IBP1693_12 LOW VOC EPOXY SYSTEMS FOR AMBIENT CURE

Juliana Francisco , Thais Claudino
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Copyright 2012, Brazilian Petroleum, Gas and Biofuels Institute - IBP
This Technical Paper was prepared for presentation at the Rio Oi & Gas Expo and Conference 2012, held between September, 17-20, 2012, in Rio de Janeiro. This Technical Paper was selected for presentation by the Technical Committee of the event according to the information contained in the final paper submitted by the author(s). The organizers are not supposed to translate or correct the submitted papers. The material as it is presented, does not necessarily represent Brazilian Petroleum, Gas and Biofuels Institute’ opinion, or that of its Members or Representatives. Authors consent to the publication of this Technical Paper in the Rio Oil & Gas Expo and Conference 2012 Proceedings

Abstract
Ambient cured Epoxy Systems are suitable for a variety of applications, especially in the civil engineering and maintenance & protective coatings market, being very well known for their excellent properties, such as adhesion, chemical and mechanical resistance. A number of solutions with sustainable properties and high performance for formulators and end users of these segments has been developed lately. The modern product portfolio includes waterborne epoxy systems, which enables paint manufacturers to create low emission and sustainable formulations, free of VOC and alkyl phenol. A certain part of the product range is dedicated to applications like fast curing primers, where others fulfill chemical resistance aspects, such as solvent resistance. This work highlights the high performance achieved when combining specific epoxy resins and hardeners, in a complete binder solution approach, also helping the formulators to find the right tailor made solution for their formulation and application needs.

1. Introduction
Protective coatings manufacturers help a wide range of industries to protect against corrosion and natural deterioration, for instance oil & gas and associated pipelines, steel structures, civil applications, power generation facilities and sugar & alcohol industry, to mention a few. The importance of the oil & gas and petrochemical industries worldwide explains why the main developments and improvements in maintenance and protective coatings focus on the medium and heavy duty segments. Coatings designed for heavy duty applications are exposed to aggressive environments such as strong solvents, marine atmospheres, UV light and abrasion, among others. Technical requirements, such as adhesion and corrosion resistance, are usually established by global or regional standards and reflect the market need for high performance coatings. Although there are many well-known solvent borne technologies that fully meet demanding technical requirements, paint manufacturers have been trying to reduce environmental impact by lowering VOC levels. These developments align with the global trend of more environmentally-friendly products and solutions for the chemical and petrochemical industry. The study focused comparisons among different combinations of waterborne technologies formulated into anticorrosive primers (zinc-rich and conventional) considering waterborne epoxy dispersion combined with waterborne hardeners. The waterborne epoxy dispersion was produced via a mechanical dispersion process which allows the production of waterborne dispersions of solid epoxy resins free of solvents, thus low or even zero VOC formulations can be prepared. The novel solvent-free epoxy dispersion also contains non ionic epoxy functional surfactants that provide excellent shelf stability to the dispersion and become part of the cured polymer matrix, increasing the water-resistance properties of the coating. The
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Master Student, Chemical Engineer – Technical Service & Development, The Dow Chemical Company Biochemical Engineer – Technical Service & Development, The Dow Chemical Company

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Rio Oil & Gas Expo and Conference 2012.

submicron particle size distribution obtained by this process contributes to the good storage stability and film formation of the dispersion and formulated coatings. The hardeners considered on this study are polyamine adducts, polyaminoamide and modified aliphatic amines; with AHEW that varies from 175 to 300 g/eq, all with water as volatile content whole or partially and some other different characteristics as solids and viscosity.

2. Experimental Procedures
Testing was performed following ASTM test method guidelines. Exceptions will be noted in the text. A brief description of the testing procedures is also provided below. Unless mentioned otherwise, all 2-pack coatings were applied in the time interval between 10 and 60 minutes after mixing both components. Substrate and Surface Preparation: Metal panels made of AISI 1020 steel were used in all evaluations, abrasive blasted to minimum degree ISO 8501-11 Sa 2½, roughness profile of 30 to 70μm. Adhesion to Metal (via pull-off strength test): Adhesion testing of both solvent and waterborne systems was performed on films applied over blasted steel, after curing for seven days at 25°C and 65%RH via ASTM D-45412. For the primers evaluations, panels with 280μm and 320μm dry films were used. Following the pull-off strength method, results will be presented as the necessary strength to remove the dolly (in MPa) and the type of failure observed. To describe the type of failure, the following codification for the layers will be used:
Table 1- Codes for pull-off strength adhesion method

Thus a failure noted as A/B would indicate adhesion loss between the Primer and the Substrate and a denotation of B failure would be intracoat adhesion failure within the primer layer. Salt Spray Corrosion Resistance: After curing the coated panels for seven days at 25°C and 65%RH, panels were scribed and ASTM B1173 was followed for salt spray exposure. After exposure at various time intervals, the blistering of the coating was determined via ASTM D714-87 4. Field and scribe creep corrosion were also noted at each time interval via ASTM D1654-085. Water Immersion Resistance (40˚C): After curing the coated panels for seven days at 25°C and 65%RH, the tests were followed according to ASTM D870-02 for both de-ionized water and NaCl 3.5% solution (prepared with de-ionized water). After the time of test, the film was analyzed for blister according to ASTM D714-874. General film aspect or color changed was observed. Solvent Resistance: After curing the coated panels for seven days at 25°C and 65%RH, the test was followed as ASTM D1308-026 for Xylene, NaOH 40% and MIBK at room temperature under immersion. After the time of test, the film was analyzed for blister according to ASTM D714-874. General film aspect or color changed was observed. Pot life: In order to determine the pot life of the 2-pack coatings, drawdowns were performed over specific time intervals following mixing of the components. Panels from each time interval were tested

for loss of adhesion and change in gloss/color for topcoats. KU viscosity measures were also made for visual pot life determination.

3. Results and Discussion
The epoxy resins and hardeners evaluated in this study, as well as their main characteristics, are described in table 2 and table 3.
Table 2 - Characteristics of epoxy resin studied

Characteristics Description EEW as supplied, g/eq Viscosity @ 25°C, cP Solids, % Volatile content Use recommendation

Epoxy Dispersion Waterborne type-1 epoxy dispersion 990 – 1080 3000 – 9000 46 – 48 water Waterborne coatings

Table 3 – Characteristics of hardeners studied

Characteristics Description AHEW as supplied, g/eq Viscosity @ 25°C, cP Solids, % Volatile content

Hardener 1 Polyamine adduct 300 5000 – 10000 50 Water Good anticorrosion properties combined with solid resin dispersion

Hardener 2 Polyamine adduct 300 2000 – 4000 50 Water Suitable for high quality corrosion protection formulations

Hardener 3 Polyaminoamide 210 25000 – 50000 50 Water Odorless water based protective and decorative coatings

Hardener 4 Polyamine adduct 300 3000 – 7000 45 Water Good anticorrosion properties combined with solid resin dispersion

Use recommendation

The formulations of waterborne anticorrosive primers were all kept at the same basis in terms of anticorrosive pigments (about 8.4%), PVC (33.0%) and volume solids (40.0%). Corrosion Resistance via Salt Spray The primers were applied using conventional air spray. After seven days curing at 25ºC and 65%RH a line scribe was done on the film and the salt spray tests run according to ASTM B117, as described in the experimental section. Comparisons were made at dry film thicknesses of 280 – 320μm. Epoxy primers based on zinc phosphate anticorrosive pigments are commonly recommended for general use in the medium / heavy duty industry. A solvent borne primer seen as the conventional standard for the market was chosen as a reference in this study. Comparison results of this market standard to the waterborne epoxy primers formulations described above are shown in Table 4.

Table 4 - Corrosion resistance results for anticorrosive primers after 800 hours of salt spray test

Corrosion Resistance - continuous Salt Spray Hardener 1 Hardener 2 Hardener 3 Hardener 4 SB Epoxy Primer 1

Field Blister No Blister 4M No Blister 4F No Blister

Blister at the scribe No Blister No Blister No Blister 4F No Blister

Scribe creep (mm) 2.8 1.9 1.3 1.0 1.7

After the 800 hours of continuous Salt Spray, all waterborne primers showed similar performance compared to the market standard products which is the SB Epoxy Primer 1. Figure 1 and 2 show the panels before and after scribe creep:
Figure 1 – Panels before scribe creep for anticorrosive primers after 800 hours of salt spray test

Hardener 1

Hardener 2

Hardener 3

Hardener 4

SB standard

Figure 2 – Panels after scribe creep for anticorrosive primers after 800 hours of salt spray test

Hardener 1

Hardener 2

Hardener 3

Hardener 4

SB standard

As part of the partial and final evaluations, pull-off adhesion was measure for each formulation and results are presented in table 5:

Table 5 – Adhesion for anticorrosive primers: Initial and after 802 hours of salt spray testing Adhesion after 800 hours Initial Adhesion Salt Spray Strength Strength Primer Failure Failure (MPa) (MPa) Hardener 1 Hardener 2 Hardener 3 Hardener 4 Solvent borne Epoxy Primer 1 15.9 16.3 14.8 18.8 11.2 B B AB B B 10.6 14.0 12.1 13.1 12.1 B B B B BY

All formulations presented very good results of adhesion, showing values above 10 MPa and acceptable failures (B). Hardener 3 presented failure AB at initial adhesion, but might be considered as a procedure failure, since the value after 800 hours is B and matches the expected result. Solvent Resistance The primers were applied using conventional air spray. After seven days curing at 25ºC and 65%RH a line scribe was done on the film and the salt spray tests run according to ASTM D1308, as described in the experimental section. Comparisons were made at dry film thicknesses of 280 – 320μm. Tests were performed considering:  NaOH 40% Immersion: at room temperature up to 1500 hours  Xylene Immersion: at room temperature up to 1000 hours  MIBK (Methyl Isobutyl Ketone) Immersion: at room temperature up to 1 hour Blistering and film evaluations are presented in table 6:
Table 6 - Blister evaluation after immersion at NaOH 40% / Xylene and MIBK

Primer Hardener 1 Hardener 2 Hardener 3 Hardener 4 Solventborne Epoxy Primer 1

NaOH 40% 1500 hours No blister No blister No blister No blister No blister

Xylene 1000 hours No blister No blister 8F No blister No blister

MIBK 1 hours No blister No blister No blister No blister No blister

All formulations showed good results regarding film appearance, with no change in color or presence of blistering after chemical agent immersion, even compared to solvent borne reference product. After this time of immersion, pull-off adhesion was measure and results are presented in table 7:

Table 7 - Adhesion after immersion at NaOH 40% / Xylene and MIBK

Primer Hardener 1 Hardener 2 Hardener 3 Hardener 4 Solventborne Epoxy Primer 1

NaOH 40% 1500 hours Adhesion Failure (MPa) 10.5 B 14.8 B 12.9 B 16.4 B 11.4 B

Xylene 1000 hours Adhesion Failure (MPa) 15.0 B 13.0 B 12.3 B 13.4 B 10.2 B

MIBK 1 hour Adhesion Failure (MPa) 16.0 B 11.1 B 16.9 B 14.9 B 8.8 B

Initial Adhesion (MPa) 15.9 16.3 14.8 18.8 11.2 Failure B B AB B B

All formulations presented very good results of adhesion, showing values above 10 MPa, minor adhesion loss and acceptable failures (B). It is possible to notice also that the solvent borne primer has shown a major loss of adhesion when exposed to MIBK for 1 hour and the waterborne formulations maintained good results. In an overall comparison, Hardener 3 and 4 have the best performance in chemical resistance, compared to the others. Water Immersion Resistance The primers were applied using conventional air spray. After seven days curing at 25ºC and 65%RH a line scribe was done on the film and the salt spray tests run according to ASTM D1308, as described in the experimental section. Comparisons were made at dry film thicknesses of 280 – 320μm. Tests were performed considering:  Deionized water immersion: at 40˚C up to 2000 hours  NaCl 3.5% solution immersion: 40˚C up to 2000 hours Blistering and film evaluations are presented in table 8:
Table 8 - Blister evaluation after water immersion

DI Water 2000 hours Primer Hardener 1 Hardener 2 Hardener 3 Hardener 4 Solventborne Epoxy Primer 1 6D 6D 4D 6MD No blister

NaCl 3.5% Solution 2000 hours 6M 6F No blister No blister No blister

As expected, immersion in deionized water is more critical compared to salt solution for waterborne coatings. All formulations presented blisters starting after 500 hours and all progressed to severe blistering after 2000 hours, while solvent borne primers remained intact. Hardener 3 and 4 presented good performance when immersed in salt solution, with no blisters after 2000 hours.

4. Conclusion
Adhesion and corrosion resistance tests showed that a waterborne system can offer excellent anticorrosion performance in a heavy duty testing environment. Besides corrosion resistance, the waterborne systems studied also showed excellent chemical resistance when exposed to NaOH, xylene and MIBK. Immersion in water, as expected, was a critical test for waterborne formulations, however two of them showed satisfying results in salt solution immersion, presenting no blisters after 2000 hours. In deionized water immersion, all waterborne formulations failed.

Considering exposure to atmospheric corrosion conditions, it is possible to conclude that the waterborne epoxy systems evaluated in this study show good performance even comparable to solvent borne. They also present excellent chemical resistance and might be considered for immersion applications (for organic solvents) and can also be object of further studies. These results highlight the potential of the waterborne technologies, not only in reducing environmental impacts but also for offering the possibility to formulate high performance coatings for severe conditions.

5. References
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ISO 8501-1 – Preparation of steel substrates before application of paints and related products – Visual assessment of surface cleanliness
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ASTM D-4541-09 - Standard Test Method for Pull-Off Strength of Coatings Using Portable Adhesion Testers, 2009
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ASTM B117-09 – Standard Practice for Operating Salt Spray (Fog) Apparatus, 2009 ASTM D714-87 – Standard Test Method for Evaluating Degree of Blistering of Paints, 1987

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ASTM D1654-08 – Standard Test Method for Evaluation of Painted or Coated Specimens Subjected to Corrosive Environments, 2008
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ASTM D1308-02 - Standard Test Method for Effect of Household Chemicals on Clear and Pigmented Organic Finishes
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F.L. Fragata, C.C. Amorim, A.P.Ordine, “Adhesion Tests in Single and Multicoated Systems – Results Analysis Obtained via Different Methods”, INTERCORR 2010, ABRACO Congress (Brazilian Association for Corrosion Studies)