February 3– 6, 2020 | Long Beach, CA

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“Challenging the Organic “Zinc Rich” Primer Standard”

By Alex Yagüe, R&D Senior Chemist,

Pinturas Hempel, Polinyà, Barcelona, Spain
David Morton, Chief Scientist
Hempel A/S, Lyngby, Copenhague, Denmark

Presented at Coatings+ 2020

February 3–February 6, 2020
Long Beach, CA

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 CHALLENGING THE ORGANIC “ZINC RICH” PRIMER STANDARD

Alex Yagüe, R&D Senior Chemist,

Pinturas Hempel, Polinyà, Barcelona, Spain
David Morton, Chief Scientist
Hempel A/S, Lyngby, Copenhague, Denmark

ABSTRACT

Zinc-rich primers are often the primer of choice during new construction of assets placed
offshore for oil & gas production. The SSPC-Paint 20 specification covers both inorganic
(Type I) and organic (Type II) highly pigmented zinc-rich coatings and the level of zinc dust
is classified by the weight of zinc in the dried film. Oil & gas specifications demand at least
Level 2 (≥ 77% and less than 85%) to meet the performance demands of this specification and
the harsh conditions experienced when offshore.

In conventional zinc-rich epoxy primers (Type II) the high levels of zinc are achieved by
adding large amounts of zinc dust particles into an epoxy matrix as a pigment. The dispersion
of the zinc is crucial to ensure electrical contiguity and hence galvanic protection of steel.
Formulation is critical to ensure the correct PVC/cPVC ratio to ensure both galvanic
protection and adequate adhesion plus mechanical properties.

This paper will examine the formulation and performance of new, activated zinc epoxy
primers compared to conventional zinc-rich epoxy primers. We will demonstrate comparable
corrosion resistance at reduced zinc levels in the dried film (Level 3 ≥65%) and show that zinc
metal levels can be reduced to as low as 31% by weight without compromising galvanic
corrosion protection while improving adhesion and mechanical properties of the dry film.
 INTRODUCTION

There is nothing new about the advantages of using zinc-rich primers to protect carbon steel
from corrosion. It was more than 80 years ago when the first zinc-rich primers with zinc
particles bound together with a polymer was used to protect steel.
Nowadays, Zinc-rich primers are often the primer of choice during new construction of
assets placed offshore for oil & gas production. The SSPC Paint Specification No.20 covers
both inorganic (Type I) and organic (Type II) highly pigmented zinc-rich coatings that are
uniquely defined by their capabilities for protecting steel exposed at film discontinuities. The
level of zinc is classified according the weight of zinc dust (as defined in ASTM D 520) in the
dried film.

• Level 1: equal to or greater than 85%

• Level 2: equal to or greater than 77% and less than 85%
• Level 3: equal to or greater than 65% and less than 77%

Oil & gas specifications demand at least Level 2 (≥ 77% and less than 85%) to meet the
performance demands of this specification and the harsh conditions experienced when
offshore.
In conventional zinc-rich epoxy primers (Type II) the high levels of zinc metal are
achieved by adding large amounts of zinc dust particles into an epoxy matrix as a pigment.
The dispersion of the zinc is crucial to achieve electrical contiguity and hence galvanic
protection of steel. Additionally, formulation is critical to obtain the correct PVC/cPVC ratio
to ensure both galvanic protection and adequate adhesion in addition to mechanical properties.

In this type of coatings, zinc sacrifices itself protecting the steel substrate which becomes
the cathode. The resistance to corrosion is dependent on the transfer of galvanic current by the
zinc primer. As long as the conductivity in the system is preserved and there is sufficient zinc
to act as anode the steel will be protected galvanically. Therefore zinc pigment particles in
zinc primers need to be packed closely together and they are typically formulated with very
high loadings of zinc dust.

Traditionally, zinc dust loadings of 80-85% by weight have been used in order to provide
long term corrosion protection to the steel (1,2). However, it has also been demonstrated that
the morphology of the particles of zinc used (spherical, lamellar) has a meaningful influence
on the final properties of the coatings (3). When lamellar zinc has been used as pigment the
final films exhibit higher electrical contact and better superficial distribution of protective
current leading to an improved cathodic protection of the substrate. Moreover, the lamellar
shape of the pigment improves the barrier properties of the primer and provides, overall,
better anti-corrosive properties to the final coating compared to spherical zinc dust. This
would allow to formulate zinc primers with a lower amount of zinc in the dry film whilst
keeping or even improving its properties in terms of corrosion protection and mechanical
properties.

Previous studies on traditional zinc-rich epoxies showed that only the zinc in the first 20-
30 microns of the coating can provide galvanic protection (4). As a normal zinc coating is
around 60-80 microns, approximately two-thirds of the zinc is too far away from the point of
corrosion to be able become oxidised, and so it is not able to protect the steel against
corrosion.

A new generation of activated zinc-rich primers improved the galvanic effect of these
coatings without increasing the zinc content (5), as this new technology increased the zinc
particles’ ability to release electrons and ensure zinc throughout all the film was providing
anti-corrosive protection.

The combination of this technology with new raw materials such as zinc flakes allows the
formulation of a third generation zinc primers with a reduced amount of zinc while keeping its
outstanding performance in terms of mechanical and anti-corrosive properties.

The percolation threshold is the lowest concentration of filler/pigment at which an

insulating material -e.g. epoxy resin- is converted to a conductive material. This means
that percolation threshold is the lowest concentration of filler at which an electrical pathway is
formed throughout a sample. The percolation threshold of zinc flakes may be up to three
times lower (in volume) than for standard zinc dust and, therefore, the amount of zinc flakes
required to catholically protect a substrate is much lower than with zinc dust.

Nevertheless, the coatings industry is still driven by different regulations such as SSPC-
Paint 20, which was issued in 1982 for the first time, that define the amount and type of zinc
that a zinc primer needs to contain. In addition, other standards (e.g. ISO 12944) even
determine the thickness and number of layers of the protective paint systems to protect an
structure in a define corrosive environment. Considering that paint industry is very
conservative, owners use to demand coatings/systems that fulfil these regulations despite of
proving similar or even better performance with innovative products.

This paper will examine the formulation and performance of new, activated low zinc epoxy
primers compared to conventional zinc rich epoxy primers. We will demonstrate comparable
corrosion resistance at reduced zinc levels in the dried film (Level 3 ≥65%) and show that zinc
metal levels can be reduced to as low as 31% by weight without compromising galvanic
corrosion protection. while improving adhesion and mechanical properties of the dry film.
 EXPERIMENTAL PROCEDURE

Salt Spray Test (SST), according to ISO 9227, neutral salt spray (8).
This method is performed in order to evaluate the corrosion resistance of a coating system
by reproducing the corrosion that occurs in atmosphere containing salt spray or splash.
The operation conditions of the salt spray test are constant spray with 5% NaCl solution at
35°C.

After ending of the exposure, blistering and rust are evaluated on both panel and around
the score (in mm from centre), according to ISO 4628-2 and ISO 4628-3, respectively.
Cracking is evaluated according to ISO 4628-4. Adhesion is evaluated according ISO4624
(pull-off tests).
After removing the coating at a score by a suitable method (mechanical or chemical
cleaning), the width of the corrosion is measured at nine points. The rust creep M is calculated
from the equation M = (C − W)/2, where C is the average of the nine width measurements and
W is the original width of the scribe (0.5 mm / 0.020 in).
Tests done on steel panels coated with 1x70 μm (2.8mils) of the paint tested. The steel
panels (10 x 15 cm x 1.6 mm ; 3.94 x 5.91 x 0.063 in) are cold rolled mild steel, and 50~75
μm blast profile.

RESULTS
Six primers with different zinc content (from 80 to 31% in weight in the final dry film)
were tested according to SST and the degradation of coatings was evaluated after 1000 and
2000 hours as per ISO 4628 (7). The amount and shape of zinc in each coatings is presented
in Table 1.

Table 1. Composition of the six coatings evaluated in SST. Amount and type of zinc used in each primer is
defined. Additionally, it is also stated the presence or not of zinc activation technology.

Amount of zinc in the Type of zinc Activated zinc

Type of coating
dry film (% in weight) technology?
Primer 1 Type 2 Level II 80 Dust No
Primer 2 Type 2 Level III 65 Dust No
Primer 3 Type 2 Level III 65 Dust Yes
Primer 4 Type 2 31 Dust No
Primer 5 Type 2 31 Flake/Dust Yes
Primer 6 Type 2 31 Flake/Dust Yes

Results after 1000 h of SST

After 1000 hours in SST significant differences in the performance of the primers were
already observed (Figure 1). Primer 3 with 65% of zinc dust exhibited the best anticorrosive
performance (only minor red rust in the scribe), showing even better results than Primer 1
which contains 80% of zinc in the dry film. A higher oxidation of zinc in Primer 3 due to the
activation technology may explain this difference. Moreover, Primer 2, with the same amount
of zinc than Primer 3, already presented some rusting points. This results will confirm than
traditional zinc-rich primers need zinc loadings over 80% in weight to provide a consistent
cathodic protection to the steel through all the structure.
On the other hand, when comparing the low zinc coatings (Primers 4, 5 and 6) it was
clearly demonstrated that cathodic protection only occurred when zinc was activated (Primers
5 and 6). It is also worthy to mention that Primer 5 presented a high amount of white salts
(zinc salts) along all the panel due to the oxidation of zinc. Finally, this result also proved that
primers with only 31% of zinc can provide galvanic protection to the steel.

Primer 1 Primer 2 Primer 3

 Primer 4 Primer 5 Primer 6

Figure 1. Panels coated with the six different zinc primers (70-80 µm) after 1000 hours of exposure to salt fog.

Results after 2000 h of SST

Salt fog exposure test was continued up to 2000 hours (Figure 2), beyond laboratory tests
requirements defined in SSPC- Paint 20 which for Type II coatings only demands 1000 hours
of SST.
Degradation of Primers 2 and 5 continued showing a higher rusting degree. Additionally,
significant rust point were observed on Primer 1 (80% zinc) contrasting with the performance
of Primer 3 which only presented slight red rust on the scribe although the zinc dust in the dry
film was only 65%.

On the other hand, Primers 5 and 6 were still exhibiting and excellent corrosion resistance
considering that the content of zinc was only 31%.
 Primer 1 Primer 2 Primer 3

Primer 4 Primer 5 Primer 6

Figure 2. Panels coated with the six different zinc primers (70-80 µm) after 2000 hours of exposure to salt fog.

CONCLUSIONS
First of all, it has been demonstrated that epoxy primers with a zinc content in the dry film
lower than 65% (Level 3) passed the requirements defined in SSPC-Paint 20 Accelerated
Laboratory Weathering Test. Additionally, Primers 5 and 6, with only 31% of zinc weight,
exhibited outstanding anti-corrosion properties lasting more than 2000 hours of salt fog
exposure test.
Secondly, these results also show that the content of zinc in epoxy primers is not directly
related with the performance of the final coatings and, therefore, paints with low content of
zinc can outperform traditional zinc-rich primers. Activation of zinc has been proven as a
critical factor to provide galvanic protection to steel when the quantity of zinc in the final film
was below 80% in weight.
Finally, the aim of this paper -supported by the experimental results- is to challenge the
traditional standard, where the amount and type of zinc use in epoxy zinc-rich primers is
defined, to review their requirements since new raw materials and technologies are enhancing
the performance of these primers despite of the amount of zinc content.

REFERENCES
(1) András Baczoni, Ferenc Molnár, Advanced Examination of Zinc Rich Primers with
Thermodielectric Spectroscopy, Acta Polytechnica Hungarica, Vol. 8, No. 5 (2011).
(2) Clive H. Hare, Zinc loadings, cathodic protection, and post-cathodic protective
mechanisms in organic zinc-rich metal primers, Journal of Protective Coatings and Linings,
September (2001).
(3) J.R. Vilche, E.C. Bucharsky, C.A. Giudice, Application of EIS and SEM to evaluate
the influence of pigment shape and content in ZRP formulations on the corrosion prevention
of naval steel, Corrosion Science, 44, p. 1287–1309 (2002).

(4) Kathy Riggs Larsen, “Zinc-rich Epoxy Primer Uses Glass Spheres, Zinc Activator to
Enhance Corrosion Resistance”, Materials Performance (2016).
(5) Santiago Arias, Jose Luna, Novel Zinc Primers with Enhanced Protection and
Mechanical Properties, NACE International,NACE-2014-3979 (2014).
(6) ISO 12944-5:2007. Corrosion protection of steel structures by protective paint systems
-- Part 5: Protective paint systems.

(7) ISO 4628:2003. Evaluation of degradation of coatings -- Designation of quantity and

size of defects, and of intensity of uniform changes in appearance -- Part 2: Assessment of
degree of blistering. Part 3: Assessment of degree of rusting. Part 4: Assessment of degree of
cracking.

(8) ISO 9227:2012. Corrosion tests in artificial atmospheres -- Salt spray tests.