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Quelle/Publication: European Coatings Journal

Ausgabe/Issue: 10/2005
Seite/Page: 38

Less metal, more protection


and mechanical properties after 24 hours (Table 4). Full
Performance of zinc-rich primers is enhanced by use of hardening of coatings to achieve salt spray resistance took
zinc flakes. seven days.
Ljudmila Kruba, Pierre Stucker, Tom Schuster.
The use of a mixture of lamellar zinc flakes and zinc dust in Improved appearance after corrosion tests
an ethyl-silicate based zinc primer has been found to The corrosion protection properties of the primers were
maintain efficient cathodic protection at much reduced zinc visually determined after the salt spray test (DIN 50 021)
contents. The new formulation also avoids the problems of and are shown in Figure 1.
porous structure, blistering, pinholing and white rust Figure 1a shows a typical picture of zinc dust coatings after
commonly found with this type of primer. the salt spray test: the surface shows blistering and white
Traditional zinc dust/ethyl silicate primers contain about rust. Using the zinc flake/zinc dust formulation changes this
70-80% by weight of zinc in the formulation. This provides a picture fundamentally: smooth and even surfaces without
very high cathodic protection, which remains effective even blistering or white rust can be seen in Figure 1b. These
after damage to the coating. However, the high zinc dust visual differences are confirmed by the microscopic surface
content produces characteristic defects: a porous structure, comparison (Figure 2).
white rust, pinholing, blistering and mud-cracking [1, 2, 4-7]. Cross-sections of the zinc flake/zinc dust and zinc dust
These issues can cause problems when overcoating. primers after the salt spray test are shown in Figure 3.
The main market requirement for zinc-based ethyl silicate The cross-section clearly shows the difference between the
primers today is any possible reduction of the zinc content in conventional and new primer systems. The zinc dust primer
the formulation. The primers should still satisfy a list of (Figure 3a) shows contacts only between dust particles. The
requirements that can be summarised as shown in Table 1. open and porous structure of these coatings explains the
appearance of white rust at the surface (Figure 2a).
Mixing flakes with dust allows zinc content to be For coatings with the zinc flake/zinc dust combination
reduced (Figure 3b) the results are different: multiple contacts
By combining zinc pigments with different particle shapes between dust/dust, flake/flake and flake/dust lead to high
(lamellar flakes and spherical dust) it has been found and lasting corrosion protection by such coatings [1,8]. In
possible to significantly reduce the heavy metal content in addition, the zinc flakes create a very good barrier effect
primers (to 25% by mass in the formulation, equivalent to both by retarding the access of corrosive media to the
11.7% by volume in the dry film) and to obtain coatings with substrate and by inhibiting the diffusion of zinc white rust
excellent corrosion protection and mechanical properties. towards the surface.
The two zinc pigments work together in giving cathodic The result is a smooth and even surface on the coating that
protection and in addition the zinc flakes create a very good practically excludes white rust formation on the surface
barrier effect, providing coatings without a porous structure, (Figure 2b). Furthermore, this combination of different
blistering, pinholing or white rust [8]. shaped zinc pigments gives an improved packing density in
the film which provides very good mechanical properties.
Solvent content is changed to optimise properties The comparison of primer surfaces after a weathering test of
Tetraethyl silicate ("TES 40"), which forms more than 21 months shows no corrosion at the surface of
polyethoxysiloxane after hydrolysis with water in acidic either coating (Figures 4a and b). This test is continuing.
medium, was used as a reactive binder to produce
self-curing zinc silicate coatings. The optimised formulation Environmental, application and performance benefits
of this hydrolysate is shown in Table 2. It may be observed The performance obtained with these new primers exceeds
that a mixture of solvents is used and the amount of solvent the requirements of customers for such coatings. Their
present in the hydrolysate itself is reduced, but that this is advantages can be summarised as follows:
offset by the much higher content of hydrolysate in the
complete formulation. Environment
The properties of the pigments are summarised in Table 3. It - Zinc content in the formulation is reduced to approximately
should be noted that the zinc flake has a small particle size 25% by mass;
and a specific surface area four times higher than the zinc - Zinc content of the dry film at 11.7% by volume is 4.5 times
dust used, and a very high anodic activity. On the other lower than in standard zinc dust primer formulations.
hand, the zinc dust has a low specific surface and surface
activity. The filler used was a china clay which is chemically Technology
inert and has a lamellar structure. - Hydrolysate is stable (for more than 6 months) yet gives
fast hardening;
Extended pot life - Very simple formulation;
The formulation and basic properties of the optimised zinc - Good dispersion without additives;
flake/zinc dust primer are presented in Table 2 and 4 and - Low settlement (no additive needed);
compared with those of a standard zinc dust primer [3]. The - Good spraying properties;
formulation of both hydrolysates and primers are shown. - Pot life more than 8 hours.
A very important market demand was that the composition
should have a pot life of more than eight hours after mixing Coating properties
of the hydrolysate with the pigments (2K system). The - Dry film thickness: 70-80µm
development of a new formulation of hydrolysate (Table 2) - Very good cathodic protection with reduced levels of zinc;
and the use of two zinc pigments with different particle - Salt spray resistance =1300 hours (=55 days) without rust;
shape and surface activity achieved a pot life of about 10-15 - Natural weathering: = 21 months without rust (test
hours (Table 4). This pot life was determined as ideal for continuing)
coatings with sufficient hardening, good solvent resistance - Good solvent resistance after 24 hours to isopropanol and

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Quelle/Publication: European Coatings Journal
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methyl ethyl ketone; in Lausanne, Switzerland. He joined Eckart Switzerland in


- Good adhesion after 24 hours and 7days - Gt0 to DIN EN 1982. He is currently sales manager for zinc products and
ISO 2409; responsible for zinc activities development at Eckart
- Very low tendency to white rust formation; Switzerland.
- Very hard and non-porous structure; -> Dr. Tom Schuster obtained his PhD in chemistry at
- High barrier effect; Aachen, Germany, in 1987. After working abroad for several
- No blistering or pinholing; years, he returned to Germany in 2001 and became head of
- Good mechanical properties. R&D at Eckart. He is also responsible for marketing of
protective coatings.
Particle shapes are the key to adequate protection
The use of two zinc pigments with different particle shapes
(flakes and spherical) has allowed an ethyl-silicate based
primer formulation to be developed with a significantly
reduced zinc content.
This mixture of particle shapes increases the number of
possible electrical contacts between particles, and in this
way compensates for the low zinc content in the system and
allows coatings to be obtained which offer high corrosion
protection.
In addition, the zinc flakes create a very good barrier effect.
The final result is a coating with high packing density and
mechanical properties without the porous structure,
blistering, pinholing or white rust often associated with this
type of primer. The results achieved exceeded the market
requirements for these coatings at a film thickness of
70-80µm.

REFERENCES
[1] E. V. Schmid, Wetter und Korrosionsschutz, Vincentz
Verlag, 1983, p. 392
[2] K. Barton, O. Kusnierik, J. Lapka, Koroze a Ochrana
Materialu, 1985, 29, No 3, pp. 44-47
[3] Wacker-Chemie GmbH, 2000, Bindemittel für
anorganische Zinkstaubfarben
[4] Andreas Tomanek, Silicone & Technik, Wacker Chemie
GmbH, 1990, München
[5] M. Mitchell, M. Summers, Protective Coatings Europe,
vol. 8, No 7, pp.12-15
[6] Clive H. Hare, Stephen J. Wright, Journal of Coatings
Technology, vol. 54, No 693, October 1982, pp. 65-76
[7] M. Taylar, G. Terzakis, Protective Coatings Europe, vol.
8, No 1, January 2003, pp. 4-8
[8] L. Kruba, P. Stucker, T. Schuster, Pitture e Vernici, N0 8,
vol 81, 2005, pp. 51-58

Results at a glance
- An ethyl-silicate based zinc primer formulation has been
developed which offers very good corrosion protection with
a much lower metal content than normal.
- The combination of zinc particles with two different shapes
(flakes and spherical) increases the electrical contact
between the particles and so maintains cathodic protection
at lower zinc contents.
- In addition, the zinc flakes provide a barrier effect and a
high packing density.
- The new formulation has also been shown to avoid the
problems of porous structure, blistering, pinholing and white
rust which are commonly found with this type of primer.

The authors:
-> Dr. Ljudmila Kruba graduated from the
Chemistry-Technological Mendeleev Institute in Moscow
and then worked at the Moscow Coatings Research
Institute, receiving her PhD in 1987. Since 2000 she has
worked for Doral and Eckart Switzerland in research and
development on zinc-based coatings.
-> Dr. Pierre Stucker obtained his PhD in chemistry in 1976

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Figure 1: Visual comparison of the primer surfaces after salt spray testing: a) standard
zinc dust (900 h), b) zinc flake/zinc dust primer (1300 h)..

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Figure 2 a-b: Comparison of the primer surfaces under microscope after salt spray
testing.

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Figure 3: Cross-section of standard zinc dust (a) and zinc flake/zinc dust (b) primers
after salt spray testing.

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Figure 4: Comparison of the surfaces of the standard zinc dust (a) and zinc flake/zinc
dust (b) primers after 21 months' weathering exposure.

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