FORMULATION OF WATER-BASED PRODUCTS

The purpose is to serve as a review of the topic of water-based products. Although these
products share many characteristics with solvent formulations, some are different.
One of the fundamental differences is in the film formation process, which in the case of
water goes through a coalescence process, which is influenced by many components of
the formulation, such as coalescents, surfactants, plasticizers, neutralizing agents, as
well as binder variables, such as emulsion particle size, Tg, stabilization, etc.
In the following sections in which we will review the components of the formulation,
we will place special emphasis on the interactions that may exist between two or more
components.
POLYMERS

Polymers used in water-based formulations.- There are two large classes of

polymers:
1) Dispersions of polymers insoluble in water, which remain insoluble over a wide
pH range.
2) Truly soluble polymers in a wide pH range.

There are also a large number of hybrid types that fall between the two.
Aqueous polymer dispersions - They are generally prepared by aqueous emulsion
polymerization, which is why they are sometimes described as emulsion or latex
polymers. They are mainly based on water-insoluble comonomers such as: methyl
methacrylate, butyl acrylate, styrene, vinyl chloride and butadiene; so they have a low
degree of solubility. Often water-soluble comonomers such as acrylic or methacrylic
acid, N-methylol acrylamide are present in low concentration (<5%) for reasons of
providing adhesion, colloidal stability or cross-linking. If the levels of the latter are
higher, the resulting polymer may have some water solubility, at least in part of the pH
range, and the product is more of the hybrid type discussed later. These dispersions
occur in a wide particle size range between 0.02 and 100  , with most commercial sizes
between 0.05 – 1  .
Emulsion polymerization produces the lower particle sizes (about 0.5  ) and
suspension polymerization (also called bead) produces sizes at the upper end of the
range. Both are based on the fact that the initiator of free radical polymerization is
soluble in both water and the monomer. Because of the low solubility of the resulting
polymer they are true dispersions over a wide pH range. The stabilization of the
resulting particles is obtained by the addition of anionic, non-ionic or less frequently
cationic surfactants that give their name to the dispersions (emulsions). Carboxylated
comonomers such as acrylic acid also lead to stabilization by anionic charge at pH
values higher than the pK a of the acid in question when the carboxyl group is ionized.
This is the purpose why a neutralizing base is frequently added to the aqueous
formulation, to raise the pH of the ionized carboxylated latex making the latex more
stable. Knowledge of this type is useful to the formulator, as the addition of a cationic
(positively charged) additive to an anionic latex can be destabilizing, as can mixing
cationic and anionic polymers or pigment dispersions. The most robust dispersions are

1
those that are non-ionically stabilized such as sterically stabilized ones, which are no
longer destabilized by the presence of cations or anions.
While the use of emulsion or suspension polymerization is restricted to radically
polymerizable monomers such as (meth)acrylate, styrene, vinyl or vinylidene chloride,
vinyl acetate, butadiene and acrylonitrile, another development is that of aqueous
dispersions. condensation, with polymers such as polyurethanes and epoxies. Although
it is possible to emulsify a conventional polymer of this type in water using a
combination of surfactants and strong agitation, it is almost impossible to obtain a
particle size less than 1  with this technique; and such a coarse emulsion is not capable
of giving a high quality finish. Instead, the generally adopted technique is to modify the
polymer to be subsequently dispersed in water, by incorporating carboxylic, sulfonic
groups or polyethylene oxide groups. The resulting polymer can be dispersed in water
with (or sometimes without) surfactants, giving particle sizes less than 1  . It is also
important in this case to distinguish dispersions that remain as dispersions over a wide
pH range and the more modified ones that are soluble or nearly so at least in part of the
pH, the latter class being defined as reducible to water and also, but inappropriately. as
“colloidal dispersions” .
Aqueous dispersions of condensation polymers frequently need to be cross-linked in the
final formulation phase, since often the Mw chosen for the preparation of the emulsion
is low in order to have a low viscosity system capable of easily dispersing in water. An
exception is polyurethane dispersions in water since they consist of high Mw polymers,
because it is possible to extend the chain of the polyurethane prepolymer during the
dispersion stage in water. Although cross-linking provides benefits, such as improving
solvent resistance.
An important characteristic of aqueous dispersions is that their viscosity in water is
completely independent of Mw. This characteristic, combined with the property of
emulsion polymerization to obtain high Mw quickly, is one of the main reasons why
emulsions (latex) are of great importance in the coatings industry. The viscosity of a
dispersion increases markedly above a volume fraction of about 0.5, so it is difficult to
increase above 0.6, this is more easily achieved with a wide distribution of particle
sizes.
On the contrary, the viscosity of the solution of a polymer, whether in solvent or water,
is a function of Mw. Thus, high concentrations of a polymer can only be obtained with
low Mw polymers.
Water-soluble polymers.- Polymers that have water solubility in a wide pH range are
rarely used as binders in water-based varnishes, due to the obvious problems of water
sensitivity. The only exception is temporary coatings, where water solubility is
advantageous. Even cross-linking rarely succeeds in totally eliminating such water
sensitivity. Instead these water-soluble polymers are frequently used as additives,
mainly thickeners, colloidal stabilizers and pigment dispersants.
The main examples are homo- or copolymers of ethylene oxide, acrylic and methacrylic
acids, N-vinyl pyrrolidone, acrylamide and various sulfonic acid-containing monomers.
Other examples are polyvinyl alcohol and various cellulosic polymers such as
polyhydroxyethyl cellulose and hydroxypropyl cellulose. When the copolymer also
contains insoluble (hydrophobic) units and is still soluble in water (generally as a
micellar system) the polymers can act as colloidal stabilizers and pigment dispersants,
since the molecule possesses the characteristics required for steric stabilization. An

2
example is polyvinyl alcohol, which is used as a colloidal stabilizer in suspension
polymerization.
Hybrid Polymer Systems.- The two most used types are:
to)Hybrids in which the polymer is intermediate in solubility between aqueous
polymer dispersion (the polymer is insoluble in water over a wide pH range) and
aqueous polymer solution (the polymer is soluble over a wide pH range).
b) Hybrids that are a combination of two different types of polymeric binder, such as
epoxy-acrylate, urethane-acrylate.

In the first case (intermediate solubility), some confusion is created and terms such as
water reducible, soluble alkali, soluble acids, hydrosols and colloidal
emulsions/dispersions are used.
It must also be remembered that certain functional groups can transform a polymer that
is insoluble in water, dispersible in water if they are present in low proportions, and
soluble in water in higher proportions. Examples are: anions, carboxylate, sulfonic and
sulfate. The protonated tertiary amino groups are cationic and PE oxide chains are non-
ionic.
However, if the concentration of such ionizable groups decreases in a polymer, then the
polymer is soluble only in the part of the pH at which the groups are ionized, e.g. above
4.2 for groups containing acrylic acid.
Anodic electrocoat systems are based on polymers that contain carboxylic groups in
such a concentration that they make the polymer soluble in water (or dispersible) at pH
higher than the effective pk a of the acid group, and it is insoluble at pH lower than said
level. At the anode, H + is generated, which causes the protonation of the carboxyl
anions and therefore their insolubilization and the deposition of the polymer on the
anodic substrate.
Similarly, in cathodic electrocoat systems, the deposition of the polymer on the cathode
occurs by precipitation of an amine due to the presence of OH - .
An important class of intermediate water-soluble polymers are alkali-soluble
carboxylated polymers, which are initially prepared at low pH as aqueous dispersions.
When the pH increases and the carboxyl groups are ionized, the polymer chains increase
their solubility and the viscosity increases significantly. The polymer is at an
intermediate stage in character (and viscosity) between dispersion and solubility. These
systems are called hydrosols and incorrectly emulsions or colloidal dispersions. An
important application of these products is reversible alkali printing inks and alkali
stripping floor polishes. Additionally, they can be cross-linked by divalent cations such
as Zn and Ca.
A final class of these polymers with intermediate water solubility is what is commonly
known as water-reducible and sometimes water-soluble. They are generally
carboxylated polymers (polyesters, acrylics and alkyds) that are obtained and presented
as solutions in water-miscible solvents, and which can be further diluted with water.
The diluted system is not a true solution, and the dilution gives rise to an unusual
rheological effect, in which the viscosity passes through a maximum. This type of
polymers are used in the coatings industry, such as OH-modified acrylics that can be
cross-linked with Melamine Formol to obtain bakeable coatings for the metal industry.

3
In the second case, hybrids that are a combination of two different types of polymer and
in which one copolymer is radical type and the other is condensation type. The best
known examples are epoxy-acrylate and urethane-acrylate. This type of products allows
combining properties of both groups, thus epoxy-acrylates are used for contact with
food, since they bring together the set of properties required for contact with food, while
urethane-acrylates combine the advantages of urethanes. (such as resistance to abrasion
and solvents) but at an intermediate cost between a polyurethane and an acrylic.
OTHER COMPONENTS
Considerations in the formulation of Water-Based Coatings.- Water-based
formulations are a complex mixture of colloidal dispersions and pigments in water.
They may also contain water-soluble polymers. Typical components are:

Polymeric Binder
Rheological Modifier Surfactants (Surfactants)
Defoaming/Antifoam Pigment
Inorganic Filler Biocide/Fungicide
Pigment dispersant Cross-linking agent
Crosslinking Catalyst
Co-solvent neutralizing agent
Surface tension depressor

The above table is not exhaustive, there may be other additives, such as UV absorbers,
flooding or floating additives, anti-skin or anti-gassing agents, etc. Although the
adjustment of the formulation is empirical, due to the number of possible interactions,
we can give some general rules that allow us to simplify the formulation work. These
rules will depend on the field of use of the coating and some characteristics of the
polymeric binder, such as size of the particle, type and concentration of the stabilizing
surfactant, pH, Tg, Mw, degree of functionalization (for cross-linking, etc.).
Water-based formulations have specific difficulties. Frequently the purpose of some
additive is to compensate or reduce some difficulty. It is instructive to consider some of
these difficulties and consider the role of the additive.
The film formation process for the aqueous dispersion of a polymer is more difficult to
control than in the case of polymers in solution in solvent and the co-solvent plays a
fundamental role in this process. Incomplete formation of the film (coalescence) can
give rise to problems of sensitivity to water, matting, cracking, and in cases of coating
on ferrous materials, give rise to the phenomenon known as “early rusting”.
Another fundamental problem with aqueous polymer dispersions is that their rheology
is less favorable for application than is the case with more Newtonian polymer solvent
solutions. Thus the viscosity of a colloidal dispersion falls very quickly as the shear
gradient increases, and consequently the viscosity at low shear is very high for good
flow and leveling, while at high shear it is very low to give good pick-up of the brush. .
The addition of a water-soluble polymer (thickener) is sometimes vital to increase the
high shear viscosity to a level acceptable for the paint application, but at the same time
it often raises the low shear viscosity, with a detrimental effect on the leveling. The use
of associative thickeners has represented an important advance since these
hydrophobically modified water-soluble polymers allow viscosity to be independently
adjusted at high and low shear. This control essentially results from the fact that the
addition of a cosolvent or a low Mw surfactant to a system containing a dispersion

4
polymer and a hydrophobically modified water-soluble polymer can reduce viscosity by
reducing the magnitude of the bond between the hydrophobic moiety. of the thickener
and/or between the hydrophobes and the surface of the latex particle. This viscosity
reduction is much more pronounced at low than at high shear gradients.
Another characteristic of aqueous dispersions is that it is difficult to obtain a good
dispersion of the pigment unlike solvent-based products. One of the reasons is the
presence of ionic impurities that can cause the pigment to flocculate, even though the
pigment is not flocculated in the wet paint it can occur during drying due to the increase
in the concentration of the dispersed particles and flocculating species. Flocculation can
also be produced by water-soluble polymers such as cellulosic types. An advantage of
associative thickeners is that their tendency to flocculate is lower. The pigment
dispersant thus plays an essential role in protecting the pigment from flocculation and
its selection and concentration is crucial. . The dispersant or set of dispersants must play
two main roles. The dispersant should assist in reducing the particle size of the pigment
aggregate and also stabilize the pigment particles formed. Anionic polyelectrolytes,
such as those derived from acrylic acid, are capable of providing both functions since
they combine high surface activity and can act as steric stabilizers. Currently, we are
looking for dispersants that have little sensitivity to water. The optimal dispersant also
depends on the type of polymeric binder since the dispersant-polymer thermodynamic
compatibility affects the final dry coating. Dispersant type selection can be made using
viscosity titration techniques.
The need to use surfactants to stabilize the latex particles and dispersants to disperse and
stabilize the pigments in aqueous formulations causes difficulties since these additives
can cause foams and pinholes, aggravated by the need for high agitation during
manufacturing that produces lots of foam. Once created, it is difficult to eliminate, due
to the high viscosity at rest that these formulations have, so the addition of antifoamers
(that is, they prevent the formation of foam) and defoamers (which favor the collapse of
the foam produced) is needed. . Antifoams and defoamers are typically of the type of
polysiloxanes, metal soaps, amides, fatty acids and their esters (eg diglycol stearate) and
alcohols (pe polyalkylene glycol). The commercial products that are usually used are
frequently mixtures of such compounds. When selecting them, it must be taken into
account that they do not have harmful effects on the coating or its appearance. For
example, they can give rise to “fish eyes” or blurring in the film, due to incompatibility
with the binder. To reduce this defect and facilitate the initial distribution of the
antifoam, an emulsifying agent or solvents that act as carriers are usually used.
Although not very well understood, the mode of action of AE seems to be the following,
it spreads over the foam interface and displaces the surfactant responsible for foam
stabilization. Thus, AE has the effect of reducing surface elasticity and/or surface
viscosity. It is appropriate to note that agents capable of reducing surface tension
without producing foam are being sought, such as acetylenic glycols and fluorinated
surfactants.
Another important difficulty with water-based products is the high heat of vaporization
of water, as well as the influence that ambient humidity has on drying, so cosolvents can
be used to provide some form of control in the rate of film evaporation and in the
MTFF.
COALESCENCE

5
Film formation of aqueous polymer dispersions.- The key in the film formation of an
aqueous polymer dispersion deposited on a substrate is the coalescence of the latex, that
is, the joint flow of the particles to form a continuous film, in which the initial particles
have lost their identity and give a film similar to that of a polymer solution in solvent.
Incomplete film formation can cause problems with sensitivity to water, lack of barrier
effect, blurring, cracking, etc.
The factors that favor coalescence are:
 Minimize surface free energy by minimizing surface area. A typical latex has a
surface area of 20 m 2 /g-
 Capillary forces produced by the evaporation of water.
 The attractive forces between particles.

And the factors that oppose coalescence:

 The viscous deformation of the polymer.
 The elastic deformation of the polymer.

The coalescence process proceeds as the result of the balance between two opposing
forces. Kendall and Padget have quantitatively treated the coalescence process in the
critical period after water removal considering the interfacial (attractive) energy term
and the elastic deformation term, which are the main practical parameters that influence
the rate and extent of coalescence. the formation of particles.
When the evaporation of water has occurred and the latex particles are in tangent
contact, two modes of organization are possible for uniform spheres in hexagonal
packing, in one of them (centered cubic) there are three spheres in contact leaving a
triangular gap between them. , and in the case of cubic packing there are 4 tangent
spheres leaving a cubic gap. The coalescence of a film without defects requires that
these voids must disappear due to the approximation and deformation of the latex
particles. If D is the diameter of the latex particles, the theoretical treatment indicates
that for the triangular voids to disappear, the following condition must be satisfied:

where E is the Young's modulus of the polymer

 the surface contact energy (that is, the energy released when two particles contact)
 Poisson's ratio (approx. 0.5)
In the case of cubic holes the condition is even more restrictive:

It is important to indicate that the first term of the previous equation is an important
dimensionless parameter in predicting coalescence:

6
 for coalescence to occur. The previous equation shows that to encourage coalescence to
occur it is necessary:
 Decrease of the Young E modulus.
 Decrease in particle size D.
 Increase in surface energy 

The effect of the other variables on coalescence is related to their effect on the three
previous parameters.
FACTOR EFFECT ON COALESCENCE
Increase Particle Size (D) Difficult
Increase Elastic Modulus (E) Difficult
Increase Surface Energy (  Favors
Increase Temperature Favors
Increase Tg Difficult
Cosolvent Addition Favors
Addition of Plasticizer Favors
Crosslinking inside particle Difficult
Addition of Surfactant Favors or hinders*

 The effect depends on a number of additional factors.

The decrease in Tg favors coalescence since the E of the polymer decreases, which also
causes an increase in the drying temperature. Cross-linking inside the particle prior to
film formation makes it difficult, since it increases E. The presence of the surfactant
may or may not favor coalescence, since in principle it affects E and  . If the surfactant
is compatible with the latex then it acts as a plasticizer and therefore favors coalescence.
The effect of particle diameter is an important effect that is frequently seen in practice.
Small particle size dispersions favor easier coalescence, with particle sizes < 0.2  .
Also the small size of the emulsion allows for better packing of the pigment particles
and better coalescence.
The above discussion of particle coalescence applies to what we have described as a
dispersion of a water-insoluble polymer that remains as a dispersion over the entire pH
range. In the case of hybrid systems in which the polymer increases its solubility in
water as the pH is adjusted, the situation is somewhat different since the pH adjustment
favors the formation of the film, making it more similar to that of a water-soluble
polymer. Thus, the formation of a highly carboxylated, high Tg polymer film is
significantly facilitated by adding a base that increases the pH.

COALESCENTS
Definition.- Coalescents reduce the Tg of a polymer in emulsion, so that film formation
can occur at the drying temperature. After the water has evaporated and the film has
coalesced. The coalescent can evaporate from the resin film so the Tg increases and the
physical properties improve. Typically, most coalescents evaporate at room temperature
an hour or two after water. Residual amounts of the coalescent may remain for days or

7
weeks, especially if it has been applied in a thick layer or if the coalescent has an
affinity for the polymer. Thus, coalescents are usually low-volatile liquids. The main
prerequisite is that they are present when the water has evaporated and that they
evaporate from the film subsequently. If this does not occur, it will remain in the film
and act as a plasticizer, keeping the Tg low.
There is a wide variety of chemicals that can be used as coalescents, ranging from
hydrocarbons, such as white spirit. Up to alcohol esters and glycol ether esters.

Coalescent Benefits:
Scrub Resistance.- In this test, an oscillating brush with a certain weight on it carries
out a certain number of double scrubs that are necessary until the paint has worn off.
The test is performed on samples that have been aged for 7 days and is a measure of the
washability of the paint. If a test is carried out with paints with various levels of
coalescent, an improvement is observed as the level of coalescent increases until a limit
is reached beyond which it remains constant or sometimes decreases. This decrease is
due to coalescent that has been retained and behaves as a plasticizer.
Print Resistance.- This is the name given to the ability of a painting to resist the mark
of an object placed on it. This property also improves with the addition of cosolvent.
Related to this property is blocking resistance and pendular hardness and they have a
similar behavior, improving with the addition of coalescent.
Color development.- If an emulsion paint dries at different temperatures (eg at 10º and
25º) if coalescence does not occur well at the lower temperature, there may be a
difference in the dispersion (scattering) of light and reflection of the surface, with the
result that a difference in color is seen between both paints. . A test can be carried out
by applying two layers with the slightly tinted paint in one case with a panel and paint at
6º (the first layer at 25º) and in another case with the two layers at 25º and comparing
the color difference.
Porosity.- Over time, facades can accumulate dust and dirt particles on the paint. If the
paint has not coalesced well, greater soiling occurs due to the “porosity” between latex
particles. Also a good coalescent seems to increase the CPVC possibly because there is
better wetting of the pigment or because the free volume of the resin has increased by
the use of the coalescent.
Mud Cracking.- It is the term used for the appearance of deep, deep irregular cracks,
with the appearance of dried earth in the paint film. This can occur at low temperatures
if the coalescent is not in the proper proportion.
Film Formation.- The formation of a homogeneous polymer film after the evaporation
of water is necessary to achieve optimal physical properties. The efficiency of a
coalescent can be measured with a temperature gradient platform under controlled
drying conditions. The temperature below which adequate coalescence does not occur is
observed by the appearance of cracking. A loss of shine and reduced residences may
also occur.
Weather Resistance.- Exterior emulsion paints must resist the effects of weather. The
resin can be modified to improve resistance to UV radiation, but the coalescent can
improve its resistance to peeling from the substrate, as well as generally improve its
physical properties. One mechanism by which paints peel involves the transmission of
water vapor from the surface through the paint film to the substrate-paint interface. The
increase in pressure at this interface creates bubbles in the paint, further entry of water

8
leads to peeling of the paint. The coalescent is believed to inhibit this process in several
ways. On the one hand, the paint is less permeable to water vapor due to the better
coalescence of the latex particles, and also because adhesion to the substrate is
improved. Also that the relaxation of tensions in the polymer matrix, due to the presence
of the coalescent, during drying and subsequent contraction is responsible for an
improvement in adhesion. Finally, the physical strength of the film is improved, being
able to resist breakage and eventual peeling.

PROPERTIES OF COALESCENTS
Insolubility in water.- When a water-based paint is applied to a porous substrate, some
of the water will be absorbed into the substrate. If the coalescer is soluble in water,
some of it will also be absorbed and there may not be enough coalescer to coalesce the
resin, requiring a higher level of coalescer.
Low freezing point.- It is required if the paint has to be stored outside in cold weather.
Although some solvents would be good coalescents for latex, they cannot be used as
they freeze at 10ºC.
Hydrolytic Stability.- Some emulsions used in WB paints have a pH around 9. If the
coalescent has a tendency to hydrolyze, there is a risk that its effectiveness will decrease
during storage. An example of such hydrolytically unstable coalescents are glycol ether
esters, as they tend to hydrolyze to glycol ethers, which are less effective coalescents.
Effective on a wide range of polymers.- Acrylic homopolymers and copolymers, and
terpolymers that include vinyl versatate copolymers are widely used as base resins in
the formulation of emulsion paints. The MFFT of these resins can vary from 0º to more
than 80º. High Tg resins tend to be used in industrial applications where the substrate
may heat up during drying. It is convenient for the paint manufacturer that the same
coalescent can be used in a wide variety of paints.
Cost and Toxicity.- Both factors must be taken into account, as well as the
effectiveness of the coalescent since the one that can be used at a lower level is more
interesting.

FACTORS THAT DETERMINE THE EFFECTIVENESS OF A COALESCENT:

Classification of Coalescents.- They have been classified into three types, A, B and C
according to where they reside in the polymer emulsion. The emulsion consists of
hydrophobic polymer chains stabilized into spherical micelles by the emulsifier. A
coalescent added to this system will reside in one zone or another depending on its
hydrophilic hydrophobic character. Hydrophobic materials such as hydrocarbons will be
located in the center of the micelle (A). Aromatic and aliphatic hydrocarbons are
generally classified as thinners and although with some coalescent activity they may not
be very efficient (they reduce the TMFF little) and may reduce the gloss of the paint,
due to incompatibility with the binder. The most appropriate coalescents are found in
zone AB, that is, at the interface with water. They are more hydrophilic than
hydrocarbons, the best known being Texanol, which is an alcohol ester. Other AB types
are ketones and glycol ether esters. ABC coalescents (C is the aqueous phase) are the
more hydrophobic glycol ethers such as butoxy ethanol and butoxy ethanol ether. They
act as good coalescents, but as they tend to distribute between the aqueous phase and the
polymer phase, they must be used in greater proportions than type AB to give similar
coalescence. Hydrophilic glycol ethers such as ethoxy ethanol or ethylene glycol are

9
class C solvents. They are not effective coalescers but are used as antifreeze and wet
edge additives.
Evaporation rate.- A coalescent must be able to soften the resin after the water has
evaporated, but it must not remain in the dry film for a long time. Since active solvents
tend to be compatible with dissolving resins the evaporation of the last traces of
coalescent can be very slow, so the paint may take several weeks to harden.

EVALUATION OF COALESCENTS
Freeze-Thaw Test.- Freezing an emulsion compresses the emulsion particles together.
The presence of a coalescent helps this process, because in the ice thawing phase a
gelled paint can be produced. Some ethylene glycol can be added as an additive to
prevent said gelation. In this application the antifreeze additive acts in competition with
the coalescent. The higher the level of coalescent, the greater the risk of gelation.
Storage stability.- In this test, the paint is kept at 50ºC and the viscosity is checked.
Heating makes the polymer chains more mobile so there is a greater tendency for
gelation. A coalescent can increase gelation if it is very active or if it is added in high
concentration. This gelation could also occur during the incorporation of coalescent into
the resin; to avoid this, incorporate it mixed with water, slowly and with stirring.
Minimum film formation temperature.- It can be measured on a platform with a
temperature gradient and the activities of different coalescents can be compared.
Hydrocarbons are not very effective, butyl diglycol is somewhat better and Texanol and
Butyl diglycol acetate are better
Binary coalescents in high Tg emulsions.- For industrial paints, the emulsions have a
higher Tg. When they are not going to be dried at high temperatures and it is necessary
to lower the MFFT, it may be necessary to use up to 20-30% coalescent.
The use of such a high level of coalescent can imply a high viscosity of the emulsion.
To reduce this increase and at the same time lower the MFFT Eastman has developed a
technique using mixtures of cosolvents, both the viscosity and the MFFT reach a
minimum at a certain concentration of the mixture.
Coalescents Toxicity.- Many of the traditionally used coalescents are based on esters,
which gives stability and odor problems. Another very well-established coalescent is
butylglycol which has toxicological problems.
Dow has developed a generation of solvents capable of offering ecological alternatives:
 Propylene Glycol n-Butyl Ether (PnB)
 Dipropylene glycol n-butyl ether (DPnB)
 Tripropylene glycol n-butyl ether (TPnB)
 Phenoxypropanol (PPH)
 Propylene glycol diacetate (PGDA)

Compared to previous coalescents: PnB is similar to butyl glycol; PGDA is slightly less
volatile than butyl glycol acetate; DPnB and TPnB fit the volatilization range of butyl
glycol and TBiB (Trimethyl pentane diol isobutyrate).
They are characterized by their low odor and low viscosity (Except PPH).

10
Coupling agents.- PnB, DPnB and TPnB have a certain solubility in water, which
makes them suitable as solubility modifiers for water-insoluble substances such as oils,
fats and surfactants.
ADDITIVES

MICROBICIDES
Microbes can degrade almost any organic compound if water and mineral nutrients are
present.
The microbes of interest in the paint industry are bacteria, yeasts and fungi. Each of
these groups has a particular set of environmental conditions that enable their growth.
Bacteria, since they require a high level of humidity in the environment, are found in
water-based paints and other fluids containing water. Fungi, which do not require such
high levels of humidity, grow on the surfaces of paints, adhesives and coatings of any
kind (water or solvent-based). Yeasts whose requirements are between the two can be
found both in the liquid medium and on the dry surface.
Bacteria are so small in size that it takes a million of them to be visible. Another factor
to take into account is their high metabolic rate, which is inversely proportional to size,
so a bacteria can require between 100 and 500 times its weight in feed every hour.
Finally, its reproductive rate is very high, being able to reproduce every 20 minutes in
ideal conditions. Both their ability to reproduce and their high metabolic rate mean that
they can cause considerable damage, since they are also found everywhere.
Fungi do not require high moisture content in their environment. A relative humidity
in air of 30% is sufficient for its growth. They tend to develop in the dry film on the
surface of liquid paints or in the final dry film. They do not grow well in watery liquids.
Although consisting of small cells, their cells grow in linear succession forming
filaments (hyphae). A mass of hyphae forms a mycelium from which spores are
released. The most common is the Penicillium genus, which is green in color due to its
spores.
In the paint industry the biggest problem caused by fungi is due to mold . It is dark in
color and blackens or grays white paints.
Yeasts are single-celled organisms, but 10-50 times larger than the average size of the
bacterial cell. Yeast reproduces by budding, the buds grow at any point in the cell. After
the yolk reaches a certain size it separates from the cell. It can exist both in a liquid
medium and in air with high humidity. They cannot be seen with the naked eye,
although sometimes they develop a slight mucus.
Prevention of microbial spoilage: Microbicides for use in aqueous coatings fall into
two categories: bactericides and fungicides. The former prevent the destruction of
liquid paint in liquid form, which is why they are also called in-can preservatives.
Bactericides can be mercurial or non-mercurial. The former include phenyl mercury
acetate and methyl mercury dodicenyl succinate. They are very active but currently their
use is prohibited.
In non-mercurials there are a wide variety of different chemical types, including:
oxazolidines, hydroxymethylamino alcohols, long chain amines and isothiazolines. The

11
range of use for these products is between 0.05 and 0.5. They have less toxicity than
mercurials, but are less effective.
Fungicides can also be grouped into the two previous categories. The mercurials
mentioned can also be used as fungicides but at higher doses, such as 0.2% by weight,
for phenyl mercury acetate.
Non-mercurial fungicides that are of most interest in aqueous coatings include:
bromoethylphenylchloroacetamide, chlorothalonil, iodopropynylbutylcarbamate,
tributyl-Sn salts and Zn oxide. The selection of the appropriate fungicide is determined
by cost and certain limitations imposed by compatibility with the binder or other
components. Levels can range between 0.5 and 5%.
Another factor to take into account is the speed at which the biocide acts, that is, the
time it takes to eliminate a given population, since the damage caused by these
microorganisms is exponential over time.
RETICULANTS

ZIRCONIUM-BASED CROSSLINKS IN WB.- Zr is an element of the IVB column

of the periodic system and its preferred oxidation state is 4, it is very stable against
corrosion. Due to its high charge and low ionic radius, it hydrolyzes and polymerizes.
Thus, Zr oxychloride is a tetramer and in solution the structure of 4 Zr atoms linked by
OH bridges remains. These tetramers can polymerize by aging, heating or reduction in
an acid medium.
Other similar polymer structures can be found in other aqueous Zr compounds. Thus,
Zr and ammonium carbonate (AZC) is an alkaline solution containing anionic Zr
species with hydrophilic groups that act as a bridge with the carbonate groups. If
hydrolytic stability is important, part of the carbonate groups can be replaced by
chelating ligands (eg tartrate ions).
Zr orthosulfate also exists as an anionic species, but is acidic in nature. Zr acetate is a
polymeric material, but its exact structure is not known. It is neutral in nature and can
also impart water repellency to the substrate after drying.
Other solvent-soluble Zr compounds (carboxylates) also have a polymeric structure,
with hydrophilic groups acting as bridges. Solubility can be regulated depending on the
type of carboxylate.
Furthermore, Zr compounds are non-toxic, which is why they are replacing Pb driers
in a multitude of applications.

Reactivity of Zr compounds: These polymeric compounds react well with oxygenated

species, especially organic ones. It reacts by forming bonds with carboxyl groups and
through H bonds with OH groups. In the case of the carboxyl group there is a direct
bond with Zr, and the resulting compound is quite resistant to hydrolysis, depending on
the steric effects around the carboxyl group. Furthermore, if the bond between the
carboxyl and Zr is at two points of the polymer chain, a cross-linked structure is
obtained.
With the hydroxyl group, the H bridge does not affect the Zr, but through the OH,
this interaction is weaker and can be broken by physical means (stirring). Other
oxygenated functional groups can give similar effects.
It is possible to vary the chain length of the Zr compound, through pH, temperature
and chelating agents, which will have a significant effect on the reaction.

12
Application in aqueous coatings: Zr compounds have been used in aqueous coatings
for the following properties:

a) Improve the adhesion of the dry film to the substrate.

b) Improve the physical and chemical properties of the dry film.
c) Modify the rheology of the paint.

a) Improved adhesion: Zr compounds improve adhesion to the substrate both in

aqueous media and in solvent, as has been proven on polyolefin or polystyrene films. In
these substrates, which have been treated by the corona effect, oxygenated species have
been formed that can interact with Zr, which in turn can be linked to the binder resin.
This scheme is applicable to metals and other oxygenated surfaces.

b) Cross-linking and improvement of properties: Zr compounds in aqueous

medium have the possibility of cross-linking with carboxylated resins, which improves
resistance to heat and scrub. ASCII with Bacote 20 (AZC) the solvent resistance of a
styrene acrylic has been improved.

c) Rheology modifier: Its mechanism is due to the action of an H bridge, which can
be broken by agitation, giving good flow and leveling. Zr compounds can react with
natural polymers, such as starch, gums and proteins, forming insoluble materials by
cross-linking, giving irreversible gels. Zr acetate and Zr and K carbonate have been
used as rheological agents.

Interaction of Zr compounds with colloidal stabilizers: Like other thixotropic

gelling agents that act via H-bonding rather than a simple thickening effect, these
compounds act best when paints contain colloidally stabilized polymer dispersions.
Paints stabilized with surfactants do not usually form gels with Zr compounds.
The colloidal stabilizer present in paints is usually at a level of 0.2-0.3 on solids, a
level comparable to that of the gelling agent. The colloidal stabilizer is a cellulose ether.
Thus the viscosity of the HEC increases notably with Zirgel K.

THIXOTROPIC

THIXOTROPICS .- Rheological control additives (thickeners) allow the paint to be

stored and applied correctly.
When selecting a thickening system, several factors must be considered: the stability
requirements of the system before use, the application method to be used, and the
desired thickness as well as the smoothness or texture of the applied film. There may
appear to be conflicting requirements, such as between preventing sagging and leveling
brush marks, which makes the task of thickener selection complicated and requires
knowledge of the properties of a wide range of products and understanding of the
rheological terms, both scientific and empirical.
The rheological properties of thickeners for a simple aqueous system can be defined
in terms of the relationship between viscosity and concentration, the equilibrium flow
curves of the apparent viscosity as a function of the shear gradient at different
concentrations, the behavior of rupture and formation of thixotropy, viscoelastic
parameters and the effects of temperature change.
The types of thickeners used in water-based products can be classified into two large
groups. One group, associative thickeners, works by interaction with the binder

13
particles. The other acts mainly by changing the rheological properties of the aqueous
phase. This class can be subdivided into two, those that, like clays and silicas, swell in
water and form crosslinks, and water-soluble polymers. The latter include synthetic
polymers, such as polyacrylates, and naturally occurring polymers, such as cellulose
ethers and microbial polysaccharides.

Microbial polysaccharides.- They are obtained by fermentation of simple sugars by

micro organisms and are separated from the medium by precipitation with isopropanol.
The best known is Xanthan gum, which is used as a thickener and stabilizer. Their
solutions are more pseudoplastic than cellulose ethers, they are practically non-
thixotropic and somewhat elastic. They are stable at pH between 2-12, are compatible
with high concentrations of electrolytes and resist cellulase enzymes.
Xanthan gum is a linear anionic polymer with 5 repeating sugar units. The chain is
made up of glucose units linked together as in cellulose. Attached to every second
cellulose are side chains of 3 sugars. In solution the molecule adopts a wheel-shaped,
helical shape with the side glucose chains aligned with the main chains. This alignment
is believed to protect the main chains from attacks by cellulase enzymes, which causes a
decrease in viscosity in cellulose ether solutions. Through hydrogen bonds, molecules
associate together. This association between highly regular and rigid cylindrical
particles explains the rheological properties of Xanthan.
Under these conditions, if a low stress is applied to these molecular aggregates, they
behave with a gel-like character, with elastic deformation. When the stress is greater or
at high shear, the molecular aggregates break and the molecules tend to align in the
direction of flow, significantly reducing viscosity.
Other microbial polysaccharides with similar behavior are Rhamsan and Welan gum.
The high pseudoplasticity of these products makes them not suitable for conventional
painting. For example, for adequate loading of the brush, a high apparent viscosity at
high shear is necessary; on the contrary, when it has been applied and is subject only to
gravity, a low initial viscosity and a certain degree of thixotropy are needed. to allow
brush marks to disappear without sagging.
Associative thickeners usually have adequate rheological behavior during and after
application. However, they may not be sufficient for stability in the container or to
reduce sagging. To rectify this, small additions of Xanthan gum (< 0.1%) are used.
They are also suitable for the manufacture of textured paints, where leveling is
counterproductive.
It has also been used in wood preservatives, creosote substitutes, for DIY applications
on wood. Its function is to keep the pigments in suspension and facilitate dripless
application to fluids that must be low in solids, to facilitate penetration into wood.
Another important application is in phosphoric-based anti-corrosion treatments. It has
good stability at low pH, while its high degree of pseudoplasticity allows the corrosive
liquid to be applied without risk of splashing or sagging on healthy areas of the metal.
In corrosion converters based on an acrylic copolymer - vinyl chloride and tannic acid,
with a pH between 1.5 and 2.0, a combination of Xanthan and fumed silica is used as a
thixotropic agent.

HYDROXYETHYL CELLULOSE (HEC).- (NATROSOL CATALOG): It is a

powder that flows easily and dissolves well in hot or cold water. Available in a variety
of types and grades it can be used to prepare solutions with a wide degree of viscosity
and pseudoplastic rheology.

14
Chemical structure: It is a hydroxyethyl ether of cellulose. Cellulose is a chain
composed of anhydroglucose units, each unit containing 3 OH capable of reaction. If
cellulose is treated with NaOH, it reacts with ethylene oxide, introducing hydroxyethyl
groups that produce hydroxyethyl ether.

Substitution: The number of substituted hydroxyl groups in any reaction is called the
degree of substitution (DS), theoretically up to 3 can be substituted (DS 3).
Hydroxyethyls can be introduced into cellulose in two ways. In the first, ethylene oxide
reacts with the hydroxyls of cellulose. In the second, ethylene oxide, reacting with the
previously substituted hydroxyls, can polymerize forming a side chain.
The average number of moles of ethylene oxide that bind to each anhydroglucose unit in
either way is described as moles of combined substituent or MS.
Solubility in water is obtained by increasing the degree of substitution. Natrosol 250,
which has a typical MS of 2.5, is the most used in latex due to its optimal solubility.
By controlling the length of the chain it can be produced in a wide range of viscosities.
Higher viscosity grades are efficient and economical and provide and are used to
increase extensibility and stability. Lower viscosity grades impart a creamy texture to
latex formulations. By modifying them, better biostability and associative behavior can
be obtained, the latter providing resistance to spatter and better viscosity at high shear.
Dispersion in water can also be improved.
Effect of shear gradient.- HEC solutions exhibit pseudoplastic behavior. Molecular
weight affects how shear affects the viscosity of the solution. Thus, the lower the Mw,
the less variation in viscosity with increasing shear.
Moisture absorption: Like other water-soluble materials, HEC absorbs moisture from
the atmosphere. This amount depends on the initial moisture content and the ambient
relative humidity. Therefore keep in tightly closed containers and in a dry environment.
Incorporation : WS polymers can form gel-coated clumps if addition is not properly
controlled. To avoid this, Natrosol R types are surface treated with glyoxal, which
cross-links the surface and produces a product temporarily insoluble in water, allowing
the dispersion of the discrete Natrosol particles. Once the cross-linked glyoxal is
hydrolyzed by water, Natrosol begins to dissolve without clumps.
Two important properties of treated Natrosol R are hydration and solution times.
Hydration time is defined as the time elapsed between the addition of Natrosol to water
and the time in which viscosity begins to develop. This period can vary from 4 to 25
minutes when the initial pH of the water is 7.2 and the temperature is 25ºC. At the end
of the hydration time, the polymer begins to dissolve. The solution time is defined as the
time elapsed between the addition of Natrosol and the time at which 90% of the final
viscosity is reached.
Effect of pH and temperature: The hydrolysis of glyoxal cross-linking is influenced
by temperature and pH. Increases in T and pH decrease hydration time. For pH above 8,

15
the hydration time may be so short that the treatment is not effective in preventing
clumping.
Addition of Natrosol to Latex: They can be added at different times during
manufacturing. Either at the beginning to increase the viscosity of the pigment
dispersion, or at a later time. It can be incorporated in powder, it can be dissolved in
water, or as a slurry in acidified water or in a non-solvent prior to addition to ensure gel-
free manufacturing. The liquid forms of Natrosol SPF-water-soluble can be used due to
their easy handling and quick incorporation.
As dry powder:

Ingredient Comment

Water (pH 7.5 or lower) Cover the stirrer blades to

avoid splashing.

Natrosol R Disperse 2 to 5 minutes

NH 4 OH or AMP 95 The pH rises and

dissolution begins

Antifoam

Dispersants, Surfactants

Condoms

Pigments Grind 20 to 30 minutes

Finished grinding proceed

to let down

Incorporation of Latex
A minimum of 20 minutes must be waited from the addition of Natrosol to the grinding
to carry out the let-down. Natrosol should not be added as a dry powder after the
addition of latex as the latex would coat the Natrosol particles and the solution time
would be greatly extended.
As a stock solution: Solutions between 1 – 3.5% in concentration can be prepared by
adding Natrosol to water (at pH <7.5) and stirring until the thickener dissolves (about 30
minutes). Alternatively, NH 3 or AMP-95 can be added to the water to shorten the
hydration time once the Natrosol has been dispersed. A condom must be incorporated
into the solution.
As a slurry: Some paints do not contain enough water to dissolve the Natrosol HEC in
the grind to dissolve the HEC. In this case the Natrosol must be slurries (dispersed, not
dissolved). The slurry is added to the grinding (pH<7.5), in this way there is maximum

16
time for dissolution. If the slurry must be added after the addition of the latex, a
minimum of 30 minutes of stirring is recommended.
The following three media are recommended for slurry:
Acidified water. Adjust the pH to 6 with acetic acid. A 20% slurry can be prepared by
adding the HEC to the water with stirring. This slurry can be kept for 20 minutes before
the HEC begins to swell. If swelling begins, the Natrosol particles are covered with a
layer of gel that will make it difficult to dissolve when incorporated into the paint.
Organic coalescents. Among these we have Texanol, butyl carbitol and carbitol
acetate. Natrosol is not soluble in these solvents. Slurry can be made up to 30%
Natrosol and can be kept for a long period of time although some sedimentation may
occur if not periodically stirred. Water-miscible coalescents are preferable over non-
miscible ones, since when the slurry is added to the paint, the water must penetrate the
coalescent barrier to dissolve the Natrosol. This occurs more quickly if a water-miscible
coalescent has been used.
Glycols. Both ethylene- and propylene glycol can be recommended. The maximum
recommended solids concentration is 20%. Although Natrosol does not dissolve in these
solvents, it will swell. Thus glycol slurries should be added to the paint manufacturing
5-10 minutes after preparation.
Liquid form. Natrosol FPS is a high solids suspension that is easy to handle and
incorporate, containing 40% solids and can be incorporated in any phase of the process.
APPLICATION PROPERTIES OF LATEX THICKENED WITH HEC.- Non-
associative cellulosic thickeners act by thickening the aqueous phase. In this part we
will study the effect of molecular weight or type of viscosity on properties such as
leveling, sag, body and resistance to dripping (spatter). High molecular weight
rheological agents give better leveling and thickening efficiency. Those with the lowest
molecular weight are beneficial for anti-drip, body and sagging resistance.

Solution and suspension rheology: In systems such as latex paints, cross-links form
when agitation is low enough. These interactions dominate the rheology and cause the
viscosity to be higher than it should be. When agitation is applied these bonds break.
Entanglement in the free liquid is what dominates the rheology and contributes to
viscosity and elasticity. The solids that are present increase the viscosity only through a
volume filling effect.
The rheology of the suspension tells us that if there is no interaction between individual
components in the paint, the rheology of the paint can be predicted by examining that of
the rheology modifier.
If we study a solution of the rheological agent, for which four solutions of different
HECs of different Mw have been prepared, but at the same proportion, it is observed
that they have a pseudoplastic behavior. All curves approximate and are independent of
the shear gradient, for high values of the same. At low shear, viscosity depends mainly
on molecular weight, at higher molecular weight, more viscosity and greater
pseudoplasticity. At high shear gradients the molecules align in the flow and the
viscosity only depends on their concentration, which explains why they tend to
approach the same viscosity at high shear if they are at the same concentration, although
their molecular weights are different.
Paint Body: Good film body is a prerequisite for single coat coverage and is directly
related to the high shear viscosity produced in brush or roller application. This viscosity
is controlled by the concentration of the rheological agent. Therefore, to increase the
body of the paint while maintaining the Stormer viscosity, the amount of low-viscosity
HEC must be increased.

17
Drip Resistance (Spatter).- It is also a high shear property, it depends on the molecular
weight of the rheological modifier. Those with high molecular weight are more elastic
and therefore impart more elasticity to the paint. Paint made with lower molecular
weight grades is more resistant to dripping during roller application. Also using the
associative Natrosol Plus.
During roller application, threads of paint stretch from the edge of the roller. If the
thickener has some degree of elasticity, these threads stretch and can stretch quite a bit
before breaking, producing drops, more apparent than if the threads break just at the
edge of the roller.
Leveling and slack.- The results in painting indicate that high Mw grades give better
leveling. The interaction between latex and the non-associative cellulosic modifier may
somewhat complicate this relationship. When a high Mw rheology modifier is used, less
concentration is needed, therefore the lower structure lowers low shear viscosity and
promotes leveling. With an increase in leveling, sag resistance generally decreases.
Another factor to take into account is the possible interaction with latex, so latex and
surfactant must be chosen in a way that minimizes the interaction.
Another cause of poor leveling is wicking (absorption by the substrate). If the water is
quickly absorbed into the substrate, the brush marks appear frozen. To reduce this
problem a large amount (low Mw) of HEC should be used.

THE RELATIONSHIP OF HEC AND OTHER INGREDIENTS.-

The effect with pigments: Cellulosic thickeners have a profound effect on the
dispersion state of pigments. These effects can be studied with a relatively simple flow
titration test, titrating with a solution of HEC and dispersant until a given amount of
TiO 2 flows.
As Titanium dioxide is a charged particle, it is reasonable that the anionic sodium
carboxymethylcellulose (CMC) has an influence on its behavior. Thus, low-viscosity
CMCs promote dispersion, while high-viscosity types promote flocculation, since they
link particles and/or entanglement of molecular chains.
Natrosol HEC is non-ionic and therefore does not bind strongly to the pigment,
although it may have some influence on the dispersion state of the pigment. Especially
high viscosity types that can impart flocculation tendencies.
Use of preservatives: Water-soluble cellulosic polymers are exposed to biodegradation
by specific enzymes of cellulose and its derivatives. A wide variety of bacteria and
fungi can be introduced into paint ingredients and unless they contain preservatives,
these organisms can produce enzymes that degrade cellulosic polymers.

Other ingredients affecting shelf life: Not all viscosity losses during storage can be
attributed to degradation of the cellulose rheology modifier. At least three other factors
must be considered:

1. Redox Agents. Ingredients may contain small amounts of oxidizing or reducing agents,
which may degrade water-soluble polymers.
2. Container corrosion. The corrosion process produces peroxides or free radicals, which
can degrade the cellulosic polymer. The use of high levels of tetrapotassium
pyrophosphate or K tripolyphosphate can cause degradation of the container. When these
phosphates are used in combination with other dispersants, the level of phosphates must
be chosen so that only that necessary to bind with the pigment is present.

18
 3. Dispersant effect. Almost all latex paints exhibit a slight degree of flocculation, due to
doublets and triplets of pigment particles and which contribute to the structure of the
paint. If the paint is formulated with an inappropriate or less efficient level of dispersant,
or if the paint is not milled efficiently, the degree of flocculation may vary with storage
time. A flocculated paint has more viscosity than a deflocculated one. If the viscosity of a
paint is measured when the paint is somewhat flocculated, and during storage a
progressive deflocculation occurs due to the dispersant until equilibrium is reached, the
paint appears to have lost viscosity.

Polymeric thickeners based on polyurethane.- Thickeners used in dispersion paints,

such as acrylics or cellulosics, are poor in flow and leveling. Generally these
polyurethane thickeners are composed of three segments and groups:

A: The hydrophilic chain of the polymer, usually consisting of one or more difunctional
polyols.

B: Hydrophobic segments.

C: Urethane groups.

The combination of hydrophilic and hydrophobic segments in a molecule gives the

polymer surfactant properties. Urethane groups provide specific adsorption and
associative properties. The mechanism is based on the hydrophobic parts adsorbing on
the latex particles. Urethane groups can form H-bonds on surfactants adsorbed on the
latex surface. These interactions are relatively resistant to high shear forces, the opposite
of what is observed with high molecular weight thickeners, such as cellulosics, and give
a pseudoplastic behavior. Polyurethane thickeners generally give more viscosity than
cellulosic thickeners at high shear.
Although the associative mechanism is plausible for multicomponent systems, it is not
plausible to explain the increase in viscosity in pure water.
A qualitative model for the thickening mechanism.- The viscosity of solutions
containing organic components increases with the concentration of the dissolved
component. In aqueous systems the phenomenon is used using aqueous thickeners.
More interesting than their difference in chemical nature is their difference in behavior.
UP thickeners belong to the group of surfactants, specifically polymeric surfactants, that
is, molecules that contain one or more hydrophilic groups and one or more hydrophobic
groups. In the presence of a water/hydro-carbide interface, the surfactant will position
itself at said interface, lowering the interfacial tension and stabilizing a two-phase
system.
In the absence of a second phase, the surfactants will form micelles above the CMC.
Contrary to monomeric surfactants, polymeric ones are not necessarily located in a
single micelle, but can belong to two, which leads to a network of micelles linked to
each other, above the CMC. As this can be achieved at relatively low concentrations,
small amounts of polymeric surfactant can give high viscosities. As the formation of
micelles is affected by the presence of a polar organic cosolvent, it is possible to
formulate polymeric surfactant concentrates that, once added to the aqueous phase,
increase its viscosity by diluting the organic component.

19
When the increase in viscosity is due to physically linked micelles, the viscosity will
depend on the number of micelles per unit volume and the number of unions between
them and ultimately these aspects will depend on the size of the micelle (R) and the
hydrophobic segment (L) that joins two micelles.
In experiences it has been found that to increase viscosity at high shear it is important:
1) The number of hydrophobic segments (2 at least).
2) The length of the hydrophobic segments.
3) The length of the hydrophilic segments, which connect the hydrophobic ones.

Influence of inorganic electrolyte and cosolvent.- The presence of ions affects the
micelle. Thus, the addition of NaCl to a solution of SER-AD FX 1010 in water initially
increases the viscosity, since the number of micelles increases, thereby increasing the
number of starting points, but subsequent additions of electrolyte increase the number of
molecules. in the micelle, decreasing the viscosity.
Adding water-miscible organic cosolvents decreases the surface tension, although the
effect depends on the type and concentration of solvent, the CMC viscosity increases
and decreases. Although its effects are difficult to predict. The main influence occurs in
highly loaded paints (PVC>80), which very noticeably influence the low shear
viscosity.
The addition of a nonionic surfactant, such as nonylphenolethoxylate, results in the
incorporation of monomeric surfactants into the micelles, with the result that more
micelles and bonding are formed, but of less strength. As there are more micelles and
bonds, the viscosity at low shear will increase, however at high shear, as the bonds are
less strong, it will decrease to the level of the solution without the additive.
The addition of anionic surfactants has a similar effect to that of the addition of
electrolytes, resulting in a lower CMC and more hydrophobic segments in the micelle,
so the lattice will gain strength. However, the hydrophobic segments of SER-AD FX
1010 will have a greater tendency to associate in one micelle than in two, so the
viscosity will decrease.
Antifoams typically increase viscosity, possibly as a result of solubilization in the
micelle, increased micelle volume, and more interactions between micelles.
Coalescing agents (not water soluble) slightly increase viscosity, possibly as an
antifoam-like effect.

Impact on the properties of the paint.- Firstly we will study the rheology of a
dispersion paint with SER AD FX 1010 compared to an HEC thickener.
At low shear the SER AD has less viscosity, but it is higher at higher shear. The
threshold value (yield value) is lower for SER AD. From the relationship between
properties such as flow, leveling, brushability and viscosity profile, better brushability,
more body, flow and leveling can be predicted with SER AD. This was found in
practice along with increased gloss, scrub- and spatter- resistance.

INORGANIC THICKENERS

Special attapulgites and kaolins have been used for many years as thickeners in WB
products. We will also see its physical and optical properties.

Special attapulgites.- It is a colloidal mineral, and it is a hydrated and crystalline Al-

Mg silicate. Fully hydrated thickens liquids without bloating.

20
Attagel mineral thickeners are mainly used for suspension and thickening. It is mainly
used in anti-drip paints (non drip). They are characterized by a high degree of
thixotropy, but when shear is applied, the viscosity drops considerably, so they improve
flow and leveling, before the gel structure is rebuilt.
They have interesting physical properties, such as inertness, ease of storage and
handling, and can be incorporated in powder form into the pigment dispersion or as a
pre-gel.
They have excellent rheological properties, such as pigment suspension, resistance to
sagging, eliminates liquid separation, reduced water sensitivity, excellent compatibility
with other thickeners, and are not attacked by enzymatic activity.
Its general characteristics are: Average size 0.1 micron; oil absorption 115, Humidity
12%, volatile matter 10%; Surface area (BET) 150 m 2 /gr.; pH 7.5-9.5 and density 2.36.
Mode of action.- When attapulgite is dispersed in water, a network of very fine
particles develops. These particles interact with each other, trapping water inside the
particle network and increasing the viscosity of the system. The resulting
liquid/attapulgite system is thixotropic in nature, that is, a gel at rest and poorly viscous
upon agitation. When agitation ceases, the viscosity gradually increases as a new
structure develops. This cycle of dispersion and realignment repeats itself indefinitely.
It is critical to achieve optimal dispersion in the liquid. Overdispersion, produced by an
excess of dispersant (TSPP, tetrasodiopyrophosphate), will space out the excess
particles and reduce viscosity. Underdispersion, caused by low shear or insufficient
stirring time, will keep the particles as clumps and decrease the number of individual
particles for the lattice.
Therefore, in most cases attapulgite is incorporated in the grinding phase (high shear),
quickly developing a high viscosity. With low shear equipment it is recommended to
use pre-gel. Pregel is a high solids premix, as the system is more populated a higher
shear is needed than in the case of lower solids.
By combining attapulgite with associative thickeners we combine the best qualities of
both, thus attapulgite provides: Reduced syneresis, resistance to sagging, increases
coverage and better color development.
In turn, the associative thickener: Less spatter, excellent leveling, better gloss.

Special kaolin products.- Al silicates and can be classified into several types:
Calcined, delaminated and hydrated. The calcined ones have been dehydroxylated by
controlled heat, producing white pigments, with improved optical properties, abrasion
resistance and inertness. Delaminates raise the aspect ratio (length/width) which
increases their reinforcing and covering properties. Hydrated grades contain some
water of hydration and certain grades are available with surface treatments or special
purpose modifications for aqueous or solvent systems.

Application in paints.- Provides high coverage and high gloss in white and pale tones,
acting as an extender for TiO 2 . Depending on the particle size and oil absorption, they
can be used from high gloss to matte finishes. Imparts brushability, durability,
resistance to humidity and scrub. Hydrated grades can improve and accelerate wet tack,
increase viscosity, accelerate drying and reduce costs. The lamellar particles control
penetration and give resistance to cracking, providing filling power.
In outdoor applications they provide opacity, durability, color and gloss retention,
controlled chalking, cleanability, film integrity, chemical resistance, ease of application,
stability in packaging and dispersibility.

21
In interior applications they are generally formulated at a higher PVC. Hydrated kaolins
with ultrafine particles and high gloss are suitable as pigments for high gloss and semi-
gloss paints. The new high opacity calcined kaolins combine special light dispersion
and high gloss. In matte finishes they are more effective than the usual extenders used
with TiO 2 .
Delaminated grades offer unique qualities for interior paints. As they are made of thin
sheets, they pack tightly, giving excellent barrier properties. They increase coverage and
color strength. Those with a larger plate diameter give an eggshell sheen. Although
calcined types have usually been used for deep mattes, due to their high oil absorption
they tend to give worse stain removal, poorer filling power and “feel”. Therefore,
combinations of delaminated and calcined kaolin are used, achieving high PVC and
pigment levels without increasing porosity. The biggest disadvantage of delaminated
kaolin compared to calcined is the poorer resistance to wet rubbing (scrub).

Amino hydroxy compounds in Water Products

These compounds are Tris (hydroxy methyl) amino methane, (Tris amino); 2-amino-3-
Ethyl-1, propanediol (AEPD); 2-amino-2-methyl 1-Propanol (AMP 95) and 2-
dimethylamino-2-methyl 1-propanol (DMAMP 80). These compounds are characterized
by being amino alcohols. They are characterized by having a primary (or tertiary) amino
group attached to a C adjacent to another C that contains a primary alcohol group. This
condition gives it some special characteristics. The two most important are AMP 95 and
DMAMP 80.
Its most important physical properties are: High strength as bases, reduction of surface
tension, volatility, low odor and toxicity, DMAP 80 forms azeotropes with water, easy
to handle (compared to ammonia or other amines).
Which translate into characteristics of interest: Wetting action, Anionic dispersion,
flocculation control, pH buffer action, solubilization of carboxylic groups and corrosion
inhibition effect.
Both products serve as codispersants with polyacrylate and polyphosphate dispersants,
giving low foaming like non-ionic humectants. Due to their volatility they do not
contribute to reducing scrub resistance.

Polyurethane Dispersions

In this work, ionic dispersions are discussed. They are solubilized by incorporating
“solubilizing” groups into the molecule, which make the polymer self-emulsifiable. The
most important commercially are the anionic ones.
To obtain them, the carboxyl group is introduced, generally with dimethylol propionic
acid. In this phase, organic solvents, such as MEK, are used to facilitate the handling of
the prepolymer. It is then neutralized with a tertiary amine, such as triethylamine. The
prepolymer thus neutralized is dispersed in water. The polymer thus dispersed is given
a chain extension using a diamine, such as ethylene di-amine. Finally, the organic
solvent from the previous steps is eliminated.
The previous syntheses are based on the following general conditions:
1) Aliphatic isocyanates are preferred, since their lower reactivity allows the prepolymer
to be dispersed in water, producing the least reaction. It also confers light stability to the
final product.

22
2) In the reaction between dimethylol propionic acid and NCO, the preferred reaction is
with the OH group. Aliphatic NOC is also preferred, since its lower reactivity ensures
minimal consumption of the carboxylic group.
The degree of hydrophilicity of the final polymer depends largely on the concentration
of the solubilizing group. A balance must be achieved between producing a stable
dispersion and making the film formed easily remulsifiable.
The production of polyurethane dispersions is generally done by two methods:
Prepolymer Mixing Process (PMP) or Solvent Assisted Dispersion (SAD) using a
solvent such as a ketone. The SAD process is easier to obtain solvent-free systems,
since high molecular weights can be obtained, before chain extension can occur. But
chain extension is difficult since the diamines or hydrazine used will react with the
ketone functionality of the solvents. Furthermore, the solvent distillation process takes a
long time and traces of solvent may remain in the polymer. For its part, the PMP
process is much faster in chain extension, but in the traditional process restricted
solvents such as NMP are sometimes used.
In both manufacturing processes, it is anionically stabilized with dimethiolpropionic
acid (DMPA), the most common method of introducing acid groups into the polymer
chain and which, when neutralized, allow their dispersion in water. A tertiary amine is
usually used, which forms a tertiary salt that stabilizes the polymer in water. The main
advantage is the reduction of the minimum film formation temperature by hydro-
plasticization. Upon application, upon evaporation of water, the salt is unblocked and
returns to its acidic nature, which is relatively hydrophobic, improving water resistance,
and the amine is released.

Cationic Types.- They are produced by introducing tertiary amine groups into the
polymer chain and neutralizing them with an acid or quaternizing them with alkyl
halides.
Crosslinking.- To improve their properties such as resistance to solvents and chemicals,
polyurethane dispersions can be crosslinked. Some options are the following:
1: Blocked isocyanates: The application of heat releases the blocking agent and the
reaction begins. Caprolactam and methyl ethyl ketoxime have been used as blocking
agents.
2: Radiation-induced cross-linking: The radiation used is UV or EB. They are prepared
in a similar way to blocked ones, although the blocking agent is replaced by a hydroxy
acrylate. In order for cross-linking to be carried out, a water-soluble photo-initiator must
be incorporated.
3: Melamine-formol resins: These resins can cross-link with acrylic polymers. In the
case of urethane dispersions, it is produced via urethane group bonding or urea bonding
at high temperature.
4: Aziridines: In this case the aziridine reacts with the carboxyl group at low
temperature. There is some doubt about the toxicity of these compounds. The advantage
is that the reaction takes place at ambient T.
5: Zr compounds: These compounds react with the carboxyl group, beginning the
reaction once the water has evaporated. The reaction is very complex and not very well
understood. It is widely used with acrylics but can also be used with polyurethanes.

6: Mixtures with other components: Various types of conventional emulsions can be

physically mixed, which will modify the properties. Their compatibility must be taken
into account and the mixing of cationic and anionic emulsions must be avoided.

23
Physical properties.- Let's look at some properties of linear polyurethane dispersions.
Appearance, viscosity.- They are typically low viscosity and milky in appearance, with
a bluish tone. Both the appearance and the viscosity depend closely on the number of
solubilizing groups. This occurs especially in anionic emulsions in which the
solubilizing groups are –COOH.
As a Generalization:
Few solubilizing groups: Low viscosity, whitish milky appearance, instability during
storage.
Normal solubilizing groups: Low viscosity, milky appearance with a bluish hue, stable
emulsions with good resistance to reemulsification.
Many solubilizing groups: High or moderate viscosity, translucent, dispersions have a
solution-like character, their films have little resistance to reemulsification.

Film-forming properties.- As a class, polyurethane dispersions exhibit good film-

forming properties even at low temperatures. Many commercial products contain
coalescents such as N-methylpyrrolidone.

General physical properties of linear dispersions.- Similar to other types of

urethanes, they produce films with excellent physical properties. Among the
characteristics of the emulsion we have:
Appearance at 25º C White emulsion with a bluish tone.
Particle size 0.2 microns
Viscosity at 25ºC 25-30 cps
Solids content 40%
pH 8.5
Minimum film formation temperature -3 -5ºC
Drying time (25ºC, 55% Humidity) 0.5 mm film on glass 30 minutes
Polyol type Polyether
Aliphatic Isocyanate Type

Regarding the properties of the film:

Tensile strength (Kg/cm 2 ) 250 – 150
Elongation % 320 - 950
Hardness A 98 - 75
Temp. Vickers softening 59 - 36
Taber abrasion (loss 1000 cycles, 1 Kg load) 35 - 6
Hydrolysis resistance (% tensile strength retention after
Immersion in water at 80º for 10 days. 100 100
Tg (DMA) 48 -5ºC

Tg influence of mixing and other conditions.- In the mixture of acrylics and urethane
dispersions, the Tg does not follow a defined rule, it can be calculated approximately
according to the formula
:

In the case of isocyanate that is unblocked by heat, the temperature and heating time
influence the Tg and properties of the film. Thus in one case the Tg can go from 19ºC

24
when it has been heated for 30 minutes to 170º to 21ºC when the heating has been for
40 minutes at 180º.
In the case of the addition of a Zr catalyst plus 16 hours at 65º, the Tg achieved is 58ºC.
While the addition of melanin resin as a Crosslinker plus 30 minutes at 170º allows
reaching a Tg of 73º.

Physical properties of mixtures of acrylic emulsions and polyurethane dispersions.-

Some general observations can be made:
1) “Hard” acrylic emulsions form films with difficulty, which is why they require
the addition of coalescent. This can lead to blocking problems. Mixing with
polyurethane dispersions favors film formation, without the need for coalescent.
2) The acrylic and urethane mixture has better adhesion on many substrates.
3) In general, it provides better aesthetic and resistance properties than pure
acrylics.

Applications.- Like its solvent analogues, it finds application mainly in inks, organic
coatings and adhesives. The main reason for its use is that this class of polymers
provides an excellent combination of physical properties:
High tensile strength and resistance to breakage.
High elasticity
Hardness range 40-95ª Shore
Excellent abrasion resistance
Good resistance to chemical agents and solvents
Good flexibility at low temperature
Among the sectors in which it is being applied we have:
Fiberglass reinforcement
Safety coating for glass bottles
Textile coatings
Paper coatings
Leather finishing
Coating for different plastics
Metal coatings
Wood varnishes
Cement floor covering

Textile adhesives
Adhesives for leather and vinyl

screen printing inks

Hole inks

Sealants

cement additives

WATER-BASED CORROSION INHIBITORS

25
The use of water-based corrosion inhibitors is expanding, which involves the addition of
anticorrosive pigments as additives. However, there are not many studies on how the
pigments used in the solvent medium will behave under these new conditions.
There are several possible types of metal-coating interface interaction, in the case of
water-based products. The processes that occur during drying have more to do with the
water-based system, while in the case of dry film, the processes are more similar to the
case of solvent-based anticorrosive paints.

Corrosion Inhibitors and inhibitory pigments.- The first can be defined as a

substance that added in small quantities, in a normally corrosive environment, reduces
the corrosion rate of a metal, an inhibitory pigment can be defined as a substance that
added to an organic coating, reduces oxidation of the underlying metal.
When describing a compound as an inhibitor it is important to describe the environment
in which its action takes place since the mechanism and effectiveness of a corrosion
inhibitor or an inhibitory pigment must be defined in relation to the environment in
which it must function.
This definition includes, in the case of paint, both the nature of the binder and the
environment to which it will be exposed. In the case of water-based coatings, the
composition of the aqueous phase may have the presence of aggressive ions as well as
the presence of other species that may intervene in the inhibitory process. Also different
environmental conditions can occur during different stages of drying or exposure in
different places or the presence of scratches or cuts on a piece.
For example, in the case of cooling water, the addition of phosphonates to the water is
effective in reducing the rate of corrosion of the steel in the pipes. Although it could be
considered an inhibitor, in reality the protective effect is due to the precipitation of
calcium phosphonate on the metal surface. Such effects are well known in some types
of paints, thus in the case of red Pb oxide based paints the effect is developed by a
reaction between the pigment and the resin. Similar circumstances can occur in complex
water systems, but these effects are not as evident.

Corrosion inhibition mechanisms.- A detailed discussion is outside this context, but

we can indicate that there are two basic mechanisms by which a corrosion inhibitor can
decrease the corrosion rate of a metal in a neutral and well-ventilated environment. In
the absence of the inhibitor, the rate of oxidation is controlled by the rate of reduction of
oxygen on the metal surface, which is in turn controlled by the transport of oxygen to
the metal. Most paints and especially primers are considered to be permeable to oxygen
and water vapor and therefore cannot prevent corrosion due to the barrier effect. Certain
anions act by repairing the oxide film formed and therefore delay the anodic dissolution
of the metal, maintaining the surface in a passive condition. This applies to most anions
present in pigments, such as chromate, phosphate, molybdate, borate, etc. , if they are
present in sufficient quantity. Cationic inhibitors, on the other hand, cause the formation
of relatively thick, precipitated films on the surface of the metal, which hinders the
diffusion of oxygen to the metal. These films are often formed by reaction of the
inhibitor with the hydroxide ion produced by the cathodic reaction of Oxygen as in the
case of the precipitation of Zn hydroxide from solutions containing Zn.

Factors that affect inhibitors.- Inhibitors that passivate anodically are only effective
above a certain critical concentration. In the absence of aggressive ions such as chloride
and phosphate the minimum typical concentration is above 0.001 mol dm -3 but

26
increases significantly with only small concentrations of aggressive ions, both
concentrations being related to a logarithmic equation:

Log C inh = n log C ag + k

With Strontium and Zinc chromates, the solubility in water is sufficient to passivate a
surface in the absence of chlorides, but even a small proportion of these (0.001 M) can
prevent the passivation of the steel. Most anodic inhibitors are only effective above a
certain pH, which may depend on the concentration of the inhibitor, although this is not
usually a practical problem in pigments. Even if the chromate does not passivate a
surface, it may have an inhibitory action but due to the deposition of Cr (III) hydroxide
on the metal surface, which delays oxygen transport. The barrier properties of the
deposited film are better if Zn is present, since in this case basic Zn chromate is formed
on the surface.
While inhibitors such as Zinc Chromate, Phosphate and Molybdate are described as
mixture inhibitors since the individual components can affect the rate of the process at
each electrode, with Zinc Phosphate and Molybdate the solubility is not high enough for
passivation by the anion, regardless of the Cl - level, and when they are effective they
reduce the corrosion rate by affecting the cathodic reaction, via the precipitation of a
basic Zinc salt or a Zinc and iron salt of the anion. Due to its low solubility, the
inhibition properties of Zinc phosphate are greatly affected by pH, since solubility is
greater in alkaline or neutral solutions.

Inhibiting Components of Water-Based Coatings.- In addition to the corrosion-

inhibiting pigments that are incorporated, there may be a large number of components
that, alone or in combination with the pigments, can modify the corrosion behavior of
the substrate. Examples include flush-rust inhibitors, dispersants and surfactants, such
as polyphosphates and polyacrylates, and biocides such as quaternary ammonium
compounds.

Conditions of the coated metal.- Three different situations can be found, although in
practice we generally find mixtures between them. The first case is that of an intact
coating applied and adhering to a clean metal surface. The second case, the coating may
have lost adhesion locally, perhaps due to blistering, and the aqueous phase under the
coating may contain aggressive ions, even if the metal surface had been clean initially.
The third case corresponds to a damaged coating, in which a portion of the metal
surface is directly exposed to the environment. All of this requires that for a protection
system to be successful it must protect in a wide range of environmental conditions.

Surface Reactions during drying.- It may occur that the aqueous extracts of most
inhibitor pigments can exert considerable effects and modify the surface of the metal in
a short period of time. For example, chromates acting as cathodic inhibitors can form
surface films in seconds while the films formed from the Zinc phosphate solution are
thick enough to be observed in the scanning electron microscope in a few hours and the
Zinc molybdate films They are also detectable after a short period of immersion.
Although the formation of these films can occur during the drying period of a latex, the
level reached is partially unpredictable, because the electrochemical corrosion process
can be modified by other components and the behavior during drying may not be
dominated by inhibitory pigments. An obvious example is the widespread use of flash
rust inhibitors, especially in paints formulated at alkaline pH. The objective of these is

27
to prevent corrosion during the drying period of the paint, examples of this type include
potassium chromate and ammonium benzoate. Both are passive inhibitors for steel and
maintain a passive surface during drying, preventing the formation of, for example, zinc
phosphate films.

Surface reactions during exposure.- In most cases the confirmation of the quality of
the paint is based on the observation of characteristics such as: blistering, corrosion
spots, corrosion in cuts, loss of adhesion in the vicinity of the cuts. , etc. Although most
of these tests are related to the corrosion rate, they do not provide a true picture of the
performance of the inhibitory pigments, although recently some direct evidence of the
alteration produced during exposure has been reported. With certain acid-type water-
based coatings there is evidence of changes during exposure, as evidenced by darkening
of the substrate surface. This alteration may reflect the formation of a surface film
during exposure or perhaps the alteration of the film previously formed during drying.
Also in alkyds pigmented with Zinc chromate, the presence of relatively thick
interfacial layers has been observed with transmission electron microscopy, which must
have formed during the exposure period. An interesting feature of these surface
processes is that they are similar to those that occur in aqueous solutions, and they can
also modify the surface pH. This applies especially to Zinc compounds whose inhibition
action is produced by precipitation of a film by reaction with the hydroxide produced by
the cathodic reaction. Since the rise in pH in cathodic zones is often considered to
contribute to the loss of adhesion, the presence of the inhibitor pigment can help prevent
it.

Evaluation of the inhibitory pigment.- Studies have been carried out in aqueous
media with extracts of inhibitory pigment solutions and also on painted metal.
Solution studies: In these cases, the composition that will be used is important, the role
of the coating, the interfacial pH, the composition and concentration of the aggressive
agents are important to determine the inhibition process that may occur. Assuming that
all this information could be available it would be possible to predict the effect of the
inhibitory pigments. In most cases, qualitative predictions can be made, for example, the
effect of outages in a similar environment can be predicted, but quantification is
difficult.
Pigment extracts: The use of these eliminates the need to understand the dissolution
mechanism of pigments, but it is still necessary to provide a realistic aqueous
environment for pigment dissolution. Such studies provide indications of the type of
behavior that can be expected from a given pigment under a range of conditions, with
no information on solubility required. However, a prediction of pigment performance
should require knowledge of how the organic binder and pigment react and how the
binder modifies the local environment.
Painting extracts: Their use is even closer to the real world, but there are still
uncertainties for extrapolation to the real world. In general, these uncertainties are
related to the volume ratio of paint/water and painted metal and paint extract, and also
to the fact that many binders are semi-impermeable to ions, allowing, for example,
movement of cations, but not anions. .
Despite this, numerous useful conclusions can be drawn from this type of study, but
quantification of various effects is not yet possible. Better understanding of the
processes that can occur beneath the coating would be needed, but this is far from
simple. We will see some of these problems and their possible solutions in the next
chapter.

28
Evaluation of the inhibition of coated metals.- Standard methods for the evaluation of
inhibitory pigments are based on: weight loss, visual observation and electrochemical
measurements. The first is not very relevant for painted metals, since the weight loss
due to corrosion is too low to measure accurately, and the second, although associated
with standard methods for assessing a paint against corrosion, only indicates whether
corrosion has taken place or not. Recently, the use of electrochemical methods for the
evaluation of organic coatings has increased, although there is still difficulty in
interpreting the data obtained. Most of these difficulties arise from the fact of the high
electrical resistance of the coating which means that the resistance associated with the
charge transfer process (corrosion) on the metal surface is often in series with a
resistance that can be of various orders. of higher magnitude.
Corrosion potential measurements, which do not involve current flow, can give an
indication of the type and condition of the surface, whether passive or not, and provide
information during the drying phase of water-based coatings and allow comparison
between the behavior of the pigment extract and coated piece. However, potential
measurements do not provide information on corrosion rates.
Recently, the use of impedance spectroscopy has increased for the study of organic
coatings. While, in theory, this system is capable of separating the resistances between
the organic film and the interface, it is still difficult to separate small resistances in the
presence of much larger ones. Most work has focused on measurements of the electrical
properties of the organic coating, which is clearly related to the protective properties of
non-pigmented coatings, but is less useful4 for pigmented coatings. New techniques
such as high impedance systems are being studied.
Thus, a realistic evaluation of inhibitory pigments requires the use of environmental
conditions similar to those found in practice. In particular continuous immersion, often
combined with electrochemical tests, continuous spraying, salt spray tests, wet-dry
cycles, prohesion tests, and gas immersion in high humidity environment can result in
very different modes of surface chemistry affecting therefore to the behavior of the
coating and therefore to the evaluation of the pigment.
A complementary approach to the study of the inhibitory effect is the chemical analysis
of the interfacial region, in which the inhibitor can produce surface films. Surface
analysis techniques such as X-ray or Auger photoelectron spectroscopy can provide
information, although removing the organic film may be complicated. Another
technique is transmission electron microscopy.
The use of water-based products opens the possibility of modifying the metal surface in
a way that is not possible with other systems, mainly due to reactions in the aqueous
phase during the drying of the coating.

PIGMENT DISPERSING AGENTS FOR WATER-BASED

PRODUCTS
Introduction.- The process of dispersing powders in liquids is used in numerous
industries: Paints, Printing Inks, Paper Coating, Textile Coatings, Adhesives,
Pharmaceutical Preparations.
In all of them, chemical additives are used to improve or accelerate the dispersion
process. The dispersion process is essentially a mechanical process to homogeneously
distribute pigment particles and stabilize them against sedimentation and/or
flocculation.

29
Although the physicochemical aspects of dispersion are well established, the
relationship between dispersion and the chemical nature of the dispersing agent is less
clear.

What is dispersion? - We understand as such the process of incorporating a powder

into a liquid medium, so that in the final product the particles are uniformly distributed
in the medium.
Three stages are clearly distinguished in the dispersion process:

I) Wetting of the powder, which involves the displacement of the layer of air
and/or moisture from the internal surfaces of the particles or aggregates of
particles.
II) Breakage of particle aggregates, generally with the contribution of
mechanical energy.
III) Stabilization, particles have a natural tendency to decrease the number of
particles due to irreversible collisions. Process called flocculation . To avoid
this, a repulsive force must be introduced into the system.

In the paint industry, pigments such as Titanium Dioxide or Zn oxide, insoluble salts
such as barite or calcium carbonate or alumino-silicates such as Kaolin (Al 2 Si 2 O 5 )
are used. In water, these pigments exhibit a surface charge that depends on the
characteristics of the oxide and the pH of the medium. Consequently, for each of them
there is a pH at which the positive and negative charges are neutralized, so the surface
charge is 0. This pH is called the Isoelectric Point of the Pigment.

Isoelectric pH of some pigments

Pigment pH
TiO2 4.7
Kaolin 4.8
ZnO 8.0
CaCO 3 9.0

Since paints are formulated at pHs far from these values, the presence of a surface
charge produces a repulsion between the pigment particles. This repulsion can be varied
by modifying the pH or by introducing an ionic dispersant.
The inorganic pigment particles retain a thin layer of water on their surface, the
thickness of which can be increased when a surfactant or polyelectrolyte is added to the
medium.
Thus the stability of the dispersion can be achieved:

a) Due to the use of a polyelectrolyte that introduces electronic repulsion between

particles.
b) Using an ionic or nonionic surfactant that imparts steric or entropic repulsion.
Some systems may use a combination of both.

Use of dispersing agents.- The effective dispersion of the pigment is very important
and can affect many final properties of the coating.
Such aspects are:

30
  The energy required to achieve a given final particle size and the color strength
required.
 Wet and dry opacity.
 Color acceptance (when working with pigment concentrates).
 Stability in packaging.
 Water and alkali resistance of the dry film.

Dispersing agents greatly influence these aspects and therefore careful selection is
necessary to maximize and optimize a paint.
Historically, in water-based products, polyphosphates were used as the most effective
dispersing agents for Titanium, carbonates and kaolin, but as the industry became more
complex, improvements in dispersants were required.
Currently, synthetic polyelectrolytes of varied composition are used that are strongly
adsorbed on the surface of the pigment to a greater or lesser extent depending on the
type of pigment and the medium in which it is used.

Methods for controlling dispersant efficiency.- .

1.- Daniel's flow point method : The pigment mixture is gently mixed with a spatula
with a dispersant solution that is added from a buret. The end point is reached when the
paste becomes liquid and begins to flow down the spatula blade. The amount of additive
in relation to that of pigment is easily calculated.

2.- Pigment demand curve method: Successive amounts of a highly concentrated

solution of the dispersant in water are added to a mixture of pigments, an incorporation
that is carried out while stirring.
The viscosity is measured after each addition and is represented graphically. The point
of minimum viscosity is that of the optimal dosage.

3.- Concentration-Aggregation Procedure: A certain amount of pigment/filler is

mixed with a sufficient amount of water to form a rigid paste. Next, the dispersant
solution is added in small quantities, mixing carefully with a spatula, until when the
spatula is passed through the mixture, it leaves no mark. This indicates the first point,
the pour point.
The second stage of this test consists of establishing the concentration-aggregation
value. To do this, a drop of the dispersed pigment is added to 1 ml of an ionic thickener
placed on a glass plate, on top of a black background. The mass is mixed completely
with little shear, if flocculation occurs, more dispersant is added until no flocculation
occurs. That's the CA point.

Factors that affect the efficiency of the dispersant.- There are several factors
that affect the efficiency of the dispersant, but the basic ones are: Chemical
Composition and Molecular Weight.
Any of the methods described above can be used to evaluate dispersant efficiency.

Chemical composition: To maximize the electrostatic repulsion between particles, it is

necessary to incorporate many ionic groups. They are generally anionic in nature, which
is achieved with the addition of carboxylic or sulfonic acid groups.

31
Among the carboxylic acids we have: Maleic anhydride, itaconic acid, acrylic and
methacrylic acid.
Among the sulfonic acids: vinyl sulfonic acid, methyl-propane acrylamide and sulfonic
acid.
All of them are copolymerizable with a large amount of monomers such as: acrylates,
methacrylates, styrene, isobuylene, vinyl ethers, and acrylamide.
Copolymers can present special properties such as better color acceptance, better
solubility in coalescents and other solvents.
Depending on the ratio of ionic groups to the total content in the additive, the greater the
efficiency of the additive, the higher this ratio, which implies a lower dosage of the
additive and a lower viscosity of the mixture at the optimal point.

Molecular Weight: In this case it not only affects the molecular weight but also its
polydispersity. Thus, it is observed, for a given family, that the higher the molecular
weight, the greater the dosage is needed, as well as the minimum viscosity reached is
also greater.
Something similar occurs when increasing polydispersity; this may require very close
control of molecular weight.
Another series of factors that can influence are the following.

Dispersant dosage: If the dosage is done at the minimum viscosity, the storage stability
may not be sufficient, thus in a paint adjusted to that level the viscosity went from 19
poises (initial) to 112 in 42 days, while if the At double that amount it remained at 21
poises for 42 days.

Type of salt: Most of these additives are used as sodium salts, but it has been found that
ammonium salts seem to perform better. This is related to the fact that these additives
are usually sensitive to water, with sodium salts being more easily solubilizable than
ammonium salts. This aspect is also improved if the copolymer is hydrophobic such as
styrene or methacrylate.
Furthermore, when ammonium salts evaporate NH 3 during drying, they release acid
groups that can cross-link with polyvalent cations such as Zr, Zn or Ti that may be
found in the formulation for other purposes, therefore improving resistance to water and
wet rubbing (scrub). .

Solubility of the dispersant in Coalescent: Sodium salts of polyelectrolytes with a

high degree of carboxyl have poor solubility in coalescents or other cosolvents, such as
those used to improve repainting on edges, which can affect the gloss of the paint.
Copolymer dispersants and ammonium salts improve this aspect.

Color Pigments.- They are normally obtained through a paste pressing process and
their particles have sizes of the order of microns or less. Its surface is generally treated
during manufacturing to facilitate dispersion. Surfactants of different chemical
compositions can be used to facilitate dispersion but have a tendency to foam.
Resinization is a well-known procedure especially for azo pigments. The rosin
precipitates on the pigment surface as Ba or Ca salt.
Polycarboxylates can also present interaction problems with multivalent cations,
causing gelation problems in pigment dispersions.

32
Styrene-acrylate and ester-acrylic acid copolymers are widely used in the ink industry as
grinding vehicles for color pigments. Low molecular weight polymers of this type are
much lower in acidity than those used with inorganic pigments.
With polymers of this type it is possible to obtain pigment concentrates of up to 40-50%
depending on the pigment and the chemistry of the polyelectrolyte, while with
surfactants the norm is 25-30%.
With careful selection of copolymer composition, acidity and molecular weight,
dispersion, stability and compatibility can be improved. Let us also remember that a low
dispersion of molecular weight and ammonia salts improve effectiveness.

FOAM CONTROL AGENTS FOR SURFACE FINISHES

Introduction.- In water - based paints there are numerous products that produce foam
and range from emulsifying agents to dispersing agents for pigments and fillers. It also
usually contains foam stabilizing agents such as cellulosic thickeners and sometimes the
polymeric binder itself.
Selecting the antifoam agent is not always easy, below we will see their properties and
how they are related to their components.

Generation and stabilization of foam.- Foam is a dispersion of a gas in a liquid. This

dispersion is inherently unstable, being subject to breakage by gravitational, mechanical
forces or thermal shock. In fact, a pure liquid will never maintain a stable foam.
For it to be stable, it is necessary that a surfactant compound be adsorbed on the liquid-
air surface, producing a surface film whose composition is different from that of the
liquid core.
To understand the reason for the stability of the foam it is necessary to understand the
nature of the surface film. The surfactant affects the surface tension in the film, so it
must be quick to avoid forces that could break it.
This ability of the films to respond to local variations in surface tension is what is
known as Gibbs elasticity and is given by the equation:

E = 2 A (d  dA)

Where A is the area and g is the surface tension.

In other words, elasticity is a measure of the change in surface tension when a change in
area occurs. If a bubble expands, the concentration of surfactants on the surface
decreases, increasing the surface tension of the film. This increase in surface tension
causes the bubble to return to its original size.
It is necessary to point out that the ability to form foam and the ability to stabilize it are
different things. Once the foam is formed, the liquid surrounding the air bubble begins
to drain due to gravity. In the absence of some stabilization mechanism, this would
cause the wall to thin until it reached a thickness that any impact, no matter how
minimal, would break the bubble and the foam would collapse. The stability of the foam
depends on their ability to maintain sufficient thickness on the bubble walls to allow

33
them to resist shocks and other deformations, and film surfaces capable of remedying
small points with little thickness.
The first effect is the Marangoni effect. Once the bubble is formed, as we have said
before, the drainage of water from its walls towards the mass of water begins. In this
process, molecules of the surfactant are dragged and causes them to accumulate at the
base of the film, causing the surface tension is lower than in the upper parts of the
bubble, creating a surface tension gradient.
This surface tension gradient forces the surfactant molecules, accompanied by liquid, to
rise to decrease the gradient, thereby filling the wall of the bubble again, stabilizing the
foam. Without the Marangoni effect, the foam would not be stable. This effect is also
capable of repairing small areas with thin walls that may occur. This gives the foam the
first seconds of life and allows for subsequent stabilization mechanisms.
Foam stabilized by the Marangoni effect is called wet or dynamic foam. In this state it
is a fragile foam capable of being eliminated by chemical foam control agents, it can be
compared to the foam of champagne.
The second stabilization effect occurs when, due to liquid drainage, the walls have
become so thin that the surfactant molecules on opposite walls tend to form bulky
molecules.
Proteins, starches and synthetic polymers are high molecular weight molecules. The
surface viscosity of this laminar film increases significantly and the stabilizing
surfactant molecules change from poorly packed layers to almost crystalline condensed
layers. A structure is formed within the film that prevents the drainage of liquid from
the bubble wall. This gelatinous layer formed contains high molecular weight
molecules, insoluble salts and fibrous compounds such as cellulose that help reinforce
the film.
A foam stabilized in this way is known as dry or static foam and is a very stable foam
and difficult to break down by mechanical or chemical means. It can be compared to the
foam on the top of a glass of beer.

Foam control methods: There are various methods of mechanical foam control from
the rotating blade that hits the foam breaking it to more modern methods based on sonic
methods that when adjusted to the appropriate frequency create waves that break the
foam. Another system is water spray in which small droplets of water are sprayed
against the foam. There are thermal methods that, by varying the temperature, affect the
surface tension and viscosity, destabilizing the foam. However, these methods are not
usually applied in industry, since foam can be produced at different points in the plant,
which is why chemical methods are preferred for foam control.
Defoaming: The term refers to breaking an already formed and stabilized foam,
generally statically. Defoaming is a surfactant agent, when introduced or applied to an
existing foam it tends to produce extreme and rapid local variations in surface tension.
Its molecules tend to accumulate at the gas/liquid interface, forcing the liquid molecules
to move, decreasing the thickness of the wall until the bubble breaks. Once the bubble is
broken, the defoamer must be mixed with the liquid to penetrate the adjacent bubble and
continue its action. It usually gives good results to combine this system with the spray
system, that is, mix the water with the defoamer and spray with said mixture.

Antifoam: Here the chemical agent prevents the formation of foam. Its properties are:
low surface tension, ability to penetrate and expand through the bubble lamella, and
prolonged insolubility.

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The foam breaking agent must be more surfactant than the foam stabilizing agent. This
facilitates its penetration into the surface layer of the foaming liquid and, as it is
insoluble, it displaces the stabilizing surfactant from the gas-liquid interface.
The layers of mixed surfactants prevent the association of the molecules and have low
elasticity. The random presence of insoluble, highly surfactant molecules in the surface
film interrupts the stabilization of the foam due to the Marangoni effect or the formation
of gelatinous surface layers, thus preventing foam from the beginning.
Composition of antifoam agents.- It is possible to use a single component as antifoam.
Hydrocarbons, alcohols or silicones meet some of the requirements to be an antifoam.
However, none of them are entirely appropriate to be a good antifoam agent. Below we
see some of their drawbacks:
Lower hydrocarbons, such as paraffins and terpentines, have been widely used in the
paper industry due to their low price. However, their low molecular weight, which
facilitates their penetration into the foam, also makes them easy to emulsify and
solubilize, which reduces their long-term effectiveness. Similarly, vegetable oils and
waxes have been used as antifoams, but hydrolysis of natural triglycerides could lead to
the formation of a foam-stabilizing soap.
High molecular alcohols such as octyl or decyl have been used in applications where
rapid foam breakdown was necessary, but long-term activity is not required.
Acetylenic alcohols have a similar action and can be used as low foam dispersants or
defoamers. The –OH group increases penetration and is used in the paper industry
where the presence of surface defects produced by active antifoams would be
detrimental. Unfortunately, its foam control effect is short-lived due to its rapid
solubilization.
Silicone oils are well known as antifoaming agents, being very insoluble they are
effective for long periods of time. Their main drawback is that dimethyl polysiloxane
oils are so insoluble that they are very difficult to incorporate into water-based systems
and often produce surface defects in painting applications.
Therefore, most of the available antifoam agents are composed of several substances in
order to emphasize some property such as penetration capacity or insolubility. In most
cases there are three main components. The first is called “carrier” oil, although it can
be a hydrocarbon, vegetable or even water in some cases. Within the carrier, the
hydrophobe is dispersed, which, as its name implies, increases the insolubility of the
final product, and a wide variety of chemical substances such as esters, ethers, silicones,
waxes and various inorganic minerals can be used as such. The nature of the
hydrophobe as well as its incorporation are very important. Finally, the incorporation of
a surfactant may be necessary to help the penetration and emulsification of the foam
control compound. The choice of surfactant is crucial for the efficacy and compatibility
of the final compound.
Selecting the appropriate antifoam agent.- In principle, a sample of the paint with the
addition of AE is subjected to a rapid test, through which air is introduced by stirring or
another similar system to form foam, in this way the best ones are selected for testing.
later with application systems more similar to reality.
For example, in paints, the material can be applied with a roller, brush, etc. and the wet
and dry application is observed. The sample is then subjected to accelerated aging for
several weeks at high temperature and its behavior is checked again. Finally, the dry
film must be checked for its gloss, hiding power, weather stability, etc.
To limit the number of choices and facilitate quick identification, AEs can be classified
into families according to their components:
Thus the carrier can be light or heavy:

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The insoluble particle can be organic or inorganic
And the polyether or silicone surfactant.

SPECIAL CARBONATES FOR WATER-BASED PRODUCTS

(Microfine Minerals)

They are an intimate mixture of two minerals Huntite Mg 3 Ca (CO 3 ) 4 and

hydromagnesite with the formula Mg 4 (CO 3 ) 3 (OH) 2 3 H 2 O, both minerals are white
that occur in fine lamellar crystals.
Once processed, they have properties similar to synthetic or modified extenders such as
precipitated carbonates, calcined China Clay and silicates.
Its lamellar particles are suitable for use as a Titanium extender. They also confer
pseudoplasticity and thixotropy, which reduces sedimentation. Surface treated grades
are available which allows their dispersibility, rheology and wettability characteristics
to be varied.
Properties:
Density 2.5
Oil absorption (g/100g) 40
Refractive Index 1.56
Specific area (m 2 /g) 15
Color (Tristimulus values)
x 95
And 95
Z 94
Bulk density (loose) Kg/L 0.23
pH (sol. 10%) 9

Water-based finishes for exterior wood

Lately, water-based finishes for exterior wood have been significantly developed. One
of the main motivations has been to improve long-term protection qualities, especially
for wood for carpentry and construction.
Comparative tests between different products have found that acrylic paints show
superior extensibility and water vapor permeability than conventional solvent-based
paints, especially under normal weathering conditions. Thus, conventional solvent-
based gloss paints have a vapor permeability of 10 g/m 2 /24 hours compared to 90 for
water-based gloss paint, at 25ºC and 0-90% relative humidity.
In experimental tests of exterior windows, water-based paints needed a maintenance
cycle of 5-8 years, compared to 3-4 years for solvent-based paints.

Problems to be solved.- Despite the technical advances in the binders used and
associated additives in recent years, there are still problems to be solved. For example:
- Application
- Blocking resistance
- Spike lift
- Application at low temperatures
- Poor compatibility with linseed oil-based fillers
- Better Tg/MFT balance to reduce thermoplasticity/staining
- Early rain resistance

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 - Short time for overlapping
- Sensitivity to poorly prepared substrates
- Lower gloss than solvent paints
- Universal dye compatibility
- Prevention of bleeding of water-soluble extractives that in tropical species such
as Iroko, Framire, Ningon, etc. It can lead to yellowing of white paints.
- Solids in Volume smaller than in Alkyd resins

Some of these problems are related to inherent characteristics of the film-forming

binder, the dependence of the binder on water evaporation in the first stage of drying,
etc.
For example, emulsion resins form a film by coalescence of the thermoplastic particles
of the binder under the conditions of high capillary pressure that occurs during the
evaporation of water. There is a temperature limit for this to occur (TMF).
If water-based paint is applied in unfavorable weather conditions (high humidity, low
temperature), drying will be impaired and the coalescent may evaporate before the
water, leading to inadequate coalescence when the water finally evaporates.
Under normal application conditions, water-based paint can dry 3 to 5 times faster than
the solvent-based product, allowing the application of 2/3 coats in a single work day.
Freshly applied water-based paint is naturally much more sensitive to high humidity and
rain, which can cause failure to dry or breakage of its integrity. A heavy downpour can
even lead to the complete loss of the paint applied to the wood.

Appearance of the finish.- It is not often recognized by the user that the quality of the
application largely determines the appearance and quality of the final product, which
can be significantly improved by a liberal and uniform application.
Brush resistance (drag) is not experienced in water-based finishes, causing painters to
apply very thin coats (due to their natural tendency to “stretch the paint”), which
inevitably produces “brush marks” and diminishes the durability of the product.
Some improvement in this aspect has been made with “associative thickeners” which
provide a rheology that allows thicker films to be applied.
The film-forming characteristics of emulsions predispose both dry and wet finishes to
“blocking”, that is, sticking two surfaces in contact. This can happen both in the factory
and on site, for example in a window between the frame and the door.
To solve it, different media are used, such as a high level of pigmentation, inert fillers
and polyolefin waxes, which give matte finishes. The use of high MFT (and Tg) resins
has contributed to solving these problems.
Grain raising is another problem encountered in waterborne finishes, particularly in
conifers such as spruce or pine. Although it is not critical in translucent finishes, where
the aim is to highlight the appearance of the wood, it can be an undesirable effect in
opaque paints applied on large surfaces. Satin or matte finishes also hide this problem.

Future Developments.- The growing need to increase durability and reduce

maintenance costs has been an important source of development. For example, the
introduction of so-called “hybrid systems” that incorporate conventional alkyds with
acrylics to obtain a better balance of properties. Obtaining a good result especially in
high brightness.
The application on treated wood to increase its durability is also an important challenge.
It should be noted that in any case it is necessary to properly prepare the substrate
before application and clean it of dust, dirt and grease deposits.

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Protection against photodegradation caused by UV radiation must also be increased by
adding UV-absorbing agents, especially in transparent finishes.

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