Surfactants for Use as Codispersants in Architectural Coatings

Bruce Fillipo, Ashland Specialty Ingredients, United States

Dick Henderson, Ashland Specialty Ingredients, United States
Xiaochun Zhang, Ashland Specialty Ingredients, United States
Courtney Usher, Ashland Specialty Ingredients, United States
Kim Gaughan, Ashland Specialty Ingredients, United States
Andrew Defusco, Ashland Specialty Ingredients, United States
Sowmitri Tarimala, Ashland Specialty Ingredients, United States


Abstract

The preparation of pigment grinds for Architectural Coatings utilizes high shear dispersion
techniques in combination with low molecular weight polymeric dispersants. The selection of a
grind dispersant is critical to achieving optimum particle size and dispersion properties including
viscosity, stability and handling as well as the final coating hiding and color characteristics.

Surfactants can be used as active co-dispersants alone or in combination with low molecular
weight dispersants to improve grinding efficiency and properties. Advantages of using low-VOC*
(Volatile Organic Compounds), non-APE (Alkylphenol Ethoxylate) surfactants in conjunction in
pigment dispersants is investigated to identify surfactant functionality and dispersant
combinations for improving efficiency and coating properties. Analytical techniques including
rheology, microscopy and surface chemistry are investigated to evaluate and document
performance and mechanisms.

Introduction

Titanium dioxide (TiO2) is the most important white pigment and is widely used in industries
including paint, colorant, papermaking, plastics, cosmetics and pharmaceuticals. Annual
worldwide TiO2 pigment production capacity is 6.55 million tons with approximately 57%
consumed in paints and coatings.
1


Titanium dioxide is used in almost every paint or coating formulation for brightness, UV
adsorption properties, resistance to discoloration and high refractive index, providing opacity /
hiding in paints. Levels used in coating formulations vary significantly dependent on the type and
total pigment loading (PVC or pigment volume concentration), but typically range from 0.05 to 0.3
kg/liter (0.5 to 2.5 lb/gal).

The purpose of this study is to evaluate surfactants as active co-dispersants alone or in
combination with low molecular weight dispersants to improve pigment dispersion properties.

Background

Titanium dioxide and pigment
dispersions are produced for the
manufacture of paint. Pigment
concentration, level of dispersion as well
as the quality and stability of the
dispersion are critical for determining
final coating properties. Pigments are
typically dispersed by shearing (e.g.
high shear mixing or milling) in a grind
Figure 1: Paint manufacturing overview
* low-VOC: < 0.5%: Enhanced ASTM Method 6886 (GC Method)
tank. To facilitate dispersion, surfactants and dispersants are used to wet-out solid pigments and
displace air, moisture and separate tightly packed agglomerated particles. Breaking-up the solid
to primary particles is required to obtain optimum optical properties including opacity.

Stability of the pigment dispersion through use of dispersants and surfactants is essential to
prevent flocculation and therefore changes in opacity, color, tint strength, gloss, viscosity and
separation / sedimentation.

Dispersed in a liquid, pigment particles are not stationary but undergo constant thermal
movement or Brownian motion. Velocity or kinetic energy of a particle in motion can be expressed
by:
M - v
2
= k - T
where M = mass, v = velocity, T = Temperature and k = constant.

As the mass of a particle increases, speed decreases at a specific temperature. As the particles
move, they undergo constant random collisions with other particles. If pigment particles are not
stabilized and there is no barrier to prevent contact, each particle to particle collision can result in
bonding and rapid flocculation will occur:
T
1/2
= 3 - q
4- k- T- N


where T
1/2
= time 50% particle count reduction, q= viscosity and N= particle number (cm
3
).

Therefore, viscosity (q) is a key parameter to increase or reduce flocculation. However, due to
limitations on maximum viscosity in liquid coatings systems, it is not viable to sufficiently stabilize.

Primarily three forces are involved as particles approach each other, electromagnetic (e.g.
attractive London-Van der Waals), electrostatic (e.g. columbic, normally repulsive) and steric
hindrance forces (adsorbed layers).

Electromagnetic forces are attractive (V
a
) and develop from particle interactions and must be
overcome to prevent pigment flocculation. London-Van der Waals forces arise due to the
influence of particle dipoles. Attractive forces increase as particles approach each other.

As noted, electrostatic repulsion and steric hindrance are primary mechanisms stabilizing pigment
dispersions and blocking flocculation. Electrostatic forces
result from development of ions at the particle surface due
to dissolution, an ionogenic source or addition of ionic
dispersant or surfactant. Pigments used in coating
systems normally have an anionic (-) charge. Anionic
pigment particles, attract a second layer of less densely
populated solution counter ions (cations, +). This system
is referred to as an electrical double layer, inhibiting
flocculation and maintaining the dispersion stability as the
charged particles repel one another. The charge for the electrostatic double layer is highest at the
particle surface and drops off rapidly in the surrounding solvent.

V
r
/ (k - T) = C - 0 - d -
2
- ln(1+ exp - s / o)
Where V
r
= Repulsion potential, C= constant, 0= dielectric constant, d= particle
diameter, , = Zeta Potential, s = distance between particle surfaces, o = Double Layer
thickness

As can be seen, particle zeta potential increases, the resistance potential increases
exponentially. Large values for o (double layer) and 0 (solvent dielectric constant; Air= 1, Mineral
Oil ~ 2, Water =80) are also desirable for electrostatic repulsion (V
r
) and dispersion stability.

Figure 2: Electrostatic Particle
Repulsion
Graphing the combined sum of electromagnetic attractive and
electrostatic dispersion stabilizing (repulsive) forces (V
total
)
between particles as they approach each other (Figure 3) shows
increasing resistance between particles to a point. Past this
maximum, the repulsion decreases rapidly and attraction
becomes the predominant force resulting in bonding and
flocculation.

Additionally, inorganic oxide surfaces have a surface charge
dependent on the pH of the system. Each pigment has an
isoelectric point (pH) where surface charge is zero. As the pH is adjusted away from the
isoelectric pH, the charge becomes imbalanced, increasing charge resulting in increased particle
repulsion. The adsorption of an ionic surfactant or dispersant to inorganic oxide alters the particle
surface and its isoelectric pH. Selection of the optimum surfactant should increase and enhance
charge and improve dispersion stability.

Steric hindrance is the second primary mechanism for stabilizing
pigment dispersions. Nonionic and ionic surfactants and
dispersants adsorbing onto the pigment particle surface can provide
steric hindrance and mechanically create a barrier hindering close
approach of pigment particles. Additionally, when functional groups
extending into the solvent come into contact with one another,
osmotic pressure increases also forcing particles apart.

Titanium dioxide particles are often coated with silica or alumina, to improve hydration and
dispersion properties and prevent potential formation of radicals due to a photocatalytic reaction.



Surface active agents and polymer dispersants reduce settling in pigment dispersants due to
electrostatic and steric stabilization. As a result, flocculation is reduced. Stokes Law describes
the rate spherical particles fall through liquids, assuming laminar flow:
3

v
s
= (1/18) - |((
p

s
) - G * d
2
)/ q|

v
s
= settling velocity, = density of particle and solvent, G= acceleration due to gravity, d =
particle diameter, q = viscosity

As can be seen, if flocculation occurs and effective particle size increases, settling rates can
increase exponentially.

Surfactants and dispersing agents are used primarily to reduce surface tension and wet surfaces
to improve the speed at which the liquid replaces the air on the pigment surface and to envelope
particles with a barrier to disperse and stabilize by ionic and steric mechanisms. The generation
of this envelope prevents random particle contact, adhesion and flocculation.

Surfactants constitute a very important group of molecules, and are present in all types of
formulations. The structure consists of a water loving hydrophilic section which can be nonionic
Figure 3: Electromagnetic and
electrostatic forces between particles
Figure 4: Steric Hindrance
Figure 5: TiO2 Surface
Treated
(ethoxylates), anionic (phosphate esters and sulfonates), cationic (quaternary amines) or
amphoterics (betaines) with an oil loving or hydrophobic group (e.g.
alcohols and fatty acids) in the same molecule. The type and
balance between the two groups is decisive for properties including
wetting and dispersing. Surfactants by nature are surface active, moving to interfaces where the
hydrophobic section orients itself away from the water and hydrophilic section protrudes into the
water phase thus disrupting hydrogen bonding at the water interface, reducing surface tension.

Experimental

Titanium dioxide dispersions were prepared with the formulation
summarized below using a commercial surface treated (2.5
%Alumina + 3%Silica) rutile TiO2 (93% minimum) with a mean
particle size of 0.3 0.4 . The initial dispersion was prepared with
a high shear Dispermat equipped with a cowles bladeThe
consistency of the initial dispersion (no dispersant or surfactant)
was a soft paste.

Water DI 33.1%
Titanium Dioxide 66.6%
Foam Control Additive 0.3%

Titanium dioxide dispersant demand curves were generated using 350g
aliquots of the prepared TiO2 paste. 15% active solutions of dispersant
and/or surfactant (wt/wt) were fed to the paste over 30 45 mins using a
syringe pump. The dispersion was mixed at 500rpm using a HAAKE
Viscotester 550 with a 2 inch (5cm) marine prop blade as the surfactant /
dispersant solutions were fed. Motor torque was measured by the
HAAKE Viscotester 550, a Searle type viscometer. For this testing we
fitted the HAAKE with an agitator blade in-place of a spindle to measure
relative motor torque. Rotational speed was set to 500rpm. The
measured dispersion flow resistance (torque) to maintain the constant
mixing speed is proportional to the viscosity. Solution feed and torque
measurement was initiated as soon as readings stabilized. pH of the
final dispersions remained between 7.5 8.2.

Additives evaluated included a low
molecular weight polyacrylate (MW
~5000) and a diisobutylene maleic
anhydride copolymer with a cross-
section of nonionic surfactants
including tridecyl alcohol ethoxylates
and anionic phosphate and sulfate
surfactants. Materials included in this
paper are summarized in Table 1.

Characterization of dispersion and
films included:
1. Rheology: Stress Strain G was measured using ARG2 rheometer, TA Instruments
2. Surface Tension: TiO
2
dispersions were diluted by 50% (~33% solids) and the surface
tension measured using pendent drop method.
3. Surfactant Adsorption: Spectroscopic Ellipsometry (Horiba Smart SE) was used to
measure the thickness of the adsorbed thin surfactant films. Flat Al2O3 and SiO2 (glass)
crystal substrates were used as models for the Al2O3 and SiO2 coated TiO2 surface.
These substrates were immersed in 3% surfactant solutions for 48hrs and rinsed with DI
water and dried with N2
Figure 6: HAAKE 550

Table 1: Surfactants and Polymers evaluated
4. Cryogenic Scanning Electron Microscopy: A sample was flash frozen in liquid ethane.
The frozen sample under vacuum at -180C was fractured and coated with Au-Pd. SEM
was held at -190C and sample surface examined in SEI (Secondary Electron Imaging)
mode.
5. Atomic Force Microscopy (AFM): Images acquired in AC (tapping) mode using an
Asylum Research MFP-3D SA atomic force microscope. Rectangular silicon cantilevers
were used (Budget Sensors Tap300Al-G, typical spring constant 40 N/m). Images were
obtained at 0.5Hz scan rate, 512x512 (line) resolution.

Results and Discussion

Polymer and Surfactant Demand Curves
Dispersion Demand Curves were generated for Titanium dioxide dispersions using the HAAKE
Viscotester 550 as specified in the Experimental section. Two polymers were included, a low
molecular weight polyacrylate and a diisobutylene maleic anhydride copolymer, with a cross-
section of nonionic surfactants including tridecyl alcohol ethoxylates and anionic phosphate
surfactants. Additives were fed 1.4 g (0.4%) to the paste over 45 mins. A sampling of results of
additives on torque / viscosity is summarized in Figure 7.

Mixer Torque is shown on the Y axis versus the grams of active dispersant added. Feeding was
initiated with a stable reading of ~12500. Torque platue for the polymers occurred at ~3000.
Torque read-out for water using the same marine prop blades is 870. Results showed both of the
low molecular weight dispersants evaluated were the more efficient than the evaluated
surfactants in reducing motor torque and therefore viscosity. Torque plateau was reaching at <
0.1% actives. None of the nonionic surfactants (low to high HLB) had a significant impact on
dispersion viscosity, all of the torque results were in a narrow range. However, the anionic
surfactants evaluated had significant impact on rheology.

Phosphate esters F5, T1 and O1 were effective in reducing dispersion viscosity. F5 achieved
similar torque to the polymeric
dispersants at ~0.2% and T1 and
O1 at ~0.4%. All three of these
phosphate esters are ethoxylated
and hydrophilic.

Hydrophobic Phosphate Esters
K, Coester and Z impact on
rheology was highly dependent
on concentration. At a low
concentration K had a significant
reduction on motor torque but
after addition of < 500ppm torque
increased steadily contrasting
with Phosphate Ester Z which
exhibited an initial increase in
torque but after addition of ~
0.1% exhibited a rapid decrease.
As can be seen the impact on viscosity / torque of the phosphate ester surfactants were not
consistent varied depending on functionality. Generally, the evaluated hydrophilic phosphate
ester surfactants predictably reduced dispersion viscosity. The more hydrophobic anionic
surfactants required generation of a demand curve to understand impact on system viscosity.

Figure 7: TiO2 Dispersant Demand Curves 350g 2:1 in Water
Based on results for individual
additives, demand curves were
generated incorporating 450ppm low
molecular weight polyacrylate. The
concentration of 450ppm is short of
the viscosity plateau measured for
individual additives and chosen to
assess impact of surfactant additives
in a polymer starved system. The
same cross-section of surfactants
was evaluated; however, additives
0.7g (0.2%) were fed to the paste
over 30 mins. An overview of
demand curves / torque results with
different additives is summarized in
Figure 8. Results are consistent with
the earlier addition of individual
constituents. The low molecular
weight dispersants evaluated were
more efficient than the evaluated
surfactants in reducing torque.
Again, none of the nonionic surfactants (low to high HLB) had a significant impact on dispersion
viscosity where all torque results were in a narrow range and close to the starting torque (~6000).
The impact on system rheology from the anionic surfactants were similar and variable to the
evaluation of individual additives where the more hydrophilic phosphate esters were effective in
reducing dispersion viscosity and the hydrophobic phosphate ester impact was dependent on
functionality and
concentration.

Increasing the level of low
molecular weight polymer (in
this case, diisobutylene maleic
anhydride copolymer) above
the plateau concentration, to
1200ppm, was evaluated. As
expected, the starting torque
readings were at the minimum
~3000 before starting the
addition of surfactant and most
of the surfactants had no
significant impact on motor torque (Figure 9). The surfactant additives were fed up to 0.7g (0.2%)
to the TiO2 dispersion over 30 mins. All of the
hydrophilic phosphate esters maintained a flat
line torque reading as well as the hydrophilic
nonionic (HLB=16). Again, the more
hydrophobic anionic and nonionic surfactants
impact on rheology was dependent on
functionality and surfactant concentration
elevating torque readings up to 5000.

Viscosity Stress / Strain Curves
All of the TiO2 samples are highly non-
Newtonian and shear thinning. Dispersion
Torque data was validated by testing samples
for dynamic mechanical analysis. Stress /
Strain (G) Storage Modulus (e.g. Elastic
Figure 10: Stress Strain G Storage Modulus Elastic
response / solid-like behavior
Figure 8: TiO2 Co-Dispersant Demand Curves350g, 2:1 in Water
LMW Polyacrylate @ 450ppm (active) + Surfactants
Figure 9: TiO2 Co-Dispersant Demand Curves 350g, 2:1 in Water
1200 ppm active Polymer Dispersant + Surfactants
response / solid-like behavior) is reported for several evaluated samples. The more hydrophilic
anionic phosphate esters F5, T1 an O1 had lower G values with F5 exhibiting lowest viscosity
and yield point. The nonionic surfactant profiles were similar to the control containing no
surfactant.

Dispersion Stability
As expected, due to differences in surfactant charge, molecular weight and viscosity, significant
variation was observed in TiO2 dispersion stability. Samples were stored for approximately 3
weeks at ambient and examined for separation, consistency (fluid or gelled), hard packed deposit
and ease of redispersibility. There was a correlation between the Viscosity Stress / Strain Curves
and sample separation. Samples with low G (e.g. < 1000 Pa) and low yield point exhibited water
separation (2% - 40%) after three weeks of ambient storage. Samples prepared only with
dispersant showed formation of a water layer >30% by volume and hard-packed sludge whereas
surfactant stabilitzed dispersions exhibited varying degree of separation and redispersibility,
Hydrophilic anionics also showed separation but generally easily reconstituted.


Combinations of polymeric dispersants and
surfactants exhibited the best overall storage
characteristics. As can be seen, the
hydrophobic anionics in combination with the
polymeric dispersants showed the lowest
level of separation and best recoverability.

Surface Tension
The surface tension of the titantium dioxide dispersions and surfactant solutions (0.1 and 0.4% in
water) was measured to assess relative level of free surfactant. Free surfactant reduces surface
tension aiding in wetting, facilitating
incorporation of pigments and
extenders. Generally, the surface
tension of the surfactant solutions and
TiO2 dispersion + surfactant showed
similar trends with only small
differences. This trend is true for the
nonionic surfactants (low to high HLB)
and the hydrophilic phosphate esters.
However, a notable exception is the
more hydrophobic Phosphate Coester
based dispersion where dispersion
surface tension was approximately 10
dynes higher. Little change between
solution and dispersion surface
tensions indicates systems are above
the critical micelle concentration and most of the more hydrophilic surfactants are more mobile in
the dispersion. The Phosphate Coester may be more tightly bound to the TiO2 surface due to its
Table 2: Dispersion Stability
Table 3a: Dispersion surface tension (33% solids)
hydrophobic functionality. As
concentration increases, the more
hydrophobic characteristic can depress
the hydration layer result in increased
dispersion system torque and viscosities.

Adsorbed Layer
Persistency and thickness of surfactant
films was evaluated by ellipsometry. As
noted, the TiO2 is surface treated,
therefore flat SiO2 and Al2O3 crystals
were used as model surfaces of the
surface treated titanium dioxide and
evaluate adsorption. Crystals were
exposed to 3% surfactant solutions for
48hrs and rinsed with DI water; dried.
Generally, adsorbed layers were more
significant on the aluminum oxide versus
silica, where all of the surfactants
evaluated developed a measurable film on the aluminum oxide but the higher HLB nonionics and
Phosphate Ester Z showed no film persistency on silica. The Low HLB Nonionic and Phosphate
ester O1 developed the thickest films on aluminum oxide and silica crystals respectively.

Cryogenic Scanning Electron Microscopy
In most cases, SEM particle size measured 30 - 1000nm but some variation noted between
different surfactant systems. Typical examples are shown below at 20000x magnification. The
most unusual was regions within the diisobutylene maleic anhydride copolymer. Phosphate Ester
F5 contains abundant, fine, spherical to rounded particles ranging from approximately 30.0
800.0 nanometers in diameter. Some agglomerates are visible in other anionic and noionic
surfactants indicating some flocculation.



Atomic Force Microscopy (AFM)
Draw down of Titanium dioxide dispersion were dried at +25C onto a glass slide in air before
imaging. Variation in structure of dried films was observed with the different surfactant and
polymer systems. Examples are illustrated in Figure 3. The most ordered film structures were
observed with the Phosphate Ester 5, the Low HLB nonionic and the copolymer. There appears
to be some flocculation in the Phosphate Ester O1, Z and Coester.

Table 3b: Surfactant surface tension (0.4% and 0.1% in water)
Table 4: Surfactant Films by Ellipsometry
Figure 11: Ti02 dispersion films cryogenic SEM
Low PVC Coatings Screen.
TiO2 Dispersions were formulated into a low PVC coating to evaluate the surfactant impact on
TiO2 dispersion on coating properties such as opacity and hiding. An example of a draw-down is
attached (Figure) showing increased opacity when using
the Hydrophilic Phosphate Ester F5 versus the copolymer
dispersant. AFM images of the coating show TiO2
agglomeration when using only the dispersing copolymer
elucidating the difference in opacity.


Conclusions

Impact on dispersion rheology with anionic phosphate ester surfactants varied depending on
functionality, hydrophobicity and surfactant concentration. Evaluation of surfactant demand
curves is critical to understand impact and optimize dispersion properties. Generally, the
hydrophilic phosphate ester surfactants predictably reduced dispersion viscosity whereas the
Phosphate Ester Diisobutylene maleic
F5 anhydride copolymer

Figure 12: Ti02 dispersion films AFM
Figure 13: 15 PVC VAE coating Ti02. Opacity is 1.5% higher with Phosphate Ester F5 versus the
copolymer dispersant. AFM shows more agglomeration with the copolymer dispersant in the dry coating
more hydrophobic anionic surfactants required analysis of demand curves to understand impact
on system viscosity. Nonionics generally did not have a significant impact on dispersion viscosity.

Dispersant Polymers were most efficient in reducing viscosity of pigment dispersions but also
exhibited significant separation and potential for hard pack deposits while low viscosities were still
obtained with some anionic surfactants and lower levels of separation observed. The use of
anionic surfactants in particular more hydrophobic PEs with polymeric dispersants gave the best
dispersion properties.
Incorporation of dispersants and surfactants into the pigment grind can have an impact on final
coating opacity and hiding where surfactants can improve results.

Several analytical characterization tools were found to be useful in understanding dispersion
properties including Atomic Force Microscopy, Surface Tension Analysis, Ellipsometry and
Rheology.

Acknowledgements

Margaret Oplinger: Ashland Specialty Ingredients Coatings Research and Development
Sharon Wilson: Ashland Specialty Ingredients Coatings Research and Development
Scott Bradley: Specialty Ingredients Analytical Microscopy
Michael Mroz: Ashland Specialty Ingredients Coatings Technical Service
Eric Dickson-Peppler: Ashland Specialty Ingredients Coatings Research and Development

References:

1. U.S. Geological Survey, Mineral Commodity Summaries, January 2012
2. Plaint Flow and Pigment Dispersion, Temple C. Patton, 1979
3. Stokes Law - Trinity College 2001