COMPARATIVE TESTING OF 31 TANK LINING SYSTEMS

COMPARATIVE TESTING OF 31 TANK LINING SYSTEMS Amal Al-Borno Charter Coating Service (2000) Ltd. #6, 4604 13th Street N.E. Calgary, AB, Canada T2E 6P1 aalborno@chartercoating.com

PROJECT PARTICIPANTS Amercoat Canada Cloverdale Paint CNRL Corrocoat Ltd. Dalco Services Inc. Denso North America Inc. Enbridge Pipelines, Inc. Hempel (Canada) Inc. Imperial Oil Resources Limited International Paint, Inc. PPG Canada Petro-Canada RS Technologies Sherwin-Williams Sigma Coatings Canada SPC Talisman Tyco Adhesives

PROJECT OBJECTIVES To examine and compare the performance characteristics of tank lining systems as selected by the study participants. To communicate performance data so as to assist in the selection of appropriate coatings for any given oil field environment. To encourage more interaction between suppliers and end-users.

Coating Number Coating Descriptor as Used on Data Sheet Coating Type % Solids 1 Epoxy Novolac Novolac 72 2 Phenolic Epoxy / Polyamino-Amide Phenolic 100 3 Epoxy /Amine and Polyamino Epoxy 100 4 Epoxy Phenolic Phenolic 64 5 Epoxy Novolac Novolac 54 6 Epoxy Novolac Novolac 72 7 Epoxy Novolac / Amine Novolac 100 8 Epoxy Epoxy 72 9 Epoxy Novolac Novolac 100 10 Vinyl Ester / Acrylic Vinyl Ester 99 11 Vinyl Ester / Urethane Vinyl Ester 99 12 Epoxy Novolac Novolac 94 13 Epoxy Epoxy 76 14 Epoxy Phenolic Phenolic 100 15 Epoxy Epoxy 95 16 Epoxy Novolac Novolac 67 17 Epoxy (Aluminum) Epoxy 60 18 Epoxy / Amine Epoxy 100

Coating Number Coating Descriptor as Used on Data Sheet Coating Type % Solids 19 Epoxy Phenolic Novolac Novolac 73 20 Epoxy Phenolic Novolac / Amine Novolac 68 21 Phenolic Epoxy / Amine Phenolic 100 22 Novolac Novolac 100 23 Epoxy Epoxy 100 24 Phenolic Epoxy / Amine Phenolic 66 25 Vinyl Ester Vinyl Ester 98 26 Epoxy / Amine Epoxy 98 27 Epoxy Phenolic Novolac Novolac 70 28 Epoxy Phenolic Novolac / Amine Novolac 80 29 Epoxy Novolac Novolac 90 30 Epoxy Novolac (Siliconized) Novolac 97 31 Phenolic Epoxy / Amine Phenolic 100

COATING TYPES Vinyl Ester (3 coatings) 10% Phenolic (6 coatings) 19% Epoxy (8 coatings) 26% Novolac (14 coatings) 45%

APPLICATION AND SAMPLE CUTTING All coatings were applied by the same applicator according to suppliers recommended procedures and under suppliers direction. Cured samples were cut using a water-jet cutting system.

TESTS at 60 C/140 F Test Conditions (ALL 28 Day Tests) Soak Adhesion CSA Z245.20 Cathodic Disbondment CSA Z245.20 Atlas Cell Test NACE TM 0174 Pressurized Atlas Cell (PAC) NACE TM 0174 Electrochemical Impedance Spectroscopy (EIS) Water: 1% NaCl in distilled water Solution: 3% NaCl in distilled water Voltage: -1.5V Thermal Gradient: 25 C Air; 1% NaCl aq.; 1:1 toluene: kerosene Pressure: 1.4MPa/200 psi Gas: 5% H 2 S, 5% CO 2, 90% CH 4 1% NaCl aq.; 1:1 toluene: kerosene 1) Untested samples 2) Water phase of PAC samples after 28 Days

HIGHER TEMPERATURE TESTS Test Atlas Cell Test NACE TM 0174 Pressurized Atlas Cell NACE TM 0174 Autoclave Tests NACE TM 0185 Conditions Temp.: 85 C/185 F, Thermal Gradient: 25 C Air; 1% NaCl aq.; 1:1 toluene:kerosene; 28 days Temp.: 100 C/212 F, Pres.: 1.4MPa/200 psi Gas: 5% H 2 S, 5% CO 2, 90% CH 4 1% NaCl aq.; 1:1 toluene: kerosene; 28 days Temp.: 100 C/212 F, Pres.: 6.89MPa/1000 psi Gas: 5% H 2 S, 5% CO 2, 90% CH 4 1% NaCl aq.; 1:1 toluene: kerosene; 168 hours Test conditions as above but including mid-cycle rapid depressurization Temp.: 125 C/257 F; Pres.: 0.34 MPa/50 psi Vapor; 1% NaCl aq.; 1:1 toluene: kerosene; 168 hours

ACCELERATING COMPONENTS IN TEST CONDITIONS Low 1 % NaCl concentration in most tests (more aggressive than 3% solutions). High thermal gradient (25ºC) for standard atlas cell test. H 2 S and CO 2 used in pressurized atlas cell and 100 ºC autoclave test. Rapid depressurization used for one of the autoclave tests. High temperatures.

GOOD PERFORMANCE CRITERIA Soak Adhesion Test: CSA FBE coatings test modified. Pass/fail 1-3 (pass = good ). Cathodic Disbondment Test: CSA FBE coatings test modified. One variable, the disbondment radius. Performance based on comparison with similar coatings and other coatings in this study. Good = less than 15 mm. Atlas Cell and Autoclave Tests: No single characteristic that can be analyzed. In this study good performance is defined as being: does not blister or crack in any phase maintains an adhesion of C - or better

SOAK ADHESION (CSA Z245.20-02) Water can be an aggressive environment to a coating system, especially at elevated temperatures. The hot water soak test examines a coating s ability to remain well adhered to the steel in immersion conditions. Conditions: Temperature: 60 C/140 F Water: 1% NaCl Solution Duration: 28 days

Adhesion Rating Adhesion Rating SOAK ADHESION TEST 3 3 Pre-Test Data Post-Test Data 2 2 1 1 0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 Coating Number 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 *Decimal value denot es t he average of t wo disparat e pre-t est scores.

Rating 4 Rating 2 Rating 1

CATHODIC DISBONDMENT (CSA Z245.20-M92) This test measures the resistance of a coating to disbondment under conditions that simulate cathodic protection. Typically the bottom of the tank is the area most prone to effect from cathodic protection owing to the placement of anodes in the tank. Conditions: Temperature: 60 C/140 F Solution: 3% NaCl Solution Voltage: -1.5V Duration: 28 days

9 12 22 7 23 10 11 25 17 2 1 4 20 31 18 21 19 30 13 29 3 6 14 15 26 8 5 27 16 28 24 Disbondment Radius (mm) Excellent Moderate CATHODIC DISBONDMENT BY COATING 40 35 30 25 Very Good Good Poor 20 15 10 5 0 Coating Number

Percentage of Coatings Percentage of Coatings CATHODIC DISBONDMENT AT 60 C BY COATING TYPE 100% 90% 80% 80% 70% 70% 60% 60% 50% 50% 40% 40% 30% 30% 20% 20% 10% 10% 2 < 15 mm 15-20 mm > 20 mm 1 5 6 8 3 1 2 3 0% 0% Epoxy (8) Novolac (14) Phenolic (6) Vinyl Ester (3) Coating Type (Number of Coatings) Coating Type (Number of Coatings)

STANDARD ATLAS CELL (Modified NACE TM0174-91) The ability of the coating to withstand immersion conditions under the stress of a thermal gradient. This test simulates the cold wall affects in non-insulated tanks and vessels. Conditions: Internal Temperature: 1 st test 60 C/140 F 2 nd test 85 C/185 F Thermal Gradient: 25 C/70 F Gas: Air Water: 1% NaCl Solution Hydrocarbon: 1:1 Toluene: Kerosene Duration: 28 Days

thermocouples controller cooling jacket sample panels heating jacket

PRESSURIZED ATLAS CELL (Modified NACE TM0174-91) This test examines the resistance of coatings to the combined affects of temperature, pressure, cold wall, and chemical environment. Determines performance in conditions that simulate pressurized vessels in sour service. Conditions: Internal Temperature: 1 st test 60 C/140 F 2 nd test 100 C/202 F Pressure: 1.4MPa/200 psi Gas: 5% H 2 S, 5% CO 2, 90% CH 4 Water: 1% NaCl Solution Hydrocarbon: 1:1 Toluene : Kerosene Duration: 28 Days

heating jackets controllers pressure gauges samples (hidden)

ATLAS CELLS AND CATHODIC DISBONDMENT DATA Coating Number Standard Atlas Cell 10/31 Pressurized Atlas Cell 16/31 Cathodic Disbondment Performance Gas Phase Hydrocarbon Phase Water Phase Gas Phase Hydrocarbon Phase Water Phase Phenolic 2 C _ C _ C _ C _ C _ C _ good Novolac 5 -- -- -- B A B - poor Novolac 6 -- -- -- C B C poor Novolac 7 C _ C _ C _ C C C very good Standard Atlas Cell Pressurized Atlas Cell Epoxy 8 B A C B A C poor Novolac Gas Phase 9 -- -- -- Gas C Phase C C excellent Vinyl Ester 10 C C C B B B _ very good Vinyl Ester 11 C C C C C C very good Novolac 12 C C C _ C C C excellent Hydrocarbon Novolac 16 Phase A A B Hydrocarbon Phase A A A poor Epoxy 18 A A C A A B+ moderate Novolac 22 -- -- -- A A A excellent Phenolic 24 A A A A A A poor Vinyl Ester Water 25 Phase B B C Water Phase B B B very good Novolac 27 -- -- -- A A A poor Novolac 28 -- -- -- A A A poor

Percentage of Coatings with Good Performance STANDARD AND PRESSURIZED ATLAS CELL AT 60 C BY COATING TYPE Standard Atlas Cell 10 / 31 Good Pressurized Atlas Cell 16 / 31 Good 100% 90% 80% 70% 60% 50% 40% 30% 2 2 3 9 2 2 3 3 20% 10% 0% Epoxy (8) Novolac (14) Phenolic (6) Vinyl Ester (3) Coating Type (Number of Coatings)

ELECTROCHEMICAL IMPEDANCE SPECTOSCOPY (EIS) Used to evaluate the integrity of coatings, their barrier properties, and predict their corrosion protection characteristics. Conducted using conditions as in other immersion tests (1% NaCl aq., 60 C/140 F, 28 days) untested coatings PAC (water phase)

Log Z at 0.1 Hz EIS DATA 10 EIS Data @ 60ºC/140ºF Untested Coating After 28 Days at 60ºC in Pressurized Atlas Cell 9 B B B 8 7 B B 6 B 5 4 B B B B B B B B B B 3 2 1 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 B - Bisters after PAC Testing B - Bisters after EIS Testing Coating Number

Log Z at 0.1 Hz EIS DATA AFTER PRESSURIZED ATLAS CELL TEST BY COATING TYPE 10 9 8 7 6 5 4 3 2 1 0?? Epoxy Novolac Phenolic Vinyl Ester Coating Type???? Some coatings that were failing looked good on EIS and some coatings that looked poor in EIS performed well as corrosion barriers. Shows limitations of EIS as an indicator of coating performance/degradation.

Log Z at 0.1 Hz Log Z at 0.1 Hz EIS DATA OF UNTESTED COATINGS COMPARED TO CATHODIC DISBONDMENT RADIUS 10 10.0 9 9.0 8 8.0 7 7.0 6 6.0 5 worst coatings in EIS 5 5.0 4 4.0 0 5 10 15 20 25 30 35 40 0 5 10 15 20 25 30 35 40 Disbondment Radius (mm) Disbondment Radius (mm)

SOME GOOD COATINGS IN 60 C/140 F TESTS Coating # Soak Atlas Cell P A C CD Phenolic 2 3-4 Good Good Good 11 mm Novolac 7 2 Good Good V. Good 10 mm Epoxy 8 1 Good Good Poor 28 mm Novolac 9 2 Poor Good < 10 mm Vinyl Ester 10 2 Good Good V. Good 10 mm Vinyl Ester 11 2 Good Good V. Good 10 mm Novolac 12 2 Good Good < 10 mm Novolac 16 1 Good Good Poor 35 mm Epoxy 18 1 Good Good Moderate 16mm Novolac 22 1 Poor in Water Good < 10 mm Phenolic 24 2 Good Good Poor 36 mm Vinyl Ester 25 2 Good Good V. Good 10 mm

SELECTION OF COATINGS FOR HIGHER TEMPERATURE TESTING Coatings not recommended for high temperatures were not tested above 60 C/140 F. Coatings that were to be tested at a different film thickness were included in all the higher temperature tests. Coatings that did not have good performance in the 60 C/140 F Standard Atlas Cell test were not tested in the 85 C/185 F test. Coatings that did not have good performance in the 60 C/140 F Pressurized Atlas Cell test were not tested in the 100 C/212 F test.

AUTOCLAVE (Optional) (Modified NACE TM0185-93) Determines performance under conditions that simulate the environment in an insulated vessel. Conditions: Temperature: Pressure: 1 st test 100 C/202 F 2 nd test 125 C/257 F 1 st test 6.89MPa/1000 psi 2 nd test 0.34 MPa/50 psi Gas: 1st test 5% H 2 S, 5% CO 2, 90% CH 4 2nd test Vapor Water: 1% NaCl Solution Hydrocarbon: 1:1 Toluene : Kerosene Duration: 168 hours Mid-Cycle Rapid Depressurization included for duplicate of 1 st set of test conditions

Percentage with Good Performance Percentage with "Good Performance" COATINGS WITH GOOD PERFORMANCE AT HIGH TEMPERATURE BY COATING TYPE 100% 100% 90% 80% 80% 70% 60% 50% 40% 40% 30% 30% 20% 10% 10% 0% 0% 0 Standard Atlas Cell (85 C) Pressurized Atlas Cell (100 C) Autoclave (100C) Autoclave with Rapid Depress. (100 C) 1 2 9 (20) 2 2 (28) 0 0 0 0 0 Epoxy (8) (8) Novolac (14) (14) Phenolic (6) (6) Vinyl Ester (3) (3) (24) Coating Type (Number of Coatings) Coating Type (Number of Coatings) 1 4 3 (2) 1 1 Autoclave with Mid-Cycle Rapid Depressurization

Standard Atlas Cell Pressurized Atlas Cell Autoclave with NO Mid-Cycle Rapid Depressurization Autoclave with Mid-Cycle Rapid Depressurization Autoclave with with Mid-Cycle Rapid Depressurization

CONCLUSIONS FOR HIGH TEMPERATURE TESTS Fewer coatings perform well, more care required in selection All 25 tested coatings performed well at 125 C/257 F in water and hydrocarbons, but other factors (see below) tended to result in coating degradation. Especially susceptible to thermal gradient with only one good performance (Number 24, a Phenolic) in 85 C/185 F Standard Atlas Cell. In the presence of acid gases and a pressure of 6.89 MPa/1000 psi 19 of 25 tested coatings performed well. Coatings tended to blister and/or suffer severe adhesion loss when subjected to rapid depressurization. Only Numbers 2, 20 and 28 didn t. However some coatings formed small surface blisters, some of which recovered after test, indicating resistance to degradation.

SUMMARY OF COATINGS WITH Good Performance (not marked = Not Tested/Not Good) Coating Number CD Test 60ºC/140ºF Standard Atlas Cell 60ºC/140ºF Pressurized Atlas Cell 60ºC/140ºF Standard Atlas Cell 85ºC/185ºF Pressurized Atlas Cell 100ºC/212ºF Autoclave 100ºC/212ºF Autoclave 100ºC/212ºF Blow-Down Autoclave 125ºC/257ºF Novolac 1 Good Good Phenolic 2 Good Good Good Good Good Good Epoxy 3 Phenolic 4 Good Good Novolac 5 Good Good Novolac 6 Good Good Good Good Novolac 7 Very Good Good Good Good Good Epoxy 8 Good Good Good Good Novolac 9 Excellent Good Good Vinyl Ester 10 Very Good Good Good Good Good Vinyl Ester 11 Very Good Good Good Good Good Good Novolac 12 Excellent Good Good Good Good Epoxy 13 Good Good Phenolic 14 Epoxy 15 Novolac 16 Good Good Good Good Good

Coating Number Epoxy 17 SUMMARY OF COATINGS WITH Good Performance (not marked = Not Tested/Not Good) CD Test 60ºC/140ºF Good Standard Atlas Cell 60ºC/140ºF Pressurized Atlas Cell 60ºC/140ºF Standard Atlas Cell 85ºC/185ºF Pressurized Atlas Cell 100ºC/212ºF Autoclave 100ºC/212ºF Autoclave 100ºC/212ºF Blow-Down Autoclave 125ºC/257ºF Epoxy 18 Moderate Good Good Good Good Novolac 19 Novolac 20 Good Good Good Good Phenolic 21 Moderate Good Good Novolac 22 Excellent Good Good Good Epoxy 23 Very Good Good Phenolic 24 Good Good Good Good Good Vinyl Ester 25 Very Good Good Good Good Good Epoxy 26 Good Novolac 27 Good Good Good Novolac 28 Good Good Good Good Novolac 29 Good Good Novolac 30 Good Good Phenolic 31 Good Good Good

SUMMARY CONCLUSIONS Most problems seen in the water phase. Higher Temperature or higher Thermal Gradient are most likely to result in coating degradation. Many coatings disbond in the presence of an impressed cathodic potential at 60 C/140 F. Emergency Depressurization tends to cause blistering/loss of adhesion. Lots of variation within a given Coating Type (resin type) don t buy generics! Need to test selected coatings in environments that simulate actual service environment.

COMPARATIVE TESTING OF 31 TANK LINING SYSTEMS Amal Al-Borno Charter Coating Service (2000) Ltd. #6, 4604 13th Street N.E. Calgary, AB, Canada T2E 6P1 aalborno@chartercoating.com