Long-Lasting Coatings Protect Industrial Equipment
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Bring on the heat presentation by FMP COATINGS INC.
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Long-Lasting Coatings Protect Industrial Equipment
- 1. www.fmpcoatings.com people technology service Development of Innovative Ultra High Temperature Coatings Provides Long Term Corrosion Protection of Process Vessels and Piping Yuguo Cui, Senior Product Development Chemist Furnace Mineral Products Inc. (FMP Coatings)
- 2. www.fmpcoatings.com people technology service Presentation Contents Materials in industrial use High Temperature corrosion – problem areas Introduction to polymeric coatings Limitations with conventional epoxy materials Next generation hybridized technology Vessel linings Live CUI solutions
- 3. www.fmpcoatings.com people technology service Challenge with Metallic Materials Today Metals are strong solid materials that can be deformed, welded or cast into shapes, it is widely used to store and convey liquids and gases for industrial use As corrosion engineers, we know that metals are elements that readily give up electrons (oxidize) The higher the temperature, chemical concentration, moisture, and ionic activity the faster the oxidization rate Forms of corrosion in industrial settings includes galvanic attack, crevice corrosion, stress corrosion cracking (SCC), pitting, bacterial attack and erosion
- 4. www.fmpcoatings.com people technology service High Temperature Corrosion Industrial processes are operating at higher temperatures and the corrosion rates are accelerating Conventional organic coatings are exhibiting limited success above 100 oC in immersion service Next generation ultra high temperature coatings are maximizing temperature resistance These solvent free coatings can withstand temperatures above 180oC while providing excellent erosion and chemical resistance
- 5. www.fmpcoatings.com people technology service High Temperature Corrosion
- 6. www.fmpcoatings.com people technology service Use of Coatings Use of polymeric coatings are an economical and viable approach to reduce metallic corrosion rates For industrial assets operating at high temperature, pressure, in a chemical rich environment there are limitations to the use of conventional epoxy based polymeric coatings Generic polymer coatings don’t work. The use of engineered surface coatings specifically designed for each end use must be considered
- 7. www.fmpcoatings.com people technology service Epoxy Chemistry – The Basics • Epoxy coatings are organic thermosetting polymers • Key properties of epoxy chemistry is molecular weight, molecular weight distribution, glass transition (Tg), and solubility • Cure by chemical reaction • Reaction between epoxide resin and an amine curing agent • 3 main components to epoxy coatings (resin, hardener and modifier)
- 8. www.fmpcoatings.com people technology service Resin Selection Type Structure Viscosity Tg Bisphenol A 15,000 cps 175 oC Bisphenol F 5,000 cps 150 oC Novolac Semi Solid at Room Temperature 200 oC
- 9. www.fmpcoatings.com people technology service Resin Viscosity 0 10 20 30 40 50 60 70 80 90 Bisphenol A Bisphenol F Novolac 3.6 f Temperature at 4,000 cps 0 50 100 150 200 250 Bisphenol F Bisphenol A Novolac Resin Tg (oC) 0 10 20 30 40 50 60 Bisphenol A Bisphenol F Novolac 3.6 f Percentage% Diluent Requirement to Drop to 4,000 cps *Viscosity of water is 1 cps
- 10. www.fmpcoatings.com people technology service Hardener Selection 0 50 100 150 200 250 Amide Aliphatic Cycloaliphatic Aromatic TemperatureoC Hardener Curing Temperature • Types of Epoxy Curatives – Polyamide – Aliphatic – Cycloaliphatic – Aromatic
- 11. www.fmpcoatings.com people technology service Use of Solvents • Solvency – viscosity reduction • Environmental impact • Sacrifice performance • Will not survive high temperature exposure Autoclave Testing 96 hrs at 120 oC at vapour pressure
- 12. www.fmpcoatings.com people technology service 100 % Solids – Solvent Free • A 100% solids coating system is defined as a coating that results in no film thickness change during application. • So how does a formulator of 100% solids coating drive down the viscosity so that the coating can be sprayed or rolled ? • The trick is the use of a high boiling point solvent (ie, benzyl alcohol) that is volatile but also reacts with the epoxide group of the coating so that the bulk of the solvent remains in the coating system. • In high temperature systems this approach does not work • To overcome the need for solvent, the system is heated to reduce viscosity
- 13. www.fmpcoatings.com people technology service Technological Gap Glass Transition Curve Cross Link Density Low Tg Higher Tg Why traditional epoxies fail at high temperature • Low Tg • Low cross link density • High free volume
- 14. www.fmpcoatings.com people technology service Inorganic Chemistry • Ceramic inorganic chemistry has been used for combustion service ranging from 370 to 800 oC since the 1980s. • Upon curing the coating forms an amorphous layer that bonds the ceramic matrix to the substrate surface • Limitations – requires post cure at elevated temperature – Not suitable for immersion service – Difficult to apply – Thin film
- 15. www.fmpcoatings.com people technology service Technology Development - Hybridization ORGANIC CHEMISTRY Contains backbones comprised of chains and/or rings of carbon (plant based) and hydrogen atoms. INORGANIC CHEMISTRY Contains backbones comprised of non carbon containing elements such as silicon (mineral based). Silicon offers extreme thermal stability and temperature resistance
- 16. www.fmpcoatings.com people technology service Ultra high temperature resistant coatings – industrial uses ULTRA HIGH TEMPERATURE LINING • Two component hybridized thermoset polyermic lining for ultra high temperature corrosion protection of process vessel (immersion service) CUI PROTECTION • Single component heat activated surface tolerant composite coating for corrosion under insulation (CUI)
- 17. www.fmpcoatings.com people technology service Two components hybridized thermoset epoxy coating- Introduction PROCESS VESSEL LINING • Corrosion prevention of process vessel (immersion service) • High temperature (>100oC) resistance • Chemical resistance (water, acid, base, solvent, petroleum) • Can be easily applied by spray
- 18. www.fmpcoatings.com people technology service Two components hybridized thermoset organic coating- Formulation • Hybridized • Si-O bond • High functionality novolac epoxy • Ceramic fillers • Combination of amine hardener chemistry
- 19. www.fmpcoatings.com people technology service Test Methods Test Method Description ASTM D648 Heat Deflection Temperature ASTM D6137 Sulfuric Acid Resistance of Polymer Linings for Flue Gas Desulfurization Systems ASTM D5499 Heat Resistance of Polymer Linings for Flue Gas Desulfurization Systems NACE TM 0174 Laboratory Methods for the Evaluation of Protective Coatings and Lining Materials on Metallic Substrates in Immersion Service NACE TM 0185 Evaluation of Internal Plastic Coatings for Corrosion Control of Tubular Goods by Autoclave Testing ASTM 2485 Evaluating Coating for High Temperature Service CSA Z245.20 Hot Water Soak Test
- 20. www.fmpcoatings.com people technology service Test Methods Test Method Description D3418 Polymers by Differential Scanning Calorimetry (DSC) ASTM D2240 Standard Test Method for Rubber Property—Durometer Hardness In House Chemical immersion/heat cycles
- 21. www.fmpcoatings.com people technology service AutoClave Testing – NACE 0185
- 22. www.fmpcoatings.com people technology service Hybridized thermoset organic coating- Autoclave test 16-1113-01A4 Pre-Test Post-Test Post Test (Angled Lighting) Figure 1 – Pre-Test and Post-Test Autoclave of Enercote ULX 1 16-1113-01A4 Pre-Test Post-Test Post Test (Angled Lighting) Figure 1 – Pre-Test and Post-Test Autoclave of Enercote ULX 1 16-1113-01A4 Pre-Test Post-Test Post Test (Angled Lighting) Figure 1 – Pre-Test and Post-Test Autoclave of Enercote ULX 1 left, pre-test; middle, post-test right, post-test, angled lighting NACE TM0185- 2006 Test duration: 7 days Test temperature: 180±6oC Test pressure: vapor pressure Aqueous phase: deionized water Gas phase: water vapor Release temperature: 64oC Release pressure: 0 Mpa
- 23. www.fmpcoatings.com people technology service Autoclave test results Sample # Testing Phase Dry Film Thickness1 (mil) Adhesion2 Blistering3 Softening4 Colour4 (Change) Intercoat Foam4,5 1 Pre-test 16.3/21.3/18.7 7 No N/A D. Brown Yes Post-test 15.2/19.3/17.4 10 No No Sl No 2 Pre-test 16.7/23.3/20.4 8 No N/A D. Brown Yes Post-test 13.2/25.5/19.9 10 No No Sl No 3 Pre-test 19.2/28.7/24.3 10 No N/A D. Brown Yes Post-test 21.1/27.2/23.0 10 No No Sl No 5 Pre-test 11.9/19.0/15.0 8 No N/A D. Brown Yes Post-test 9.8/16.9/13.7 10 No No Sl No 6 Pre-test 13.0/19.7/16.8 9 No N/A D. Brown Yes Post-test 13.6/18.6/16.3 10 No No Sl No Sample #1, sprayed; #2, sprayed then brushed; #3 brushed; #5 brushed; #6 brushed, post cured at 100oC 1. Film thickness measurement per ASTM D7091-13. Rating is Low/High/Average of at least five measurements. 2. Adhesion performed per NACE TM0185-2006, Section 5.3.2.1. Adhesion rated per ASTM D1654-08 3. Blistering evaluation per ASTM D714-02(2009) 4. Softening, Colour change, and Intracoat Foam per NACE TM0185-2006, Section 5.3. 5. Intercoat foam is determined using a microscope set at 40x magnification Adhesion (ASTM D1654-08) Softening, Colour Change, Intercoat Foam (NACE TM0185-2006, Section 5.3.1) Rating: Coating removed (mm): Rating: Description 10 0 (cohesive failure) N No change 9 Over 0.0 up to 0.5 Sl Slight change 8 Over 0.5 up to 1.0 M Moderate change 7 Over 1.0 up to 2.0 Sv Severe change
- 24. www.fmpcoatings.com people technology service In house Autoclave testing • Autoclave in lab, passed 210oC test
- 25. www.fmpcoatings.com people technology service Atlas Cell Testing • NACE TM 0174 • Long term testing • Great simulation test for chemical exposure at high temperature • Provides cold wall effect simulation • Can also be used under pressure • Blistering and adhesion loss • Good wet adhesion testing • Hybridization improves results
- 26. www.fmpcoatings.com people technology service Cold Wall Effect
- 27. www.fmpcoatings.com people technology service Atlas Cell Testing Poor wet adhesion Blisters at thin coating Hybrid Material
- 28. www.fmpcoatings.com people technology service 2K Spray Application Performance Benefits Lower intercoat porosity Single coat application reduces the risk of intercoat failure Improved edge retention > 75 % Improved pit coverage Improved adhesive strength
- 29. www.fmpcoatings.com people technology service Heated Spray • Two methods – Single leg hot pot – Plural component spray Characteristic Single Leg (heated) Plural Component (heated) Ease of Application Requires skilled technician Requires skilled technician Cost of Equipment $7, 000 USD $30,000 - 50, 000 USD Solvent consumption Flush every 30 min (dependant of the pot life and exotherm) Flush at the end of spray Pot Life Min 30 min No limit Max Material Viscosity 20,000 cps 80,000 cps Max Temperature 38 oC 65 oC
- 30. www.fmpcoatings.com people technology service Plural Component Mixing A B MIX Dual Heated hose Proportioner FluidHeaters Gravity or pump feed heated supply Volume-balanced hoses S Max length depends on pot-life Mix line
- 31. www.fmpcoatings.com people technology service Single component heat activated composite- Live repair • Heat Activation – No product pot life limitations – Live hot work repair up to 150 oC – Rapid return to service < 30 minutes • No Abrasive Blasting Required – Power tool cleaning – Hand tool cleaning • Solvent Free – No VOC – Safe to apply to hot surfaces
- 32. www.fmpcoatings.com people technology service Single component heat activated composite- Test • Surface preparation: hand tool / power tool cleaning • Application method: brush applied • Temperature to apply the coating: 75-150 oC • Final cured temperature: same as temperature to apply the coating. (example 130oC)
- 33. www.fmpcoatings.com people technology service Single component heat activated composite- Test results • No blistering was observed during application • Dry to touch time: 15-6 min for 75-150oC • Recoat after dry to touch, thickness up to 12- 15 mils • Pull off strength >3,500 psi (24MPa) • Thermal stable at 260oC (500oF)
- 34. www.fmpcoatings.com people technology service North American Total Applied Cost per Sqft in USD Coating Material Solvent Content by Volume Surface Preparation Cost per sqft Actual Material Cost per sqft Material Application Cost per sqft Total Estimated Cost Latent Curing Hybrid Polymer 0% $0.77 $2.98 $0.67 $4.42 per sqft Solvent Based Multi-Polymeric Matrix Coating 49% $2.72 $6.14 $0.67 $9.53 per sqft
- 35. www.fmpcoatings.com people technology service Single component heat activated composite for CUI- Case study • Surface preparation: hand tool cleaning • Application: brushed applied • Temperature: 120oC
- 36. www.fmpcoatings.com people technology service Conclusion • Two component hybridized thermoset epoxy coating with the introduction of silicon-oxide, ceramic fillers, passed the 180oC autoclave test and can be applied as corrosion protection for process vessel immersion service at ultra high temperature. • Single component heat activated composite can be applied and cured when the facilities are running at temperature 75-150oC with minimum surface preparation for CUI service.
Editor's Notes
- The demand for high temperature coating protection is growing in the power generation and oil and gas industry as operations run at higher and higher temperature Conventional polymeric epoxy based chemistries have had limited success in providing corrosion resistance above 100 oC (212 oF) in immersion service. The requirement for zero solvent, VOC compliant coatings is adding to the formulating complexity. Next generation, high temperature hybrid coatings are pushing the envelope of temperature and wear resistance through the use of inorganic ceramic technology. These solvent free coatings are capable of withstanding temperatures as high as 180 deg C (360 oF) in immersion service while providing excellent erosion and chemical resistance.
- The demand for high temperature coating protection is growing in the power generation and oil and gas industry as operations run at higher and higher temperature Conventional polymeric epoxy based chemistries have had limited success in providing corrosion resistance above 100 oC (212 oF) in immersion service. The requirement for zero solvent, VOC compliant coatings is adding to the formulating complexity. Next generation, high temperature hybrid coatings are pushing the envelope of temperature and wear resistance through the use of inorganic ceramic technology. These solvent free coatings are capable of withstanding temperatures as high as 180 deg C (360 oF) in immersion service while providing excellent erosion and chemical resistance.
- Most common generic lining and anti corrosion coating is epoxy based chemistry
- Let’s begin by understanding epoxy chemistry. Epoxy coatings are thermosetting polymers. They are typically two component systems. An epoxide resin and an amine hardener.. Both components are in liquid state. They remain in a liquid state until they are mixed together and the polymer reaction begins. As a formulator, we can control the rate of reaction and to make it happen as fast or as slow as possible.
- A first step in formulating for high-temperature applications is to select the proper base resin. In making this selection, the main properties of concern are functionality and glass transition temperature (Tg).
- One of the approaches to reduce the visicosity of a novolac system is to heat or add a diluent to the resin to reduce the resin system
- The second component is the hardener or curing agent. The most important consideration is how volatile the material is and whether is contains ingredients that will be volatile at service temperature. Many curing agents contain a volatile catalyst that will help to speed up the cure reaction.
- To overcome the need for solvent we use heat. A volalite solvent with a high boiling point. The benzyl alcohol acts as a diluent and a catalyst to speed up the reaction.
- CTE- coefficient of thermal expansion Organic epoxy coatings will undergo both physical and chemical changes when heat is applied; this will usually result in undesirable changes to the properties of the coating. The degradation of epoxy-amine reaction at high temperature proceeds by rupture of the bonds in the cured network, at 240 deg C this is most noticeable. The primary indicator to determine suitability of a coating system for high temperature service is the glass transition temperature. The glass transition temperature, Tg, can be defined as the temperature at which the coating changes from the rigid state to a rubbery state. The lower the Tg the more flexible the coating system which means that there is more spacing between the cross linked network and lower cross link density. To optimize Tg it is important to also achieve a very tangled and high cross linked polymer. The Tg is also strongly affected by the presense of solvents or diluent loading. The Tg is is function of cross link density of the coating. The Tg will also change with the cure temperature of the coating Every system, however, will have an ultimate Tg determined by its formulation that cannot be further enhanced by an increase in cure temperature.
- We’ve seen how organic chemistry can degrade at higher temperature. Let’s now explore inorganic chemistry these Icoatings have played an important role in providing protection to combustion equipment such as furnaces and boilers operating at really high temperatures above 480 deg C. These slurry coatings are formulated as a mixture of ceramic oxides and silica-based polymers. Upon curing the inorganic ceramic coating forms an amorphous layer that bonds the ceramic matrix to the substrate surface, providing high thermal stability. The addition of an epoxy resin to an inorganic coating would provide the desirable benefit of ambient temperature lower temperature cure with higher thermal stability.
- conceive a higher temperature epoxy based coating our approach was to hybridize the coating system with inorganic chemistry aimed to enhance the thermal and mechanical resistance property of the coating film.
- To qualify the coatings a methodology for evaluation of high temperature coatings for immersion service needed to be determined. An important consideration for engineers and owners is that the testing requirements for a given coating system should attempt to best simulate the intended service environment. In high temperature service this becomes increasingly important as the polymeric crosslinking and the physical stability of the polymer begins to change with increasing temperature. Therefore, a coating with great chemical resistance and/or abrasion resistance at room temperature may behave very different once exposed to a high temperature environment. For the purposes of our evaluation we selected a few well recognized test methods including autoclave, atlas cell and taber abrasion.
- We have also a modified version of chemical immersion and abrasion testing that to help simulate higher temperature service. The proprietary tests will not be discussed at this time.
- Atlas cell testing also measures the ability of the coating to withstand the temperature gradient between the internal and external surface (cold wall effect) under the influence of pressure, temperature, and the internal environment
- 800 to 1600 micron film build in a single pass 7000 psi – 782 bar Brushing or trying to trowel down a coating over the pits is a difficult task. You cannot effective wet into the valley of the corrosion pit
- Here are two methods to spray heated coatings. 1st is to use a standard single leg airless pump that is equipped with supply containers and paint hose. In this system the coating is fully mixed and the pump dispenses the heated mixed material. The problem withthis approach is the pot life. Most high solids coatings have a short pot life, so as an applicator you run the risk of seizing your equipment if you’re not closely monitoring the pot life and peak exotherm temperature. In this part of the world I’m not sure how feasible this application method can be as the ambient temperature can be very high. 2nd approach is to use a plural component pump. Instead of a single leg this pump consists of two separate pump legs that dispenses the material separately until it hit a static mixer where the two components are mixed together. Let’s compare the two methods…
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