"PERFORMANCE TESTING OF ANTI-CORROSIVE COATINGS David A.

Claydon International Protective Coatings Akzo Nobel England

Abstract: The Protective Coatings Industry still lacks a globally recognised laboratory test protocol for the evaluation of high performance coating systems prior to field use. The advent of new and more stringent VOC legislation has resulted in new product technology entering the market place without extensive track record and as such, laboratory performance testing has become increasingly important. The key to successful testing is in attempting to correlate with actual field exposure, i.e. predicting any mode of failure. This paper will review the various approaches to performance testing under development in Europe and North America with particular emphasis on in -house work relating to the combination of accelerated cyclic corrosion testing and thermal cycling. INTRODUCTION As the Protective Coatings Industry moves into the 21st century, coating manufacturers can no longer rely on the extensive track records of their time served product ranges to convince customers of their suitability for use. As each day goes by these products are increasingly phased out due to the various strict VOC and raw material legislations around the globe, and there is nothing more certain than legislation becoming even more strict! Coating manufacturers have had to re-invent their product ranges using new and alternative technologies in order to meet both legislation requirements and customer performance expectations, without the luxury of proven long term performance in service. This has, of course, shifted the emphasis onto laboratory testing of the new coating materials and, in particular, accelerated anti-corrosive and crack resistance performance testing.

Over the last few years an increasing amount of performance based specifications have entered the market place or are currently being developed. These have been developed by both recognised standard institutes, e.g. ISO, NACE, and customer end-users, e.g. Shell, Norsok and Bridge Authorities. The principle aim with these specifications is for coating systems to meet a set of pre-determined laboratory performance based requirements that vary depending on the service end use. At this present time there is no globally recognised performance based specification that has full 100% industry acceptance, this is particularly true for the Oil and Gas market. There is a differing opinion in the methodology of the specification and the number of tests that need to be carried out. However, the goal is the same, in that it is to ensure high quality coating systems are approved for use. Laboratory prequalification testing has been particularly pushed to the forefront via the Offshore Industry due to the seriousness of their requirement for asset protection. The key to successful laboratory performance testing is being able to obtain some kind of correlation with field performance. It is important to note that there is no magical test that will accurately predict field performance and give assurances on expected lifetime. However, by utilising a range of tests the strengths and weaknesses of a given coating system can be determined and prevent inadequate product entering the market place. It is the scope of this paper to review the methodology behind various tests that can be used to predict the anti-corrosive and crack resistance behaviour of new coating systems. This paper will review both industry recognised methods and in-house methods that can be used and the valuable information they can provide.

CONDITIONS IN THE FIELD No sooner has a coating system been applied it is under attack from the various external stresses forced upon it by the surrounding environment. In the case of the offshore environment, this is a combination of extreme corrosive conditions, along with possible temperature fluctuations, UV exposure and the movement of moisture in and out of the coating film. If you combine this with the coatings own internal stress then you have a severe environment in which the coating has to perform. As time goes by, these stresses can take their toll on the coating system and make it more prone to failure, in the form of cracking or blistering failure, and subsequent corrosion onset. Some new coating systems will resist this better than others and thus extend the lifetime to first maintenance. Field performance testing in relevant environments does, of course, reproduce these conditions and any subsequent mode of failure over a period of years rather than months, and can be very site specific. In terms of laboratory performance testing, it is these conditions that need to be reproduced in an accelerated manner to provide correlation with any mode of failure in weeks or months rather than years. W e shall now look at laboratory tests used to evaluate the anti-corrosive properties of coating materials. LABORATORY PERFORMANCE TESTS Cyclic corrosion tests (CCTs) Accelerated cyclic corrosion tests are fast becoming the industry norm for the evaluation of the anti-corrosive behaviour of atmospheric coating systems. They have been shown to more accurately predict performance in the field than the traditional salt fog test (ASTM B117, ISO 7253). This has been well documented by various independent corrosion institutes and industry associations over the last 5-10 years, and although the author does not wish to labour the point here, reference will be made to this throughout this paper where relevant. The success of CCTs has revolved around the cyclic conditions of temperature fluctuation, UV exposure and degree of wet and dry out which is generated during the test, rather than the static set of conditions as in the salt fog test. This all adds up to impart a more realistic stress onto the coating system in an accelerated manner, something the salt fog test does not do. There are quite a few slightly differing CCT

methods documented but all are variations on a theme which normally includes a salt fog period, dry out or freeze period, and a UV/condensation period, all utilising standard industry available equipment. Descriptions of the common methods employed are detailed below:72 hours Salt Fog (ASTM B117, ISO 7253) with artificial sea water (ASTM D1141) Norsok Cyclic Test (based on NACE TM0184) 16 hours dry out (23C) 80 hours UV at 60C/ condensation at 50C, 4 hours/ 4 hours cycle (ASTM G53) Total duration = 25 weeks 168 hours Prohesion (ASTM G85, Annex A5) ASTM D5894 168 hours UV at 60C/ condensation at 50C, 4 hours/ 4 hours cycle (ASTM G53) Total duration = 24 weeks 168 hours Prohesion (ASTM G85, Annex A5) with artificial sea water (ASTM D1141) Draft NACE (Based on Shell) 168 hours UV at 60C/ condensation at 50C, 4 hours/ 4 hours cycle (ASTM G53) Total duration = 12 weeks 72 hours Salt Fog (ASTM B117, ISO 7253) 24 hours freeze at 20C Draft ISO 23040 72 hours UV at 60C/ condensation at 50C, 4 hours/ 4 hours cycle (ASTM G53) Total duration = 25 weeks All of these tests are employed in prequalification testing of coating systems. One can consider those tests which use the salt fog (5% NaCl) or artificial sea water as the electrolyte as being more akin to offshore conditions, whilst the ASTM D5894 test uses a blend of Sodium Chloride and Ammonium Sulphate which is more industrial or onshore.

Although the tests are slightly different, one thing that is constant is that a scribed area is placed into the coating test panel down to the substrate. This is required to represent a defect area and any subsequent corrosion onset, which is the principal mode of failure measured in this type of testing. This mode of failure manifests itself during test in the form of blistering at the scribed area as the corrosion creeps at the coating/substrate interface. Some of the blisters formed may fail further by cracking (see Photograph 1). This blistering mode of failure is commonly seen on field exposed test panels which have been scribed (see Photograph 2) therefore the mode of failure is very similar. The extent of blistering and possible cracking and the associated measured corrosion creep will allow comparisons of new systems against controls of known performance.

Differences in performance may well be observed for a given coating type when comparing between the ISO 20340 test, which has a thermal temperature gradient of 20C to +60C, against the remaining tests which have a smaller temperature gradient of +23C to +60C and do not include the low temperature freeze. An example, is given in Photograph 3. As you can see, there is a considerable difference in performance and highlights the importance of the larger thermal cycle in some areas.

Photograph 3 +23C to +60C thermal cycle -20C to +60C thermal cycle

The measurement of corrosion creep associated with CCTs can provide valuable information such as:(i) Ranking of similar generic coating types. Graph 1 shows the measured corrosion creep values for three different zinc epoxy/epoxy intermediate/topcoat systems in the CCTs mentioned above. As you will see, all the tests give a similar ranking of the systems and allows us to make a considered conclusion on performance. This is particularly useful when comparing new coating systems against similar generic systems of known performance. Compare this with Graph 2, which shows the measured corrosion creep in the salt fog test. As you will see here, all the systems perform similarly and it is not possible to give a clear ranking. In-house testing is currently concerned with obtaining correlation in ranking between the various CCTs and field exposure of some 20 coating systems of various generic types, and known performance, ranging from zinc epoxy primed, pure epoxies, modified epoxies, glass flake epoxies and solvent free epoxies. Field exposure is taking place at a highly corrosive coastal exposure site in the North East of England (4 metres from North Sea tide). So far, between 8 and 18 months exposure time has elapsed.

Photograph 1 Failure at scribe in CCT Blisters

Photograph 2 Failure at scribe on field exposure Blisters

Table 1 shows some approximate results so far with regard to corrosion creep from the scribed area. Some correlation is already being seen, High Solids Epoxy Systems 1 & 2 both show excessive corrosion creep in the cyclic corrosion tests. This poor Table 1 D.F.T. (m) 1 x 500 3 x 150 2 x 200 2 x 150 2 x 150 1 x 450 1 x 75 1 x 200 1 x 50 1 x 75 1 x 200 1 x 50 Exposure Site 10mm Creep 19 Months 8mm Creep 12 Months 6mm Creep 12 Months ~1mm Creep 15 Months ~1mm Creep 15 Months ~1mm Creep 15 Months ~0.5mm Creep 13 Months 0mm Creep 13 Months

performance has also been highlighted in the exposure site work. It is envisaged that between 3 and 5 years exposure will be required in order to apply some accurate correlation (if any!).

Coating Type

Norsok CCT 4200 Hrs 14 8 7 5 6 6 4

Corrosion Creep Values (mm) ISO 20340 ASTM D5894 4200 Hrs 4032 Hrs 13 8 6 5 7 8 3 8 10 7 3 5 6 1.5

Draft NACE 2688 Hrs 6 4 6 3 3.5 4.5 2

High Solids Epoxy 1 High Solids Epoxy 1 High Solids Epoxy 2 Pure Epoxy 1 Modified Epoxy 1 HS Modified Epoxy 1 HS Zinc Epoxy 1 Epoxy MIO 1 Urethane 1 Zinc Epoxy 1 Epoxy MIO 1 Urethane 1

0.5

Graph 1:Corrosion Creep Comparison of Zinc Primed Systems using CCTs 7 Corrosion Creep (mm) 6 5

Graph 2:-

Corrosion Creep Comparison of Zinc Primed Systems using Salt Fog Test (4032 Hrs)
7 Corrosion Creep (mm) 6 5 4 3 2 1 0 Salt Fog Test

4 3 2 1 0 Norsok Cyclic ASTM D5894 Draft NACE ISO 20340

Test Type

(ii) Differences in surface preparation. Application of coating systems over shot or grit blasted steel can lead to differences in performance at the scribed areas (see Photograph 4). The three coat zinc epoxy primed system here shows worse performance over shot blasted steel. This sort of information can well lead to the recommendation that for optimum performance grit blasting should be employed. This difference in performance is not seen in the salt fog test (see Photograph 5).

(iii) Differences in dry film thickness. In the real world, coating systems are rarely applied at the recommended specified thickness. Application at double or triple thickness is not uncommon, particularly at complex areas. Photograph 6 shows the difference in performance of a three coat zinc epoxy primed system in a CCT when applied at standard and double thickness. Again, the salt fog test does not highlight this (see Photograph 7). It is interesting to note that in many prequalification approval protocols only the standard specified thickness is tested. New high solids coating systems may be more prone to increased corrosion creep at the scribe area due to increase internal stress.

Photograph 4 CCT Result Top: Grit blasted steel Bottom: Shot blasted steel

Photograph 6 CCT Result Top: Standard thickness Bottom: Double thickness

Photograph 5 Salt Fog Results Top: Grit blasted steel Bottom: Shot blasted steel Photograph 7 Salt Fog Result Top: Standard thickness Bottom: Double thickness

Crack resistance testing The issue of crack resistance of coatings is a very important one. Cracking is a common mode of failure in many different service end use areas, and a problem the customer does not like. Once a coating system has cracked, the ability to provide adequate corrosion protection has been seriously comprom ised. The natural ageing process of a coating film via the various stresses it experiences will make the coating more prone to cracking. Some coatings will be more prone to cracking than others. Reproducing cracking failure in the laboratory is a key area of test method development within the Protective Coatings Industry. Some in -house work in which a cyclic corrosion test was modified to simulate an increased thermal stress of 30 to +80C, along with salt fog, condensation and UV, did not produce the des ired results on a known system of poor crack resistance, even when over-applied. No cracking from the scribe defect occurred. Areas of stress concentration such as welds, weld spatter, complex angles etc., tend to be the areas in which cracking is commonly seen. Taking this fact in hand and replacing the scribe area with a weld area, and including stripe coating, has produced some success in Norsok cycling testing with regard to reproducing cracking failures (see Photograph 8). Testing is ongoing against controls of known performance. At this stage, not all test parallels crack and further work is required to ascertain the overall validity of this type of testing.

Typical conditions required are: 1. Thermal cycling (hot/cold as per field temperatures). Coatings respond to decreasing temperatures by volumetrically contracting which produces a tensile stress. On increasing temperatures, coatings expand producing a compressive stress. The low temperatures are particularly important as they increase internal stress within the coating and therefore can be more destructive with regards to crack initiation and propagation. 2. Movement of moisture in and out of film (wet and dry). Serious cracking failure can be caused by the volumetric expansion of water within the coating film upon freezing. Changes in the moisture content of coating films create stresses (sometimes called hygroscopic stresses). 3. Test panel with areas of high stress concentration (welds, angles). The first signs of cracking in service can usually be seen in complex areas such as welds, corners, sharp edges, weld spatter etc., where stress levels are highest. 4. Over-application of coating system (internal stress, practical application). Over-application, particularly at complex areas is a major cause of cracking problems due to increased internal stress within the coating. All the above conditions impart an overall stress on the coating system which will cause accelerated ageing and produce early cracking failure. The issue of crack resistance is becoming ever more important, and the development of test methods to concentrate on this issue may well become part of future performance specifications.

Photograph 8 Cracking at weld area in Norsok Cyclic test In general, specific tests for crack resistance need to be developed. When developing specific tests for evaluating the crack resistance of coatings it is important to include conditions in which the coating experiences an accelerated stress similar to that experienced in the field and put together in a cyclic test method.

Already, some specific tests are finding their way into performance specifications. Two such specifications are the NACE TG260 Standard for offshore maintenance coatings and the Dutch Water Board (RWS) test specification. The NACE TG260 Standard includes a dry thermal cycling test in which the coating system is applied to a C-channel test piece and subjected to 30C to +60C in a two hour cycle. The total test duration is 3 weeks, 252 cycles. On completion of the test, the coating system is inspected for any signs of cracking with the naked eye and with a stereo microscope. This test utilises a programmable thermal cycling chamber. The Cchannel test piece (3 x 2) provides stress concentration at the corners (see Photograph 9).

The coated panels at standard and double thickness are subjected to the following cycle:Cycle Time 10 minutes 3 minutes 7 minutes 30 minutes 10 minutes 57 minutes 3 minutes Process 40C Black Panel UV + Water Spray Cooling 40 to 15C (no UV) -15C + UV Heating 15C to +75C + UV 75C Black Panel + UV Cooling 75C to 40C + Water Spray

One Cycle = 2 hours Test Duration is up to 1500 hours. This test has shown that the use of UV can induce cracking failure in high build epoxy coatings. Epoxy coatings that had been overcoated with a durable topcoat (e.g. polyurethane) tended not to show cracking failure. However, failure was seen where expected and, as such, correlation with field result was achieved. The principal drawback of this method is the expensive equipment (WOM) required and will not be accessible to all. This opens up the avenue of test method development using less expensive, more accessible equipment (e.g. salt fog, UV chamber, freezer) and reproducing similar cracking failure. In-house methods have concentrated on the combination of thermal cycling, deionised water immersion, application at standard and up to x4 recommended thickness, and the use of welded complex angle test pieces. The idea behind the test was to get all the elements of stress within one 24 hour cycle and test for up to 4 weeks with extended immersion at weekends but, above all, would be able to produce cracking failure where expected and none where not, in a relatively short period of time. A description of the method is as follows: Immerse test piece in aerated deionised water at 23C over weekend. On Monday through Friday carry out the following:-

Photograph 9 The RWS method was developed around reproducing failures seen in the field. The test involves the use of a weather-o-meter programmable chamber (the test is referred to as the WOM test). The coating system is applied to a 150mm x 100mm panel with three evenly spaces grooves machined into the panel (see Photograph 10). The grooves provide the area of stress concentration in which crack initiation and propagation occurs.

Photograph 10

9.30 a.m. Remove test piece from immersion and freeze samples at 30C for 2 hours. 12.00 p.m. Heat up to +90C in 1 hour. 1.00 p.m. 3.30 p.m. Dry out at +90C for 2 hours. Place back in immersion.

The short term goal is to ascertain what level of cracking is acceptable in this test. It could be that the test is too aggressive. Further testing of control systems of known performance will help to answer this question.

The thermal cycle of 30C to +90C was chosen as representative temperatures in which cracking occurred in the field. The thermal cycling between 30C to +90C is carried out in a programmable thermal cycling chamber (see Photograph 11). These chambers are useful in the fact that they can be programmed to carry out any thermal cycle between 70C up to +120C (depending on model). Photograph 12 3 coat system at x 2 d.f.t. Cracking expected

Photograph 11 Thermal cycling chamber Testing is in its early days, but a degree of success has been achieved in reproducing expected cracking phenomena after one week of testing, in addition to no cracking observed where expected, however, more generic type of coating systems do need to be tested. The test piece is approx. 75mm x 100mm in size. Photographs 12-16 show typical examples of the results obtained. The cracking tends to initiate and propagate at the weld areas.

Photograph 13 1 coat system at x 4 d.f.t. Cracking expected Although there are panel movements every day of the working week, this test does have the benefit of being able to produce cracking failure after only 1 week of testing in some cases. Early work has shown that over-application does have an important role in whether or not a coating will crack and to what extent.

long term evaluation. It is hoped that those systems which have shown themselves to crack quite early in the thermal cyclic test will be the first to show signs of cracking in the field in order to add some credence to the test, however, this could take a few years. Further investigation will also attempt to find any correlation with the Internal Stress Test results of the coating systems themselves. SUMMARY Photograph 14 3 coat system at x3 d.f.t. No cracking expected Cyclic corrosion tests provide information on the anti-corrosive ability of a coating system in terms of blister, rusting, chalking and corrosion undercreep from a defect area or scribe. The tests can also give valuable information relating to the effect of over-application, surface preparation and overall ranking of systems with regard to preventing corrosion onset at a defect. They are superior to the traditional salt fog tests in all aspects, particularly that of correlation with known field performance. Simulation of cracking phenomena requires development of specialised tests which principally use thermal cycling and complex test pieces with areas of stress concentration. A significant number of control coating systems of know performance need to be evaluated in order to obtain some kind of correlation as Thermal Cycling tests can easily be too aggressive and give erroneous results. Over-application of coatings is a key issue in crack resistance testing. Coating systems which have good anticorrosive properties may be prone to cracking and subsequent delamination failure which may not be picked up in a CCT test and vice versa. The combination of CCT and a Thermal Cycling test, similar to those described in this paper, will go a long way to providing valuable information for new coating systems and their performance expectations/limitations. This is particularly important in aggressive corrosive environments. Over the coming years, it is predicted that customers will increasingly demand anti-corrosive data, and data relating to crack resistance for new coating systems as an effective replacement for field track record. This could well become a common feature in all performance based specifications, particularly for those end users who have experienced problems in the field.

Photograph 15 2 coat system at x3 d.f.t. No cracking expected

Photograph 16 2 coat system at x 2 d.f.t. Cracking expected In an attempt to obtain some correlation with field exposure, large girder and pipe sections with weld areas have been exposed at our coastal exposure site for