ZINC SILICATE OR ZINC EPOXY AS THE PREFERRED HIGH PERFORMANCE PRIMER

Mike J. Mitchell International Protective Coatings Akzo Nobel

For many years the conventional wisdom when designing anti-corrosive paint systems for long lifetimes has been to utilise zinc primers. The type of primer normally specified has been zinc silicate, typically zinc ethyl silicate. This is because within the parameters of zinc silicates the solvent based ethyl silicates have been found to be more generally tolerant than the water based alkali metal zinc silicates. This technology has been especially dominant in the U.S.A. The reason for using this type of technology has been discussed many times but is primarily related to the fact that zinc silicates can be pigmented at extremely high levels of zinc dust giving zinc-zinc metal contact and, consequently, excellent cathodic protection properties akin to those obtained from galvanising. Due to the difference between S.Gs of what is basically a silica matrix (at 2.5) and cured epoxy (at 1.1), consideration of the level of zinc present in a film by weight is almost irrelevant when comparing these two binders (or any organic binder with a silicate binder, although it is relevant when considering performance within the same binder type). Table 1 illustrates the differences in volume terms between typical commercial zinc rich products, normally around 86% w/w for zinc silicate, and often 90% w/w for zinc epoxy. Table 1 Zinc Silicate 86% w/w Zinc Dust Weight Volume 86 12.1 5 1.9 9 3.6 68.8 79.5 Zinc Epoxy 90% w/w Zinc Dust Weigh Volume 90 12.7 1 0.4 9 8.1 59.9 61.8

Zinc Dust Additives Binder % Zinc Dust by Volume Pigment Volume Concentration

Worldwide experience has shown that the performance of single coat zinc silicate systems is significantly greater than that which can be obtained from single coat zinc epoxies. This has been shown by the performance as a single coat on refineries, offshore platforms and bridges in locations as diverse as Japan, Australia and the U.S.A. This field experience is backed up by much laboratory data both from accelerated corrosion and electrochemical testing.

The performance of single coats of zinc silicate has been confirmed by our own work [Figure 1], where ASTM B117 salt spray testing shows less corrosion in the scribe for zinc silicate and epoxy, and electrical impedance testing [Figure 2] shows galvanic protection from the zinc silicate for prolonged periods, and zinc epoxies for much less. All of these results can be clearly explained by the volume of zinc in the dry film as shown in Table 1. Figure 1

Zinc Silicate (50 microns d.f.t.) 1000 Hrs ASTM B117 Salt Spray (28x mag. Stripped area at scribe)

Zinc Epoxy (50 microns d.f.t.) 1000 Hrs ASTM B117 Salt Spray (28x mag. Stripped area at scribe)

Figure 2
Corrosion Potential vs Time for Primers
0 0 -200 Ecorr/mV vs SCE -400 -600 -800 -1000 -1200 Time/Days 50 100 150 200 Zinc Silicate Zinc Epoxy 250

However, it is interesting to note that that when zinc silicates are evaluated in the more recent ASTM G85 Prohesion test, which is wet and dry cycling with primarily an ammonium sulphate fog rather than sodium chloride, that this difference is much less clear cut [Figure 3]. These results perhaps illustrate some of the history and reasons for the domination of zinc silicate based systems in the Protective Coatings Industry, given that until a few years ago the salt spray was the predominant method of accelerated corrosion testing.

Figure 3

Zinc Silicate (60 microns d.f.t.) 1000 Hrs Prohesion (28x mag. Stripped area at scribe)

Zinc Epoxy (65 microns d.f.t.) 1000 Hrs Prohesion (28x mag. Stripped area at scribe)

The use of zinc silicate on a worldwide basis for high performance anti-corrosive systems has been linked to a number of other phenomena. The advent of grit blasting which allowed the production of the clean angular surfaces necessary to obtain good adhesion and electrical contact for these unusual paints (with organic coatings adhesion is often related to the presence of polar groups). The growth of the Oil Industry, especially for offshore production, has been high over the past years, with an expectation of long term corrosion protection. Initially the silicate was the primer for largely thermoplastic systems but in recent years epoxies and polyurethanes have replaced these.

The second of these items has been most critical as much of the worldwide oil industry has emanated from the Mexican Gulf region, and engineers in this area have greatly influenced U.S. engineering, generally with a consequential influence on anti-corrosion paint specifications on a worldwide basis. The formulation and chemistry of zinc silicates is quite complex, giving the benefits of the technology, as well as a number of consequent problems. Adequate films only form when the coating is pigmented above the Critical Pigment Volume Concentration (CPVC), i.e. the polymer present does not fill all of the voids between the pigment particles and, consequently, the film is porous. With typical zinc silicates up to one third of the dry film can be air space. When attempts are made to pigment at lower levels to allow this space to be filled with polymer then the propensity for the film to crack on curing is greatly increased. Thus the zinc silicate film is inherently porous, causing difficulty in overcoating due to air release from the porous primer. In the greatest majority of cases zinc silicate is topcoated. As the topcoat soaks into the zinc silicate, air is forced out which can cause popping or pinholing in the topcoat. There are well established methods of attempting to alleviate this problem, in North America the general procedure is to apply a mist coat of the coating specified to be applied over the zinc silicate. In practice this is the intermediate coat thinned down and applied as a separate coat and allowed to flash off prior to application of the full intermediate coat. Because this coating is often specified as a possible option rather than part of the full specification, it is often the cause of many contractual wrangles in practice. In Europe the tendency has been to use a separate coating as a tie coat or sealer coat for the zinc silicate, formulated specifically to penetrate and seal off the porous zinc silicate. This, in my opinion, greatly clarifies the situation and is also the most efficient method of overcoating the zinc silicate. The pinhole phenomena should not be underestimated, various offshore surveys have suggested that these are one of the primary causes of paint systems having shorter than expected lifetimes.

Traditionally in the U.S.A. the fabrication process has been such that the problem of the porosity of zinc silicate was alleviated because the primer was allowed to weather for prolonged periods before application of the topcoat system. In this time the zinc particles could react with moisture and atmospheric carbon dioxide to form zinc salts, which can fill up the porosity, giving a more densely packed film. Provided these salts are efficiently removed from the surface, then the coating becomes much easier to overcoat as the film has much reduced porosity. Now in many countries the fabrication process is such that all of the painting is done as one process on one site (this is now also more the case in the U.S.A.), which means there is no weathering of the zinc silicate, no salt formation, and no reduction in porosity. Consequently, the potential problems with pinholing are large and real. The second unique feature of zinc silicates compared to normal organic coatings is their curing mechanism. With the most widely used solvent based zinc silicates this is basically a moisture curing reaction, which is also believed to involve some reaction with the metallic zinc and the steel surface. This reaction only occurs when there is sufficient moisture present in the atmosphere, typically a minimum relative humidity of 50-60%. If this humidity is not present during the drying process there is a danger of silica just precipitating out and then there is a danger that optimum film strength may never be obtained, even with subsequent steaming or water spraying. In the U.S.A. this has been less of a problem because much offshore fabrication and painting has been done in the Mexican Gulf area, where temperatures and relative humidities are high. Also, where the fabrication process is undertaken in the traditional way, where the zinc silicate primer is allowed to weather, then the build up of zinc salts in the porosity of the film also helps increase the mechanical strength. In my experience problems with zinc silicate based systems tend not to be in long term performance when everything is done absolutely correctly, but rather in the following ways:(a) (b) Breakdown at pinholes as previously described. Inadequate cure, giving cohesive failure when overcoated with high build epoxy systems, apparent when not being able to spot blast to a sound edge and also suffering from extensive mechanical damage, edge breakdown etc. This has been the mode of failure of many zinc silicate based systems applied under difficult curing conditions, and has also resulted in first maintenance taking place after 1-2 years rather than the expected 10 years.

The conventional wisdom has always been that zinc silicates and zinc silicate based systems will always out-perform zinc epoxy and zinc epoxy based systems, however, although this is clear with single coat primers the situation is not as obvious when considering topcoated systems. This has led, in Europe primarily, to a re-evaluation of the performance of various zinc primed systems, by both paint manufacturers and external bodies, to attempt to determine whether there are real benefits to be gained by using zinc silicate primers. TOPCOATED ZINC PRIMERS The first series of work, run in conjunction with the accelerated corrosion testing of the single coat primers, took the same primers overcoated with a thin coat (60 microns dry film thickness) of polyurethane aluminium and subjected to the same corrosion tests. These results are shown in Figure 4 and illustrate clearly that in a topcoated situation there is little difference in corrosion (rust build up) at the scribe. Again, the E.I.S. results confirmed the accelerated test results, with little difference being observed between epoxy and silicate zinc primers and readings being difficult to obtain in most cases, especially in the early stages. Results were very dependent on thickness of the topcoat and the time for the electrolyte to penetrate to wet out the zinc (and steel) is dependent on this. This largely explains a

variation in time reaching the most negative potential (potential of zinc). After this, when steel is wetted the potential rises. After around 600 days all systems were showing the potential of steel and testing was terminated [Figure 5]. Figure 4

Zinc Silicate (60 microns) Polyurethane (60 microns) 1000 Hrs Salt Spray 28x mag. Stripped area.

Zinc Epoxy (65 microns) Polyurethane (70 microns) 1000 Hrs Salt Spray 28x mag. Stripped area.

Zinc Silicate (80 microns) Polyurethane (80 microns) 1000 Hrs Prohesion 28 mag. Stripped area.

Zinc Epoxy (70 microns) Polyurethane (80 microns) 1000 Hrs Prohesion 28x mag. Stripped area.

Figure 5 Corrosion Potential of Topcoated ZRPs, in 0.5m NaCl (Equilibrated with Air)
Time/Days
100 120 130 140 170 200 230 250 280 305 330 340 360 420 460 510 550 570 610 75 0
0

Corrosion Potential (mV)

-200 -400 -600 -800 -1000

Zinc Epoxy/PU Zinc Silicate/PU

HIGH BUILD ANTI-CORROSIVE SYSTEMS The effect of using thicker high build topcoats was then investigated, in this case utilising conventional high build epoxy technology. Testing was undertaken using Salt Spray (ASTM B117), Prohesion (ASTM G85) and E.I.S. Accelerated corrosion testing lasted in excess of 7000 hours, at which time no face breakdown was evident on any of these two coat systems [Figure 6]. This is not an unusual feature of high performance coating systems, and to attempt to show differences normally careful and thorough examination of an intentionally damaged area (scribe) is made. Here the criteria is the amount of underfilm creep or corrosion emanating from the damage. Assessments are made visually and finally by evaluation of underfilm corrosion following removal of the coating. No significant differences could be observed between zinc epoxy and zinc silicate primed systems. At the same time, panels were exposed at an aggressive coastal/industrial site (probably best described as CSI/M in ISO 12944), around 3-4 metres from the sea and near to output from a power station and aluminium smelter. After one year no differences could be observed.

Figure 6

Zinc Silicate/Tie Coat/HB 7152 Hrs Prohesion

Zinc Epoxy/HB 7152 Hrs Prohesion

Zinc Silicate/Tie Coat/HB 7152 Hrs ASTM B117

Zinc Epoxy/HB 7152 Hrs ASTM B117

With regard to E.I.S. testing, after 961 days no corrosion potential was measurable due to thickness of the topcoat (120-150 microns), i.e. insufficient electrolyte is in contact with the zinc primer [Figure 7]. Figure 7 - Corrosion Potential vs Immersion Time of Zinc Primers/High Build, in 0.5 NaCl (Equilibrate with Air)
Time Days 800 -280 Corrosion Potential (mV) Zinc Silicate/HB -290 Zinc Epoxy/HB 900 1000

-300

-310

-320

ACCELERATED CORROSION TESTING OF TYPICAL SYSTEMS USING ZINC SILICATE OR ZINC EPOXY PRIMER The systems described to date are simplified versions of those normally used. They were of relatively low total dry film thickness and contained no weather resistant topcoat. In practice, in most instances in aggressive environments, 3-4 coat systems are used, typically with a total dry film thickness of 250-350 microns. These thicknesses are typical of those found for high durability systems in ISO 12944 for aggressive environments C5I and C5M. Table 2 shows results for various generic systems of this type tested by both cyclic test (prohesion, drying and QUV ASTM D5894), salt spray (ISO 7253) and prohesion (ASTM G85). In no cases does any face breakdown occur and judgement once again must be made on the basis of underfilm corrosion at the scribe. For comparison, non-zinc primed systems are also shown. It can be clearly seen from these, that despite higher overall dry film thicknesses, benefits are obtained from the zinc primers in corrosion creep from the scribe. This can be translated to performance at damaged areas and edges.

The conclusions which can be drawn are that there is no significant difference between the zinc epoxy based system and the zinc silicate based system, and that both zinc based systems give better performance than epoxy barrier coats direct to steel. Table 2
System Zinc Silicate Tie Coat HB Epoxy Acrylic Urethane 75m 25m 200m 50m 350m 75m 200m 50m 325m 75m 125m 200m 75m 125m 200m 75m 125m 200m 75m 145m 220m 75m 125m 225m 500m Test Method ASTM D5894 Cyclic (4200 Hours) Result 2mm scribe creep. No film defects.

Zinc Epoxy HB Epoxy Acrylic Urethane

ASTM D5894 Cyclic (4200 Hours)

2mm scribe creep. No film defects.

Zinc Silicate HB Epoxy MIO

ASTM G85 Prohesion (6000 Hours)

5mm scribe creep. No film defects.

HS Zinc Epoxy HB Epoxy MIO

ASTM G85 Prohesion (6000 Hours)

5mm scribe creep. No film defects.

Zinc Epoxy HB Epoxy MIO

ASTM G85 Prohesion (6000 Hours)

5mm scribe creep. No film defects.

Zinc Silicate HB Epoxy MIO

ISO 7253 Salt Spray (6000 Hours)

1.5mm scribe creep. No film defects.

Zinc Epoxy HB Epoxy MIO

ISO 7253 Salt Spray (6000 Hours)

1mm scribe creep. No film defects.

Epoxy Mastic

ASTM D5894 Cyclic (4200 Hours) ASTM D5894 Cyclic (4200 Hours) ASTM G85 Prohesion (6000 Hours)

4mm scribe creep. No film defects. 7mm scribe creep. No film defects. 6.5-7mm scribe creep. No film defects.

Epoxy Glass Flake

350m

Epoxy Mastic Epoxy Mastic

150m 150m 300m 450m

Epoxy Mastic

ISO 7253 Salt Spray (6000 Hours) ISO 7253 Salt Spray (6000 Hours)

3.5mm scribe creep. No film defects. 4.5mm scribe creep. No film defects.

Epoxy Mastic Epoxy Mastic

225m 225m 450m 500m 500m 1000m

Epoxy Glass Flake Epoxy Glass Flake

ISO 7253 Salt Spray (6000 Hours)

4.5mm scribe creep. No film defects.

EXPOSURE TESTING OF TYPICAL SYSTEMS USING ZINC SILICATE OR ZINC EPOXY PRIMER Exposure results in an aggressive coastal environment are shown in Table 3. Again, it can be seen that there are insignificant differences between the zinc epoxy and zinc silicate based systems. All zinc primed systems perform better than those without zinc primer. Table 3
System Zinc Silicate Tie Coat HB Epoxy Acrylic Urethane 75m 25m 200m 50m 350m 75m 200m 50m 325m 500m Test Method 30 Months Coastal/Industrial Exposure (Sea 3-4m at high tide) Result 1mm scribe creep. No film defects.

Zinc Epoxy HB Epoxy Acrylic Urethane

30 Months Coastal/Industrial Exposure (Sea 3-4m at high tide)

0mm scribe creep. No film defects.

Epoxy Mastic

30 Months Coastal/Industrial Exposure (Sea 3-4m at high tide) 30 Months Coastal/Industrial Exposure (Sea 3-4m at high tide) 30 Months Coastal/Industrial Exposure (Sea 3-4m at high tide)

4.2mm scribe creep. No film defects. 20mm scribe creep. No film defects. 1-2mm scribe creep. No film defects.

Epoxy Glass Flake

350m

Epoxy Primer Epoxy Glass Flake

25m 375m 400m

OTHER EVALUATIONS Largely because of unexpectedly short times to major maintenance for anti-corrosive systems on offshore structures, the Norwegian Government has required all parties of the Norwegian Offshore Industry to come together to determine methods of selecting better coating schemes. Many of the original problems are believed to be due to failure within the zinc silicate, most likely because of poor curing, (in cold climates fabrication takes place inside, when cold air at relatively low relative humidity is warmed up the RH becomes even lower). Concurrent with this, there has been a major shift by fabrication yards to move away from zinc silicates because of the problems already described, even the construction of environmentally controlled paint shops has not proved totally effective. Prior to commencement of this work, largely undertaken by the SINTEF Materials Technology Group at Trondheim, the widely held belief was that zinc silicates, applied correctly, would give undoubtedly superior performance to any other systems. The work undertaken at SINTEF consisted of comparing field exposure (actually exposed on an offshore platform) with the results obtained from various accelerated corrosion tests. The conclusion drawn from these tests was that there were no penalties in performance from using zinc epoxy based systems and, in fact, in some instances, these appeared to perform better than those based on zinc silicate. Significant productivity improvements have been made in offshore fabrication by moving away from zinc silicates.

IMPACT AND OTHER DAMAGE RESISTANCE One reason widely given for using zinc silicate rather than zinc epoxy primers is a claimed greater resistance to handling damage. To verify this, panels were prepared with zinc silicate and zinc epoxy as single coats and topcoated. The normal laboratory method of damaging panels by a controlled cut is not really representative in any of practical damage which is caused by impact or gouging. In this type of damage the relatively soft zinc metal can be smeared on to the surface and left in the blast profile, giving a degree of protection for a period depending upon the environmental conditions. Following the gouging impact the primers alone and the topcoated systems were examined by scanning electron microscopy and were also subjected to XRMA for elemental mapping [Figure 8]. Results obtained were as follows. As would be expected from previous experience with zinc silicate primers, with the untopcoated panels significantly more zinc was left on the surface with the silicate than with the epoxy zinc. With the silicate the zinc did appear to be smeared over the surface, whereas with the epoxy zinc only a few discreet spheres were apparent and, in terms of quantity, significantly less. When the primers are topcoated prior to testing, then in both systems only traces of zinc remain on the surface. In this instance the zinc silicate, although cured to solvent resistance, may not have fully cured and, consequently, gives a cohesively weaker film than previously. This result appears to represent what is often observed in practice. Figure 8

Zinc Silicate

Zinc Epoxy

Zinc Silicate/Polyurethane

ZincEpoxy/Polyurethane

CONCLUSION The work undertaken and the data surveyed both confirm the widely held view that single coat zinc silicate primers will give better performance than single coat zinc epoxies, at equal film thicknesses and when both materials meet accepted definitions of zinc rich. However, the conclusion to be drawn from both in-house and external work is that when these primers are topcoated very similar performance is obtained from a wide range of corrosion tests. This allows the eminently more practical and user friendly zinc epoxy to be used as the basis for high performance anti-corrosive specifications, rather than zinc silicate, thus avoiding problems of mudcracking, poor cure at low humidities and pinholing. Zinc epoxy based systems will give consistent quality, together with controlled rapid build up of paint systems during the construction process. One further interesting feature to note is that with current technology it does not appear likely that solvent based zinc silicates can be formulated at less than 250 g/litre VOC, and water based alkali silicates, although giving occasions good results have been shown to exhibit very limited tolerance to application conditions. It has been possible for many years to formulate zinc epoxies at less than 250 g/litre VOC, albeit often slow curing and somewhat impractical products. However, recent advances in epoxy curing agent technology has allowed the formulation of faster and lower temperature curing higher solids epoxies which are now being sold in the U.K. to meet the very strict VOC legislation now enforced.