2003 Spring Advanced Coating Fundamentals Symposium

EFFECTS OF CARBOXYMETHYL CELLULOSE AND ETHYL(HYDROXYETHYL) CELLULOSE ON

SURFACE STRUCTURE OF COATINGS DRAWN DOWN FROM POLYSTYRENE SUSPENSIONS.
Alexandra Wallstrm Lars Jrnstrm Peter Hansen Jouko Peltonen
Dept. of Chem. Eng. Dept. of Chem. Eng. STFI Dept. of Phys. Chemistry
Karlstad University Karlstad University Box 5604 bo Akademi University
SE-651 88 Karlstad SE-651 88 Karlstad SE-114 86 Stockholm FIN-20500 bo
Sweden Sweden Sweden Finland
ABSTRACT
The surface structure of coating layers drawn down from polystyrene suspensions was investigated. The effects of
two different soluble cellulose ethers, ethyl(hydroxyethyl) cellulose and carboxymethyl cellulose, were compared.
Each of the suspensions was investigated at three different concentration levels of the soluble cellulose ethers. An
Atomic Force Microscope was used to investigate the surface structure of coating layers drawn down on polyester
substrates from aqueous polystyrene (PS) suspensions. The surface structure was interpreted by calculating the pair
distribution function ( ) r g , where r is the radius of a ring centered at a particle.
The colloidal stability of the polystyrene suspensions was also investigated by means of rheology. The relative
viscosity was calculated in order to elucidate the colloidal stability and degree of flocculation.
Ethyl(hydroxyethyl) cellulose possesses temperature responsive properties, and the suspensions were investigated at
two temperatures, 23
o
C and 55
o
C. The effects of the concentration of cellulose ether on the relative viscosity
indicated that ethyl(hydroxyethyl) cellulose, at least at the higher temperature, destabilized the PS suspensions by a
capillary induced phase separation mechanism
INTRODUCTION
Characterization of the surface structure of coating layers is important since the particle orientation and the degree of
order of the surface determine the gloss and affect the penetration of fluids, e.g. printing inks.
The micro-roughness associated with the particle alignment on the surface of the final coating plays a major role in
determining the gloss of the coated paper [1] and the gloss is one of the most important surface factors and
influences the quality of the printing. An enhanced micro-smoothness has been shown to improve the missing dot
performance and the print gloss. Therefore the importance to characterize the surface structure and the pigment
particle alignment, especially since investigation has shown that there is a correlation between runnability, paper
gloss and particle alignment that goes down to the micro-roughness [2].
The current state-of-the-art analysis of surface structures, i.e. the distribution of pigment particles in the uppermost
layer, is restricted to quantitative or-semi-quantitative methods such as comparison of micrographs or to indirect
methods such as roughness and porosity measurements. However, by pair distribution function, ( ) r g analyses,
quantitative information about the surface structure of the coatings, the size of the ordered domains and the degree
of order of the pigments can be provided. The pair distribution function is here used to describe how added water-
soluble polymers affect the surface structure in the dry coatings, i.e. after the completed consolidation process.
The pair distribution function method makes it possible to quantify the concept of surface structure. In this study,
simple model coating colors consisting of spherical polystyrene pigment particles and water-soluble cellulose ethers
(polymers) were chosen. Two different water-soluble polymers were studied: one non-temperature responsive
polymer (carboxymethyl cellulose, CMC) and one temperature responsive polymer (ethyl(hydroxyethyl) cellulose,
EHEC). The pair distribution function method can readily be used for evaluation of more complex model colors,
such as systems also containing dispersions binders (polymer latexes) or for monodisperse spherical mineral
pigments. However, the method is primarily developed as a laboratory method for examination of the effects of
different soluble polymers and binders on the distribution of pigment particles in the dry coating layer.
2003 Spring Advanced Coating Fundamentals Symposium
The use of temperature responsive polymers in paper coatings has been subjected to a number of studies. The effects
observed in the wet coating colors are not always visible in the final dry layers. Especially EHEC has been the
subject of numerous investigations [3,4]. However, the mechanisms behind the flocculation in EHEC-containing
coating colors are still open to debate. The results presented in this study support the so-called Capillary Induced
Phase Separation (CIPS) mechanism [5, 6].
The basic physics behind the CIPS mechanism is the well-known phenomenon of capillary condensation. The
formation of a capillary phase is driven by a lower interfacial free energy of the capillary phase/solid interface as
compared to the solution phase/solid interface. This is opposed by the higher free energy density of the capillary
phase. Moreover, the free energy of the capillary phase reduces as the surface separation is reduced due to a
reduction of the volume of the capillary phase and smaller interfacial area between the capillary and reservoir
phases. As a consequence, an attractive force between the surfaces appears as soon as the free energy balance favors
the formation of a capillary phase.
Knowledge about the mechanism behind temperature responsive flocculation is in general a prerequisite for
industrial application of EHEC in coating colors. The CIPS mechanism is expected to be more pronounced the
closer the suspension is to the cloud point of EHEC. The CIPS mechanism is believed to involve a long-range
attractive force that arises between surfaces when the solution is near the phase separation [7]. The suspensions were
studied at 23
o
C and 55
o
C.
EXPERIMENTAL
Materials
Aqueous suspensions based on polystyrene pigment (PS, DPP 711 from Dow Deutschland Inc., Germany) and
water-soluble cellulose ethers were prepared. Two different cellulose ethers were used: ethyl(hydroxyethyl)
cellulose (EHEC, Bermocoll CL 616 from Akzo Nobel Surface Chemistry, Sweden) with a MW of 70,000 g/mol.
and carboxymethyl cellulose (CMC, FF 10 from Noviant Oy, Finland) with a MW of 66,000 g/mol. The cloud point
for the grade of EHEC used here was about 65
o
C. The water-soluble polymers were purified by centrifugation and
ultra-filtration with 10,000 MWCO filter (Sartorius AG, Germany) and added to the PS suspension prior to the
coating experiments and the viscosity measurements. The PS suspension used contained particles with a radius ( a )
of 0.125 m. The particle size was measured with the AFM image analysis program.
Methods
The effect of the cellulose ethers on the surface structure and on the viscosity of the suspensions were investigated at
three different concentrations of cellulose ether in the range from 0.2 parts (by wt.) per hundred parts of dry pigment
(pph) to 5.0 pph. The solids content of the final suspensions were around 20 % (by wt.). The EHEC- or CMC-
containing PS suspensions were adjusted to pH = 8.0 and stored for approx. 18 h at constant temperature (23
o
C or
55
o
C) prior to further experiments. The temperature of each individual suspension was kept constant throughout the
remaining steps of this study, e.g. the suspension stored at 55
o
C was also drawn down on a polyester substrate at
55
o
C and dried at 55
o
C. The coating films were drawn with a bench coater (K Control Coater K101, RK Print-Coat
Instruments Ltd., U.K.). The thickness of the dry coatings was about 15 m, i.e. multiple layers consisting of
several layers of PS particles were formed.
The structure of the uppermost layer was investigated by means of Atomic Force Microscope (AFM, Explorer 2990,
Topometrix, USA) operating in contact mode [8]. The topographic images of the surfaces were taken and processed
by an image analysis program. The particle center positions in the uppermost layer were acquired in a binary
projection. The pair distribution function analysis was adapted to a flat surface, i.e. a two-dimensional system.
However, the real surface structure is three-dimensional, which required some approximations to be made: Particles
2003 Spring Advanced Coating Fundamentals Symposium
that diverged, with the respect to next neighbor, more than a particle radius from the average local surface were
excluded. I.e., particles located far down were treated as holes. The remaining surface particles were projected in the
average surface plane. The surface structure was then interpreted by calculating the pair distribution function ( ) r g ,
where r is the radius of a ring centered at a particle i [9]:

( )
( )

=
|
.
|

\
|
+
=
N
1 i 2rr
2
r
r
i
n
0
A
N
1
exp
r g [1]

where N is the number of particles,
0
A is the average area per particle (i.e. / 1 where is the average number
density of particles) and ( ) r n
i
is the number of particle centers contained in a ring of radius r and thickness r
centered at particle i . In the pair distribution function [Eq. 1], the distribution of particles around particle i is
normalized with respect to a homogeneous (random) distribution of particles given by the function ( ) r n
gas


( ) ( ) ( )
2 2
gas
r r r r n + = [2]

which equals the number of homogeneously distributed particle centers contained in the ring at a particle density of
. The effect of the normalization is that ( ) r g approaches the limiting value 1 with increasing degree of disorder.
The radial distance r was represented in a discrete form of ( ) ... , 2 , 1 = = m r m r with
max
r = 16 particle diameters.
A theoretical pair distribution function [Eq. 3] can be fitted to the experimentally obtained pair distribution function
[Eq. 1]. This enables additional information about the degree of order and the size of the ordered domains for the
different systems. The theoretical pair distribution function [Eq. 3] is based on the structure of a triangular
(hexagonally packed) order, ( )
triang
r g . The peaks in ( )
triang
r g were broadened by a normal distribution, with a
standard deviation ( ) r [Eq. 4] to account for the statistical fluctuations of the particle positions around the
triangular lattice points. The calculated pair distribution function is

( ) ( )
( ) ( ) ( )
1

r
exp 1 dx
r 2
x
exp
r 2
r
x r g r g
2
2
1/2
triang
+ |
.
|

\
|

(
(

|
|
.
|

\
|
=

[3]

where x is the distance from the position the particle would have in a lattice of perfect triangular order. The
standard deviation ( ) r is given by

( )
|
|
.
|

\
|
|
.
|

\
|
+ =
2/3
0
b
r
1 r [4]

The empirical fit to ( )
exp
r g can be optimized by using the three parameters
0
, and b . This optimization is done
with respect to the positions and amplitudes of the peaks in the experimental ( ) r g curve. The parameter
correlates to the size of the ordered domains.
2003 Spring Advanced Coating Fundamentals Symposium
The viscosity of the suspensions and the corresponding aqueous phases were measured by a rotational rheometer
(MCR 300, Physica Messtechnik GmbH, Germany). The relative viscosity (
r
) was taken as a measure of the
degree of flocculation and was calculated as

o

r
= [5]

where are the viscosity of the suspension and
o
the viscosity of the aqueous phase. All viscosity measurements
were performed at the same temperature as the suspensions had been stored at (23
o
C or 55
o
C). The geometry used
was double gap for the suspensions measured at 23
o
C and for the aqueous phases at both temperatures, and
concentric cylinders for the suspensions measured at the higher temperature.
RESULTS AND DISCUSSION
The distribution of PS particles was strongly affected by the concentration of the water-soluble polymer. This could
be exemplified by AFM images of dry layers of PS-CMC blends at 23
o
C (Figure 1).

Figure 1. AFM images of PS layers containing 0.2 pph CMC (left) and 2.0 pph CMC (right) at 23
o
C.
In order to facilitate comparison between AFM images and to estimate the degree of order and the size of the
ordered domains for the different systems, the pair correlation function ( ) r g was calculated from information about
the particle positions. The particle positions were determined from the topographic AFM images and images
analysis.
The degree of order could be estimated from the experimental ( ) r g curve as the value of the dimensionless length
( 2a r ) until the systematic variation in ( ) r g vanish, i.e. the distance until peaks no longer can be observed in the
( ) r g graphs. The peaks relate to how many particles away the ordering structure of the hexagonal lattice remains.
The width of the peaks also reflects the degree of order and the height of the peaks reflects the short-range degree of
order. It was observed that the added cellulose ethers decreased the degree of order of the dry coating layers. This
was valid for both ethyl(hydroxyethyl) cellulose and carboxymethyl cellulose. This was reflected in the pair
distribution function as a fast decay of the number of peaks with increasing concentration of the cellulose ethers.
This is shown for the CMC-containing suspensions at two temperatures in Figures 2 and 3.
2003 Spring Advanced Coating Fundamentals Symposium

Figure 2. The ( ) r g curves for CMC-containing PS layers at 23
o
C.

Figure 3. The ( ) r g curves for CMC-containing PS layers at 55
o
C.
This order-disorder behavior was approximately independent of the temperature, even if a slightly higher degree of
order was observed for layers containing 0.2 pph CMC when dried at the lower temperature compared to the
corresponding layers dried at 55
o
C. The doublet observed around 2 2a r is evidence for hexagonal close packing
in two dimensions, and the feature at 2 2a r can be taken as an indication of the resemblance to or deviation from
the hexagonal packing.
For the EHEC-containing suspensions, the temperature significantly affected the distribution of particles in the dry
layer (Figure 4-5). At the higher temperature (55
o
C), the structure of the layers prepared from EHEC-containing PS
2003 Spring Advanced Coating Fundamentals Symposium
suspensions was less affected by the concentration of the cellulose ether than at the lower temperature (23
o
C). The
function ( ) r g at the higher temperature showed a low degree of order, also at low concentration of cellulose ether
(0.2 pph EHEC).

Figure 4. The ( ) r g curves for EHEC-containing PS layers at 23
o
C.

Figure 5. The ( ) r g curves for EHEC-containing PS layers at 55
o
C.
The ( ) r g curve for 0.2 pph EHEC at 23
o
C was quite similar to ( ) r g curve for 0.2 pph CMC at 23
o
C, even if a
slightly higher degree of ordering was observed for the CMC-containing system (Figure 6), this is shown by the
more pronounced double peaks at 2 2a r and 3 2a r for the CMC-containing system. However, at 55
o
C a
2003 Spring Advanced Coating Fundamentals Symposium
substantial difference between the two cellulose ethers was observed (Figure 7). The ( ) r g curve for 0.2 pph EHEC
at 55
o
C showed significantly less surface order than the corresponding CMC-containing layer. This corresponds
well to the AFM images of the dry coated layer at 55
o
C (Figure 8).

Figure 6. The ( ) r g curves for PS layers containing 0.2 pph cellulose ether at 23
o
C.

Figure 7. The ( ) r g curves for PS layers containing 0.2 pph cellulose ether at 55
o
C.
2003 Spring Advanced Coating Fundamentals Symposium

Figure 8. AFM images of PS layers containing 0.2 pph CMC (left) and 0.2 pph EHEC (right) at 55
o
C.
Theoretical ( ) r g curves were fitted to the experimental ( ) r g curves. The three parameters (
0
, and b ) were
optimized with respect to the positions and amplitudes of the peaks in the ( ) r g curve.
Since the two parameters
0
and b are dependent on each other and determines the standard deviation, the
parameter that estimates the size of the ordered domains gives most information about the degree of order on the
surface. A low value of corresponds with a smaller size of the ordered domains.
The values of the parameter obtained by the fitting of the theoretically obtained ( ) r g curves to the experimental
( ) r g illustrates that the degree of order and the size of the ordered domains decrease with an increasing
concentration of cellulose ether (Table 1). The value of for the higher concentrations of cellulose ether (2.0 and
5.0 pph) was half of the value of at the low concentration (0.2 pph).

Polymer pph
Temperature
(
o
C)
* /2a
Temperature
(
o
C)
* /2a
CMC 0.2 23 2.9 55 2.5
CMC 2.0 23 1.5 55 1.6
CMC 5.0 23 1.6 55 1.6
EHEC 0.2 23 2.8 55 1.6
EHEC 2.0 23 1.4 55 1.3
EHEC 5.0 23 1.4 55 1.3
*
The correlation length, , was normalized with respect to the particles diameter, 2a.
Table 1. The Correlation length .
The values of also supported the observation that the degree of order decreased at the higher temperature (55
o
C)
for the EHEC containing systems (Table 1).
2003 Spring Advanced Coating Fundamentals Symposium
The fact that the degree of ordering observed at low content (0.2 pph) of EHEC at 23
o
C was slightly less compared
to the corresponding CMC-containing layer can be an effect of differences in adsorptive properties and the
corresponding differences in flocculation behavior between the two water-soluble polymers. It has been reported
elsewhere that EHEC adsorbs on latex surfaces to which CMC does not adsorb [10].
The aqueous phase of the suspensions was separated by centrifugation, and the viscosity was measured (Figure 9).
The viscosity measurements at 23
o
C showed that the viscosity of the aqueous phase of the 0.2 pph EHEC
suspension was almost identical to that of water, even if EHEC was more efficient as a thickener of the aqueous
phase at high concentration than CMC. This indicated that at the low concentration (0.2 pph) almost all EHEC was
adsorbed. The viscosity of the aqueous phase of the CMC-containing system at the low concentration (0.2 pph)
differed slightly from that of water, which indicated that CMC was not absorbed.

Figure 9. Viscosity of the aqueous phase of the PS-suspensions at 23
o
C. Measured viscosity of water at 23
o
C is
added as a reference.
As a reference to the influence of concentration on the aqueous phase viscosity as depicted in Figure 9, viscosity
values of pure solution of the cellulose ethers has been measured (Figure 10). The pure cellulose ether solutions
where adjusted to pH=8 before the rheology of the was measured at 23
o
C. This gives additional information about
the systems and more evidence that EHEC is adsorbed at the polystyrene particles since the viscosity for the EHEC
solution was higher than the viscosity of the CMC solution at the same concentration.
2003 Spring Advanced Coating Fundamentals Symposium

Figure 10. The viscosity-concentration relation for the two cellulose ethers at 23
o
C.
The relative viscosity (
r
) of the polymer-containing suspensions was calculated and taken as a measure of the
degree of flocculation (Figure 11). The relative viscosity of the CMC-containing suspensions indicated that the
suspensions were flocculated at high concentrations of CMC, probably by a depletion mechanism. No flocculation at
all was observed at 0.2 pph CMC. Depletion flocculation needs a certain concentration to be activated, i.e. a
concentration threshold is required for the depletion mechanism to overcome the electrostatic stabilization. For the
systems with a higher amount of CMC, a depletion flocculation mechanism was likely to be operative. Depletion
flocculation is a particle destabilization induced by the addition of a free polymer. A depletion layer is formed next
to the particle surface in the presence of a free non-adsorbing polymer. Upon close approach of the particles,
essentially no soluble polymer will remain between the particles. This creates a reservoir of pure solvent that in turn
will create an osmotic pressure gradient that leads to an attraction between the particles and flocculation will occur.

2003 Spring Advanced Coating Fundamentals Symposium

Figure 11. The relative viscosity for the CMC/EHEC-containing suspensions at 23
o
C.
An important feature of depletion flocculation is that it exist a certain concentration region for flocculation, below
and above this region no depletion flocculation will be observed. At low concentrations of free polymer, the
depletion layer is at its maximum thickness, which should promote attraction, however the osmotic pressure
differences is so small at low polymer concentration that flocculation will not occur. As the polymer concentration is
increased above the overlap concentration, the depletion layer thickness decreases while the osmotic pressure
increases [11, 12, 13]. Thus the degree of flocculation is not expected to increase at very high concentrations of non-
adsorbing soluble polymer (due to reduction of the depleted volume at high concentrations), in good agreement with
Figure 11. The corresponding pair distribution functions (Figures 2-5) are in accordance to the flocculation behavior.
For the EHEC-containing PS suspensions, the flocculation started already at a very low addition level and a further
increase in concentration level did not substantially affect the value of the relative viscosity (Figure 11). Thus a
bridging flocculation mechanism is very likely. Bridging flocculation is expected to occur already at low
concentrations, in good agreement with Figure 11.
Bridging is considered to be a consequence of the adsorption of segments of individual polymer molecules on the
surface of more than one particle. Only a portion of the polymer chain is in direct contact with the solid surface.
Each polymer chain is attached in sequences separated by non-adsorbing segments, which extend away from the
surface into the solution together with tails at each end of the polymer. Since segments and tails extending from one
particle can absorb onto another particle, flocculation of suspensions can be modeled by a bridging mechanism in
which polymer chain binds two or more particles together [14, 15]. Bridging flocculation occurs when the polymer
chain is long enough and the surface coverage by adsorbed polymers is low [16, 17]. The flocculation has often an
optimum at some concentration. Too low polymer concentration makes the flocculation less effective. At very high
2003 Spring Advanced Coating Fundamentals Symposium
concentration of adsorbing polymer only a few free surface sites are available for bridging and the limit of steric
stabilization is reached at very high concentrations [16].
A weak maximum in flocculation may be observed at some low concentration of adsorbing polymer in the case of a
bridging mechanism, which in fact was observed for the EHEC-containing suspensions in Figure 11 at high shear
rates. The corresponding pair distribution functions (Figure 4-5) differ from the expected behavior, since the high
relative viscosity at low levels of EHEC did not resulted in the expected low degree of order. The 0.2 pph EHEC
suspension may be an example of a suspension where the flocculated structure does not resist the capillary forces
that are present during drying.
Measurements of relative viscosity at 55
o
C (Figure 12) revealed a different behavior of the EHEC-containing
suspensions compared to those observed at 23
o
C. At 55
o
C, the relative viscosity was dramatically affected by the
concentration of EHEC, and the relative viscosity increased with increasing concentration of EHEC. On the other
hand, the relative viscosity of the CMC-containing suspensions at 55
o
C closely resembled the behavior observed at
23
o
C.

Figure 12. The relative viscosity for the CMC/EHEC-containing suspensions at 55
o
C.
The differences in relative viscosity of the EHEC-containing suspensions between 23
o
C and 55
o
C can be explained
by the fact that EHEC is a temperature responsive polymer. CMC is not a temperature responsive polymer, and
consequently, the temperature did not substantially affect the behavior of the CMC-containing suspensions. The
influence of EHEC concentration on the relative viscosity at 55
o
C (Figure 9) did not showed the expected behavior
for bridging flocculation, since the relative viscosity started to increase with increasing concentration of EHEC.
2003 Spring Advanced Coating Fundamentals Symposium
However, this behavior can be fully understood if capillary induced forces are assumed. Polymer adsorption is a
prerequisite for bridging flocculation as well as for capillary induced phase separation (CIPS). Flocculation by
capillary induced phase separation has been reported to occur in EHEC-containing suspensions at temperatures close
to the cloud point of EHEC [5, 7]. The cloud point for the grade of EHEC used here was about 65
o
C. The capillary
induced forces act over long distances and the flocculation mechanism involves a considerable mass transport of the
soluble polymer to the region between the particles. Due to the mass transport involved, the degree of flocculation is
expected to increase with increased concentration of the soluble polymer. Another effect would be that the kinetics
of flocculation would be relatively slow, which may influence both the formation and the breaking-up of the particle
aggregates. A capillary induced phase separation mechanism may explain the less ordered structure observed at
55
o
C for the layers containing 0.2 pph EHEC (Figures 3-4). The pair distribution function at 0.2 pph EHEC
resembled those at 2 and 5 pph, if the suspensions were held at 55
o
C (Figure 5). Besides capillary induced phase
separation, adsorption of soluble polymers may also lead to bridging flocculation. Thus it is likely that the observed
effects for the EHEC-containing suspensions at 55
o
C was a combination of bridging flocculation and capillary
induced phase separation (CIPS). The temperature responsiveness of EHEC and differences between EHEC and
CMC are illustrated in Figure 13.

Figure 13. The relative viscosity versus the amount of water-soluble polymer added, at a shear rate of 100 s
-1
.
CONCLUSIONS
A novel method for analyzing the particle ordering in the surface layer of the coatings has been developed. This
method is based on pair distribution function analysis. This method was used in order to establish the relation
between flocculation and consolidation for two model colors containing two different water-soluble cellulose ethers.
2003 Spring Advanced Coating Fundamentals Symposium
AFM supported by pair distribution analysis is a powerful tool in the description of surface structures and order-
disorder phenomena that occur during consolidation of coating layers. The degree of order in coatings drawn down
at 23
o
C decreased at increasing concentration of cellulose ether. This was valid both for the CMC and EHEC
containing systems. For the EHEC-PS systems, coating at elevated temperature increased the degree of disorder of
PS particles at low concentrations of EHEC. For the CMC-PS systems, the temperature did not substantially affect
the distribution of PS particles in the dried layers.
The relative viscosity of the systems indicated that different flocculation mechanisms occurred for the EHEC- and
the CMC-containing PS suspensions. In the CMC-containing PS systems the flocculation was induced by depletion
flocculation and in the EHEC-containing systems the flocculation seemed to be induced by bridging mechanism and
by capillary induced phase separation. (CIPS).
ACKNOWLEDGEMENTS
The financial support from the Swedish Pulp and Paper Research Foundation, the Knowledge Foundation and the
Swedish Agency for Innovation Systems (VINNOVA) is gratefully acknowledged.
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