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TiO2 Impact on Paint Weather

Resistance
A comparative study between test methods.

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J. Rommens, A. Verhaege, G. Michiels, Chemours, Belgium; M. Diebold, Chemours,
USA09.04.17
Abstract
Titanium dioxide pigments play an important role in protecting white and light colored
paints against the influences of weathering. Careful pigment design enables the best
protection and guarantees maximum coating lifetime. During the development of
pigments and paints it is important to study and measure weathering influence in the
most representative way. In this paper, a comparison is made between accelerated
methods for studying weathering and outdoor exposure of several industrial paints. The
impact of titanium dioxide on weather resistance, as well as the correlation between the
testing methods, is evaluated and discussed.

Introduction
Titanium dioxide is a well-known white pigment; but beyond its exceptional whitening
power, it can also increase the durability of a paint. TiO2 has a positive effect on the
weather resistance of a coating due to its UV absorbing capacity. TiO2 absorbs UV
light, which provides protection from UV degradation to the underlying resin molecules.
After UV absorption, however, the energy of the UV photon must be transformed to
another form of energy. In the clear majority of UV light absorption events, the energy
absorbed by the TiO2 is changed into heat, without damaging the paint film. However,
the UV light energy is sometimes changed into chemical energy in the form of chemical
radicals. These radicals form on the TiO2 surface, but are mobile enough to travel to
resin molecules, where they initiate a series of degradation reactions that ultimately lead
to film failure. This process is called photocatalysis. Proper treatment of TiO2 pigments
can reduce photocatalysis to a great extent, thereby turning the pigment into an efficient
UV protecting agent without the negative photocatalysis effects. Such TiO2 grades are
referred to as “durable” grades. The efficiency of this treatment can vary between
different TiO2 pigment types and can lead to important differences in a coating’s
weather durability.

Super durable grades have a layer of silica, alone or in combination with other
materials, on their surface that prevents these radicals from forming. This silica layer is
applied by the TiO2 manufacturer during pigment production. The fact that different
grades of TiO2 have different radical formation rates is reflected by the labeling of TiO2
grades as being “non-durable”, “durable” or “super durable”. Note that these
designations do not apply to the pigment itself—TiO2 is titanium metal rust and as such
is thermodynamically stable—but rather to the effect that the TiO2 grade has on film
durability.

The formulator has a choice of ingredients when developing a new super durable paint
or modifying an existing one. The first choice is the correct resin, and super durable
paints must use highly durable resins. Since these resins tend to be quite costly
compared to their low-durability counterparts, it is essential that the formulator select the
other ingredients in a way that maximizes the durability performance and value of the
resin. Using the right super durable TiO2 grade is a critical aspect of this. To develop
and select the most durable paint, weathering tests are essential.
Accelerating Paint Weather-Resistance Measurements
Studying the weather resistance of a coating can be a complex matter. The best and
most reliable method for studying the weather resistance of a coating system is outdoor
exposure over several years. However, during the development of a paint system, it is
often necessary to assess the weather resistance in a much shorter time frame.
Therefore, different accelerated weathering techniques have been developed. Before
we compare some of these, it is important to understand the complexity of the
weathering process. There are different ways a coating can degrade during exposure to
weather. In this study, we limit the discussion to white paints.

1. One pathway is direct degradation of the resin which is related to the effect of direct
UV light. This degradation will mainly occur at the surface in a pigmented system.

2. A second degradation mechanism is the photocatalytic degradation related to the


photocatalytic activity of TiO2. Reactions with free radicals produced at the surface of
the TiO2 will occur in the vicinity of the TiO2, because of its photocatalytic activity.
Degradation will mainly occur at, or close to, the surface here also, because UV light is
absorbed and cannot reach beyond the surface of the coating.

3. A last degradation pathway is temperature. Change in temperature can cause


different kinds of damage depending on the paint system. These include color changes,
adhesion failures, or cracks. Increased temperature will also accelerate many chemical
reactions. We will not discuss thermal degradation because its rate is independent of
the grade of TiO2.

Since photocatalysis is one of the mechanisms which can cause degradation of a paint
system, one can assume that reduced photocatalysis will, at least partially, slow down
the weathering degradation. So, measuring the photocatalytic activity of TiO2 will be a
measure of the weather resistance of a coating system containing such pigments. This
can be done by measuring the effect of TiO2 on the light degradation of a simple
organic molecule like isopropanol. This is an over-simplified method, since in a true
paint many more complex reactions are taking place.

An elegant way of predicting the photocatalytic activity of TiO2 is the measurement of


the encapsulation efficiency of the pigment. For silica-encapsulated TiO2, this can be
done by measuring acid solubility.

However, this test only measures one aspect of degradation, and will not always be an
accurate prediction for final paint degradation.
The only way to get a realistic idea about the true weather stability of paint is to do a
lengthy outdoor weathering study of the pigmented paint. Throughout the years,
different methods to study degradation in an accelerated way have been developed.
Since the degradation is caused by UV light (energy), there are different ways to
accelerate it by increasing the rate of energy addition.

There are three methods to do so. The first: increase the temperature. However, as
previously stated, this does not affect TiO2. Secondly, one can increase the amount of
energy per photon by using more energetic light, such as UV-B light. A third method is
increasing the number of photons, or light intensity. This is done using weatherometers
with Xenon lamps (WOM).

Trying to accelerate the degradation is risky, since the different degradation reactions
do have varying dependence on light intensity. The photocatalysis reaction changes
with the square root of the light intensity, whereas the direct degradation of the resin is
directly proportional to the light intensity. This implies that usage of high intensity UV
light will increase the direct resin degradation more than the photocatalysis. Based on
this, we can already assume that accelerated methods do not necessarily correlate well
with true weather exposure.

The best way to accelerate the weather exposure is natural accelerated exposure
(EMMAQUA). In a typical exterior exposure, panels are attached to racks with the
painted portion facing the sun. In the natural accelerated test, panels are mounted
facing away from the sun and towards a bank of mirrors. The mirrors reflect the sunlight
onto the panels. This concentrates the sunlight, increasing its intensity by a factor of 10
or more. The advantage of this type of exposure is that the balance between the
different types of UV light is maintained at the same level as it is found in sunlight, and
so we need not be concerned with unnatural reaction pathways that are initiated by UV-
B or UV-C light. This accelerated test is however not yet well established in international
standards and will not be further included in this study.

Now that we understand the different influences at play when trying to accelerate
weathering, let us look at some examples of weatherability testing, and how TiO2 plays
a role.

Experimental Methods
Having a standard method for measuring/assessing durability is one of the challenges in
the coatings industry. Not every paint application has weathering standards. This study
uses two internationally recognized standards for the construction industry. The first one
is the GSB standard (GSB AL 631), using QUV-B as accelerated method (DIN EN ISO
11507). The second one is the Qualicoat standard, using Xenon light exposure (ISO
16474-2). Requirements for both standards are shown in Tables 1 and 2.

Results and Discussion


During the last decade, Chemours has evaluated 10 different industrial coating systems,
including over 20 different TiO2 types. There were seven polyester coil coat systems,
one primid crosslinked polyester powder coat system, one refinish polyurethane coating
and one high-bake melamine polyester automotive topcoat system. All these systems
were evaluated with QUV-B, Xenon exposure and Florida exposure. This is the ideal
basis for a comparative study per both standards.

In Figure 1 the correspondence between QUV-B exposure and Florida exposure is


shown. According to GSB, 300 hours should be an equivalent measure for one year of
Florida exposure (standard), and 600 hours for three years of Florida exposure. The
former gives a reasonably good correlation, but there are already some TiO2 pigment
responses that do not correspond (Figure 1a). Longer exposure leads to much less
correlation (Figure 1b). Figure 2 shows the correspondence between WOM and Florida,
per Qualicoat. The correlation gets worse with longer exposure here as well (Figure 2).

This general overview suggests that one must be careful with accelerated weathering.
Based on QUV-B, 70 percent of the coatings would qualify for GSB standard class, the
same based on Florida. QUV-B would only qualify 50 percent for Master and 23 percent
based on Florida exposure. For Class 1 Qualicoat, almost all systems would qualify
based on WOM and Florida. Only 40 percent would qualify for Class 2 based on WOM,
but much less (27 percent) would qualify for Class 2 based on Florida. From looking at
the graphs, one can see not only is the number of qualifications less after Florida
exposure, but that the types of paints that qualify under Florida can vary from those
qualified under accelerated methods. Certain paints would qualify under WOM and not
under Florida, and the reverse is also true. One can certainly draw the wrong
conclusions when only using accelerated weathering, ruling out systems which might
qualify in real-life weather exposure.

The influence of TiO2 is demonstrated in Figures 3a, b and c. Here a primid crosslinked
polyester powdercoat with 33 percent TiO2 load was evaluated with different TiO2
types. Twelve different TiO2 types (chloride and sulphate) were evaluated. All coatings
were exposed in duplicate under QUV-B, Xenon and Florida and evaluated according to
GSB and Qualicoat. Although the same resin was used in all coatings, a different
performance could be seen after Florida exposure. The most durable coats were
obtained with so called “super durable” TiO2 grades (C2, C3 and C10). The least
durable coats were obtained with less durable TiO2 grades (C0, S2, S4 and S5). This
difference is obvious after 3 years Florida but not, or hardly, visible after WOM or QUV-
B exposure.

Conclusions
It is clear that common accelerated artificial weathering methods can lead to the wrong
conclusion, especially when going to the most durable paint systems. Paint producers
must be cautious when basing customer performance warranties on the results of
accelerated testing alone. It is also clear that TiO2, as an ingredient, plays a role in
enhancing durability of white paints. However, testing this in an accelerated way with
artificial light is difficult and can be inaccurate, especially for long-lasting systems. Super
durable TiO2 grades are designed to give optimal protection against UV light. This is
confirmed in paint studies using Florida exposure, the most realistic and reliable test
method. Conclusions using accelerated studies must be treated with sufficient care.
Study Compares
Accelerated Aging
Tests
6/16/2015 11:19 AM

T esting the corrosion resistance of paint systems for marine environments is

important when selecting coatings as well as validating surface preparations. The most reliable
testing method is exposing coating samples in the field in harsh environments that are
representative of the conditions where the coating will be applied, which is time consuming,
costly, and sometimes not possible for practical reasons.
As a solution, coating selection for marine environments is often based on results from
accelerated corrosion tests conducted in a laboratory, such as the conventional salt
spray tests or cyclic corrosion tests. Among cyclic corrosion tests used to qualify
offshore coatings, two major test methods are generally selected: ISO 20340 Annex A,
and ASTM D5894 as cited in NACE standards TM0304, TM0404, and SP0108.
Although both are recommended for assessing paint systems for offshore applications,
these testing methods differ regarding test duration and salt solution (three months in
synthetic seawater for ASTM D5894 vs. six months in sodium chloride [NaCl] for ISO
20340), sample preparation with a scribe (a 90x2 mm vertical scribe for ASTM D5894
and a 50x2 mm horizontal scribe for ISO 20340), and cycle times.
Since little information is available comparing both testing methods in ranking coatings
for offshore and marine environments, researchers with the French Corrosion Institute
and Total in France studied the behavior of 12 different coating systems applied on
abrasive blasted steel panels using the two different accelerated corrosion test
methods. Despite significant differences in the two tests, such as duration, salt solution,
sequence of cycles or scribe orientation, rather similar material ranking was observed
apart from one epoxy coating. Details of the study and the performance of the different
paint systems are presented in CORROSION 2014 paper no. 3762, “Comparison of
accelerated ageing tests as per ISO 20340 Annex A and NACE SP0108 standards,” by
N. LeBozec, C. Hall, and D. Melot.

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