex will be discussed as
affected by the spacer length of the HEUR thickener; the
5.2.2. Influence of the addition of HEUR thickener on the
thickening obtained will be quantified and interpreted in
interaction between latex particles as determined by
terms of (desired) network viscosity (hn) and undesired dis-
persion viscosity (hd). In Section 5.4 finally, the influence of turbidimetry
the thickener concentration and the latex particle size on the For stable, thickened latices the influence of the added
rheology and phase behavior will discussed. HEUR thickener on particle interaction can be elucidated by
measuring the turbidity of a latex as affected by the addition
5.2. The particle interaction as affected by addition of of the thickener. In this subsection, turbidity measurements
HEUR will be discussed, performed on latex A thickened with C12
end-capped HEUR thickeners with a varying PEO spacer
length.
5.2.1. Calculation of the two-particle interaction potential
In order to obtain an impression of the influence of HEUR
thickener added on the interaction between latex particles,
two-particle interaction curves have been computed using
the Self-Consistent-Field theory of Scheutjens and Fleer and
co-workers [16–18]. The HEUR polymers have been mod-
eled as tri-block co-polymers of the type C6A100C6 where C6
represents an alkyl group attached on a hydrophilic back-
bone A of 100 monomer units. All conformations of triblock
co-polymers are generated on a hexagonal latice restricted
on both sides by impenetrable surfaces (modeling two-par-
ticle surfaces) M latice sites apart. The conformations are
weighted by the Boltzmann factor calculated using the fol-
lowing Flory–Huggins x parameters:
Fig. 7. Excess free energy per surface area Aint/kTL calculated for two
xCA = 0:5, xCS = − 3, xCW = 1:6, xAS = 0, xAW = 0:5 plates immersed into a HEUR solution as a function of plate distance M,
for volume fractions HEUR polymer in the bulk FHEUR varying between
0.001 and 0.05.
 A.J. Reuvers / Progress in Organic Coatings 35 (1999) 171–181
In order to simulate the first stage of drying of a paint, the
turbidity and (in the next paragraphs) also the rheology of
HEUR thickened latices will be monitored as a function of
volume fraction latex particles, keeping the concentration
thickener per volume particles constant. For this experiment
the concentration HEUR has been kept constant at 11.3 mg
HEUR/cm3 latex particles.
Within the examined concentration range the turbidity of
the unthickened hard-sphere latex decreases at increasing
concentration which is in accordance with theory [19] (see
Fig. 8). Upon addition of a thickener the turbidity of the
latex might as well increase as decrease.
According to theory [19], an increase of turbidity upon
addition of a thickener can be explained by the introduction
of a well in the two-particle interaction curve, resulting in an
increased number of temporary particle doublets in the latex
(see Fig. 9); at sufficient well depth phase separation is
induced below certain volume fraction particles. A decrease
of turbidity upon the addition of a thickener is caused by the
introduction of a repulsive force exerted by the hairy layers
of adsorbed thickener molecules, preventing the particles
from coming close together.
According to the calculations in the previous paragraph
the added HEUR thickener introduces both a repulsive inter-
action (because of adsorption) and an attraction well
(because of bridging). The measured influence of the thick-
ener added on the turbidity tells us which force dominates
the spatial particle distribution.
From Fig. 8 it can be concluded that both a decrease of the
volume fraction particles and a decrease of the PEO spacer
length reinforce the influence of bridging on the averaged
spatial particle distribution; at a spacer length of 8000 g/mol
phase separation is induced for F , 0.57; at a spacer
length of 12 000 g/mol the bridging starts to dominate par-
ticle distribution below F = 0.53; nevertheless the thick-
ened latex remains stable at least down to F = 0.29.
At increasing volume fraction particles, the influence of
the well in the interaction potential on both the spatial par-
ticle distribution and (see below) rheology is reduced; on the
Fig. 8. Turbidity of latex A (a = 45 nm) as affected by addition of
C12–HEUR thickeners with different PEO spacer length; 11.3 mg HEUR/
cm3 particles; l/a = 6.6; pH = 9.0; [NaCl] = 0.14 M.
177
Fig. 9. Influence of the spatial particle distribution on the turbidity of a
concentrated latex.
other hand, the influence of the short-range repulsive force
on particle distribution and rheology increases, especially at
the highest spacer length of 35 kg/mol.
5.3. Influence of the spacer length of the HEUR thickener
on the rheology of thickened latices
The influence of the spacer length of the HEUR thickener
on the rheology of thickened latices has been examined for
the same samples that have been analyzed with turbidity
measurements in the previous paragraph. In Section 5.3.1
the rheology measured at 45.3 vol% latex particles will be
discussed. In Section 5.3.2, subsequently, it will be demon-
strated how the viscosity created by an associative thickener
in a highly concentrated latex can be split up into a polymer
network contribution and a dispersion contribution from the
thickener. In Section 5.3.3 this procedure will be applied in
order to evaluate the influence of the HEUR spacer length
on the two modes of thickening.
5.3.1. Rheology of 45 vol% latex A thickened with C12-
HEUR thickeners
In order to elucidate the degree of thickening taking place
in the liquid phase of the latex through network formation of
HEUR molecules (in combination with SDBS surfactant)
the liquid phase of latex A (at F = 0.453, pH 9.0 and
0.14 molar NaCl) has been separated by centrifugation
and, subsequently thickened with 0.94 wt% HEUR. This
concentration has been chosen in order to measure the max-
imal possible thickening in the liquid phase of the latex,
which would take place at the absence of the adsorption
of HEUR thickener on the latex particles. If the HEUR
thickener will not adsorb on the latex particle surface, the
low-shear viscosity of the thickened latices would be equal
to the product of the relative latex viscosity ( = 12) and the
viscosity of the HEUR solutions. However, Fig. 10 and
Table 2 show that the actual low-shear viscosity of the
thickened latices is much higher which proves that the thick-
ening of latex A is almost completely caused by the inter-
action between the HEUR thickener and latex particles. This
conclusion cannot be generalized. At increasing polarity of
the latex particle surface, for example, the contribution of
the thickener–particle interaction to thickener efficiency is
expected to be reduced.
Now it is time to address the following questions:
1. How can we split up the viscosity created by the addi-
178 A.J. Reuvers / Progress in Organic Coatings 35 (1999) 171–181

shear thinning of h(j), measured for j , 0.4 kT/a3, can

Fig. 10. Filled symbols: 45.3 vol% latex A particles (a = 45 nm)
+ 11.3 mg C12–HEUR/cm3 particles; open symbols: 0.94 wt% HEUR dis-
solved in the liquid phase of latex A.
tion of an associative thickener to a highly concentrated
latex, into a favorable polymer network viscosity hn(j)
and an unfavorable contribution to the (relative) disper-
sion viscosity hd(j)?
2. How are these different modes of thickening affected by
the spacer length of the HEUR thickener?
Question 1 will be addressed in the next sub-paragraph
and Question 2 will be answered in Section 5.3.3.
5.3.2. Determination of the two modes of thickening of a
concentrated latex
In order to answer Question 1 we will examine the rheol-
ogy profiles (log h vs. log j) of the thickened latices at
values of F sufficiently high to loosen the influence of brid-
ging attraction on spatial particle distribution; thus, the
added thickener has to reduce the turbidity of the latex.
Under this condition and at sufficiently low shear stresses,
a thickened latex may approximately be regarded as a hard-
sphere latex (with effective volume fraction particles Feff
and an effective radius aeff) dispersed in a Newtonian liquid
phase; then, the viscosity of the thickened latex as a function
of the shear stress is described by:
h(j) = hn × hd (j)
where hd(j) represents the relative hard-sphere viscosity
hd = F(Feff , ja3eff =kT), as described in Section 3.2; hn repre-
sents the Newtonian ‘liquid phase’ viscosity induced by the
dynamic polymer (thickener) network, in which the latex
particles may act as junctions.
If F is sufficiently high to loosen the influence of the
bridging attraction and if the relaxation time of
hd(j) .. relaxation time of hn(j), then the degree of
be used as a finger print for Feff. The procedure for the
estimation of Feff from the degree of shear thinning of
h(j) has been reflected in Fig. 11 for 53.8 vol% latex A
thickened with C12 –12 K HEUR. From Fig. 8 it can be
concluded that the condition on F is obeyed for this
system. Fig. 11 reflects that, for j , 0.4 kT/a3, the visc-
osity profile of the thickened latex coincides with the visc-
osity profile of the unthickened latex at F = 0.592 ± 0.03,
if the former viscosity profile is divided by a factor of 150
and shifted along the x-axis with a factor 59.2/53.8. Thus,
for j , 0.4 kT/a3 the viscosity of the thickened latex h(j)
can be considered as the product of a Newtonian network
viscosity hn (with a value of 150 mPas) and a relative hard-
sphere dispersion viscosity hd(j) corresponding with Feff =
0.592 and a radius aeff = ([59.2/53.8]1/3 × 45 nm =)
46.5 nm. This means that the adsorbed thickener yields an
(undesired) increase in the volume fraction particles with a
factor 1.10.
For j . 0.4 kT/a3, the hard-sphere approximation
becomes open to question because the hairy layer may
deform under shear; besides, the assumption that hn does
not depend on j will no longer hold. The shear-thinning
behavior observed at the upper end of the viscosity profile
in Fig. 10 is very likely to be caused by shear thinning of
hn(j).
5.3.3. Influence of the HEUR spacer length on the two
modes of thickening
Let us now examine the influence of the HEUR spacer
length on the two different modes of thickening, using the
rheology profiles measured as a function of volume fraction
particles for latex A thickened with 11.3 mg C12 –HEUR/
[cm3 particles].
The viscosity profiles measured at the highest volume
fraction particles have been used to derive the factor Feff/
F obtained at different PEO spacer lengths according to the
procedure outlined in the previous subsection; the results
are shown in Table 3: the (unfavorable) increase of F
(6) through addition of C12 –HEUR turns out to rise at increas-

Table 2
See legend Fig. 10

hliquid phase × hd(j → 0), [Pas] hlatex + HEUR(j → 0), [Pas]

C12-12 K 0.029 1.84

Fig. 11. Determination of the effective volume fraction spheres Feff for
C12-20 K 0.033 2.60
C12-35 K 0.048 41.1 53.8 vol% latex A particles (a = 45 nm) + 11.3 mg HEUR/cm3 parti-
cles; pH = 9.0.
 A.J. Reuvers / Progress in Organic Coatings 35 (1999) 171–181 179

Table 3

Rheology of latex A and B as affected by addition of C12–HEUR; pH = 9.0

Conc. HEUR Volume fraction latex Feff/F: Factor of increase of h (j → 0) hn (j → 0) hd (j → 0)

[mg/cm3 spheres] spheres F* corresponding F through adsorbed HEUR at F* [Pas] at F* [mPas] at F*
with h(104s − 1) = 0.2 Pas

Latex A +
C12-35 K 11.3 0.455 1.32 ± 0.005 52 35 ± 5 1500
C12-20 K 11.3 0.484 1.185 11 52 210
C12-12 K 11.3 0.472 1.10 3.0 73 41
C12-12 K 24.4 Phase separation 1.20
C12-12 K 45.2 0.307 1.24 0.66 120 5.5

Latex B +
C12-12 K 3.3 0.577 13
C12-12 K 5.7 Phase separation
C12-12 K 11.3 Phase separation
C12-12 K 22.6 Phase separation
C12-12 K 45.2 0.361 0.65

ing PEO spacer length. HEUR thickener on the rheology and phase behavior of
Although the adsorbed HEUR yields an undesired latices will be discussed on the basis of measurements per-
increase of F, yet this increase remains strongly limited formed on two latices with identical surface composition but
through the bridging attraction induced by the HEUR poly- different particle radius a (latex A: a = 45 nm, latex B:
mers; the bridging attraction enables strong interpenetration a = 84 nm).
of the hairy HEUR layers on neighboring latex particles. F
is expected to increase much stronger if the HEUR mole- 5.4.1. Phase behavior
cules would contain only one hydrophobic end-group per Upon addition of a certain minimum amount of HEUR
molecule. both latices turn out to be destabilized (through bridging
From now on it is assumed that the latex paint must be flocculation) within a certain particle concentration range
formulated at a volume fraction particles F* corresponding (see Fig. 13); the particle concentration up to which phase
with a high-shear viscosity h(104 s − 1) of 0.2 Pas. At F*, the separation occurs reaches a maximum at a critical HEUR
rheology of the thickened latices has been examined in more concentration cpHEUR . Beyond cpHEUR restabilization of the
detail (see Table 3). It turns out that h(j → 0) and, thus, latices occurs.
the degree of pseudoplasticity of the paint reduce at decreas- The influence of HEUR concentration on the stability of
ing PEO spacer length. Employing the factor Feff/F and the the latices can be explained by the calculations presented in
relation between hd (j → 0) and F for latex A (see Fig. Section 5.1, predicting a critical bulk concentration of
3(a)), the contribution of hd (j → 0) to h(j → 0) at F* has HEUR at which a maximal well depth in the two-particle
been calculated. Subsequently, the favorable network visc- interaction potential is induced. The smaller sized particles
osity hn(j → 0) induced by the HEUR thickener has been of latex A offer a larger surface for HEUR polymers to
calculated with eqn (6).
From Table 3 it can be concluded that the reduction of
the spacer length of the HEUR thickener yields an in-
creased level of network viscosity and a reduced level of
dispersion viscosity at F*. Together, this results in a reduc-
tion of both the degree of pseudoplasticity ( → improved
leveling behavior) and the rate of increase of the viscosity
during the drying of the paint ( → longer open time), as
illustrated by Fig. 12. Unfortunately, the reduction of the
PEO spacer length is limited through the introduction of
bridging flocculation below a critical spacer length (see
Section 5.2).

5.4. Influence of thickener concentration and latex particle

Fig. 12. The low-shear viscosity of latex A as affected by the PEO spacer
size on the rheology and stability of thickened latices length of the C12–HEUR thickener added; 11.3 mg HEUR/cm3 particles;
pH = 9.0; ↑ : h(104 s − 1) = 0.2 Pas; solid lines indicate: h(104 s − 1) >
Finally, the influence of the concentration of the C12-12 K 0.2 Pas.
180 A.J. Reuvers / Progress in Organic Coatings 35 (1999) 171–181
Fig. 13. Low-shear viscosity of latex A and B as affected by the concen-
tration C12–12 K HEUR thickener added; pH = 9.0; ↑ : h(104 s−1) = 0.2
Pas; solid lines indicate: h(104 s − 1) > 0.2 Pas.
adsorb on than the latex B particles. Therefore, the amount
of HEUR that must be added to reach the critical bulk
concentration of HEUR is expected to be higher for latex
A. This is in accordance with our observations (see Fig.
13).
For latex B instability appears to occur up till higher F
values and within a larger concentration range of HEUR
than for latex A. This can be understood by the larger con-
tact area between the latex B particles resulting in a deeper
well in the interaction curve. In order to obtain stable paints
at moderate HEUR concentrations latex B should be thick-
ened with the C12-20 K instead of the C12-12 K thickener.
For latex A Feff/F ( = the factor of increase of F through
thickener adsorption) has been determined as a function of
the C12-12 K HEUR concentration according to the proce-
dure depicted in Fig. 11. In Table 3 it can be seen that Feff/F
increases strongly upon raising the HEUR concentration in
latex A from 11.3 up to 24.4 mg/cm3 spheres. Again, this is
in accordance with the previously calculated interaction
curves. At further addition of the thickener the increase of
Feff/F slows down, probably because the state of particle
surface saturation is approached. For latex B Feff/F could
not be determined since the addition of the C12 –12 K HEUR
induced an increase of the latex turbidity within the whole
concentration range examined.
5.4.2. Rheology
At a fixed volume fraction particles F, the level of both
the dispersion viscosity hd and the network viscosity hn turn
out to increase at increasing HEUR concentration. The
increase of hd is caused by an increase of the value of Feff.
The increase of hn arises from an increase of the number of
bridges between particles and maybe also from the reinfor-
cement of the bridged micelle network in the liquid phase
through SDBS expelled from the particle surface.
At a fixed value of the high-shear viscosity
(h(104 s − 1) = 0.2 Pas), however, hd is reduced and hn
increases if the HEUR concentration is raised (see Table
3); this results in a reduced dependence of the low-shear
viscosity on the solid content as shown in Fig. 13; thus, it is
concluded that open time can be extended by raising the
thickener concentration. Unfortunately, open time is
extended at the expense of a reduced solid content of the
paint and, thus, at the expense of the filling capacity of the
paint. Besides, an increase of the thickener concentration
may cause re-coatability and water sensitivity problems.
5.5. Conclusions
From turbidity measurements it turned out that the addi-
tion of an HEUR thickener to a concentrated latex induces
both short-range repulsive forces and long-range attractive
forces between the latex particles. This interaction can be
explained by the bridging of hairy layers of adsorbed HEUR
polymer between neighboring latex particles. If the attrac-
tive forces become too large, undesired phase separation
may be induced in the latex. The experimental results
could qualitatively be interpreted very well by two-particle
interaction potentials computed using the Self-Consistent-
Field theory of Scheutjens and Fleer.
It is demonstrated how (under certain conditions) the
viscosity, created by the addition of an associative thickener
to a highly concentrated latex can be split up into a polymer
network viscosity and a contribution to the (relative) disper-
sion viscosity. The polymer network viscosity arises from a
space-filling dynamic network of water-soluble thickener
bridging between particles and/or micelles. The contribu-
tion to the dispersion viscosity arises from an increase of the
effective volume fraction particles through adsorption of the
thickener.
According to these analyses, reduction of the PEO spacer
length of tri-block HEUR thickeners yields an increase of
network viscosity and a reduction of dispersion viscosity. It
can be reasoned that this is very favorable for improvement
of the open time and the leveling behavior of water-borne
paints. However, reduction of the PEO spacer length of the
HEUR thickener is limited by the introduction of undesired
phase separation (bridging flocculation) below a certain
PEO spacer length.
Rheology measurements indicate that the open time of a
water-borne paint improves at increasing concentration of
HEUR thickener. Unfortunately, this improvement is
 A.J. Reuvers / Progress in Organic Coatings 35 (1999) 171–181 181

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