Innovative Amine Curing agent for Epoxy Resins New Water-reducible Curing Agent for Civil Engineering g & Concrete Coatings

Transcription

1 Innovative Amine Curing agent for Epoxy Resins New Water-reducible Curing Agent for Civil Engineering g & Concrete Coatings Presented at a meeting of the Thermoset Resin Formulators Association at the Hilton Suites Chicago Magnificent Mile in Chicago, Illinois, September 15 through 16,

2 Outline How did we design a new WB Curing Agent? Design Criteria for WB system for concrete Bench marking studies Formulation comparisons Formulation Properties Failure Modes and Performance testing Summary Adhesion Conclusions Chemical spot and stain Osmotic Blister resistance and Water Vapor Transmission 2

3 Epoxies in Civil Engineering for Concrete Protection Potable water tank linings Warehouse floors Garage floors Chemical resistant coatings Concrete repair 3

4 New WB Amine Curing Agent Designed to Meet Emerging Market Needs Curing Agent Property Disperses Liquid Epoxy Resin Freeze / thaw stable Heat stable Easy Water Addition Low lower temp (50ºF) Product Design Target Value* Benefit New WB Amine Yes Cost effective 5 cycles 10 º F overnight / R.T. 8 hrs. 5 cycles 120 º F overnight / R.T. 8 hrs. Water soluble down to < 25%wt solids Storage Stable Storage Stable Low Solids for Sealers <20,000 cp Easy to Use 3,000 cp Higher Solids > 60 % in water only Cost effective 60% N.V. in water Low Amine Value < 150 AMV (on solids) Cost effective 120 BoS Lower Color 9 Max Low color systems <10 4

5 New WB Amine Curing Agent Designed to Meet Emerging Market Needs Starting Formulation Property Formulation Design Target Value* Benefit New WB Amine Long Pot Life > 2 hrs Easy to Apply 2-5 hrs. Higher mixed paint solids Lower VOC Fast Dry Times (Circle Dry or walk on) 50-60% NV (vol.) Economical 52% 0-50 g/l < 12 hrs VOC Compliant in SCAQM district! Fast Return to Service 0-45 g/l 11 hrs Good Hardness Development >4B in 24 hrs; >HB in 3 Days Fast Return to Service 4B overnight; F at 7 days Good Chem. Resist. (MEK Double Rubs) >100 after 7 day cure Resistant to Many Chemicals High >85 for clears Excellent Appearance 92 for clear systems 5

6 The New WB Amine Curing Agent is Easier to Handle than Competitive Products cp) Vis scosity ( 100,000 90,000 80,000 70, ,000 50,000 40, ,000 20,000 10,000 0 Competitor B-6 (@ 60%N.V.) New WB Curing agent Competitor B-6 (@80%) Com petitor A-7 (@55%) Competitor A-4 (@70%) Temperature (ºF) 6

7 New WB Amine Curing Agent for Concrete Additional Benefits No co-solvent for more formulation latitude Low odor = GREEN Unused paint gels overnight for easy disposal Stable gloss throughout pot life Excellent adhesion to wet concrete Easy water (Zero VOC) clean-up = GREEN 7

8 Starting Point Formulations Provide a Fast Start for Your New Paint Formulation Projects Enamels with this New WB Amine Curing Agent for Concrete Protection A) Gray Enamel with Fast Dry Medium gloss gray enamel (SPF mix ratio with Bis-A LER B) Gray Primer with Long Pot Life and Improved Chemical Resistance Low gloss gray primer (SPF mix ratio with Bis-F LER 8

9 Starting Point Formulations Provide a Fast Start for Your New Paint Formulation (continued) Clears based with this New WB Amine Curing Agent for Concrete Protection and Sealers C) Clear Concrete Sealer is Economical High gloss clear (SPF 1623), 3:1 mix ratio with Bis-A LER D) High Gloss Clear Top Coat with Less Induction and Better Chemical Resistance High gloss clear (SPF 1622), 3:1 mix ratio With Bis-F LER 9

10 Two Grades of Liquid Epoxy Resin Give Formulators a Choice Liquid Bis-A Epoxy Resin Most Popular Grade for Coatings and Civil Engineering RT Viscosity of 130 P = 13,000 cp Liquid Bis-F Epoxy Resin Widely used in Composites, Electronics and Adhesives y, RT Viscosity of 35 P = 3,500 cp Good chemical resistance Superior chemical resistance Cost-effective resin grade ~10% over std. Bis-A LER EPON Resin 828 EPON Resin 863 EPON Resin 863 offers: Lower induction times Longer pot life (working life) Better chemical resistance 10

11 Low Gloss, Gray Primer Starting Formula Gives Coating with Longer Pot Life Wet Properties Mix Ratio (volume) 4:1 140 Gloss, Viscosity and Pot Life LER-type Bis F epoxy 120 VOC, Mixed 37 g/l 100 % N.V. 48% (vol) 59% wt. Induction time min. Pot-life ~3 hrs. Value Visc. (KU) Gloss (@60º) Dry Time, Set to Touch 45 min. 0 Dry Time, Dry thru hr. Pencil Hardness 24 hrs. 7 Days Time (min.) Gloss measurements are on Leneta Charts 1 SF 1620, Low Gloss primer for Cement 11

12 Medium Gloss, Gray Enamel Starting Formula provides a Coating with Fast Dry Wet Properties Mix Ratio (volume) 31 3:1 LER-type Bis A epoxy 140 Gloss, Viscosity and Pot Life VOC, Mixed 46 g/l % N.V. 50% vol % wt 60 PVC 20% 40 Visc. (KU) Induction Time 1 ~30 min. 20 Gloss (@60º) 0 Pot-life ~2 hrs Dry Time, Dry to touch 45 min. Dry Time, Dry thru 10 hrs Pencil Hardness 24 hrs. 7 Days Value Time (min.) after induction Gloss measurements are on Leneta Charts 1 SF 1626, 3:1 Enamel for Cement 12

13 High Gloss, Clear Starting Formulations Starting Formulation 1622 New WB Amine Curing Agent & LER (Bis-F) Starting Formulation 1623 New WB Amine Curing Agent & LER (Bis-A) Curing Agent Component Component Weight (lbs) Gallons (US) Weight (lbs) Gallons (US) New WB Amine Lutensol OP DI Water Total Part A Epoxy Component Bis-F LER Bis-A LER Total Part B Grand Total These are starting point formulas. They are designed to demonstrate the performance of the curing agent and not intended to be a final formula. 13

14 Formulation Benchmarking studies Enamels Physical properties Adhesion performance and mode of failure Clear coats Physical properties Adhesion performance and mode of failure Enamel + clear coat Adhesion study 14

15 SPF 1626 Outperforms Commercial Do-it-Yourself Systems Property Medium Gloss Gray 1 Commercial DIY #1 Commercial DIY #2 Commercial DIY #3 Commercial DIY #4 Mix Ratio (vol.) 3:1 3:1 3:1 3:1 2:1 Induction time 30 Min. 5 min min. 30 Min. 15 min. Pot 77ºF 2-3 hrs 8 hrs. 1.5 hrs 2.5 hrs 4 hrs. 48 VOC, g/l 48 <50 <100 <100 0 before tinting % N.V. (wt./vol.) 59% / 50% 43% / 33% 59% / 48% 62% / 49% 50% / 45% Recommended 1 coat / coat / coat / 1 coat / 6-10 Application mils wft mils wft 7-11 mils wft mils wft Pencil Hardness, Initial / 7 Days In Can Appearance after overnight induction 2 coats, total film mils wft 4B / F 3B/F 5B / F HB/F 5B/B Gelled Liquid Skins over liquid Gelled Skins over liquid Pull-off Adhesion (ave.) 865 psi 475 psi 450 psi 400 psi 425 psi (0% failure to cement) (20% failure to cement) (45% failure to cement) (85% failure to cement) (2% failure to cement) 1 SPF 1626 based on E828 / EK

16 SF 1626 Enamel Penetrates Further and Gives Adhesion that Fails the Concrete Commercial Enamel SF :1 Enamel (EK 8547 w/e828) Property 7 days a/d) Commercial Enamel 3:1 Enamel formulation based on New WB Amine Curing agent / Bis-A LER Pull off Adhesion, psi. 500, , 975 % cohesive failure of cement 50, , 100 Weight of cement removed, g. 0.30, , 1.29 Adhesions measured with elcometer with 2.0 cm diameter dollie 16

17 Zero VOC, Clear SPF 1622 Outperforms a Commercial Clear Formulations Property Commercial Commercial Commercial Clear coat Clear Coat Clear Coat DIY #1 DIY #2 DIY #3 Starting Formula 1622 Clear coat 2 Mix Ratio (vol.) 2:1 3:1 2:1 3:1 Induction time 5 min 10 min 15 min. 30 min. Pot 77ºF 1.5 hrs 6 hrs 4 hrs 3 hrs VOC, g/l 250 max 250max 100max 0 % N.V. (wt./vol.) 66% / 61% 1 42%/ 45% 52% / 42% 54% / 43% Pencil Hardness, Initial / 7 Days 3B / HB 5B / B 3B / B >5B / HB In use appearance Clear White emulsion White emulsion White emulsion In Can Appearance after overnight Gelled Soft Gel Liquid Gelled Pull-off Adhesion (average), psi 400 (32% failure to cement) 300 (<5% failure to cement) 238 (50% failure to cement) 450 (<5% failure to cement) 1 Estimated based on MSDS information 2 SPF 1622 based on E863 / EK

18 SF 1622 Clear Exhibits Better Adhesion than Commercial Clear Commercial Clear coat SF :1 Clear (EK8547 & E863) Property 7 days a/d) Commercial Clear coat (New WB Amine Curing Agent/ Bis-F LER) Starting Formula 3:1 Clear coat Pull off ffadhesion, psi 350, , 500 % cohesive failure of cement 25%, 40% >95%, 90% Weight of cement removed 024g 0.24 g, g 052g 0.52 g, 049g 0.49 Adhesions measured with elcometer with 2.0 cm diameter dollie 18

19 Adhesion Study for Enamel + Clear coat Systems Commercial Clear Commercial Clear Commercial Enamel No Enamel Clear coat Adhesion Failure mode % loss of adhesion to cement % cohesive failure of cement Force (psi) Net weight of coating + cement removed 1 0% 100% g 2 3:1 Enamel Commercial DIY Clear coat 0% 100% g 3 (EPON 828/ New WB Amine) Clear coat 0% 100% g 4 (EPON 863/New WB Amine) 0% 100% g 5 99% 1% g 6 Commercial DIY Commercial DIY Clear coat 3:1 enamel 98% 2% g 7 Clear coat 80% 20% g 8 (EPON 863/New WB Amine) 5% 95% g 19

20 Failure Mode Analysis Chemical Spot testing Osmotic Blister testing Water Vapor permeability testingti 20

21 New WB Amine Curing agent has Better Chemical Resistance than Commercial Systems 24 hrs RT. (CTCH) uncovered Solvent MEK Gas VOC Green Simple White Vinegar ) Anti Fre eeze (Dex cool Transm mission Fluid mustard Yellow Brake Fluid ield Washer flu uid Windsh 30% Su ulfuric Acid 10% Na aoh Motor Oil (10W30) 100 do ouble rubs tane 1 hr cover red) (89 oct Total Score New WB Amine Curing agent/ Bis-A LER in a Med. Gloss Gray formulation agent/ Bis-A LER inamed Commercial DIY #1 < Commercial DIY #2 < Commercial DIY #3 < Commercial DIY # Relative Scale 10= Best=No Effect 21

22 Mode of Failure Blistering Two types of blister formations Traditional blistering is where a chemical permeates a coating and at the coating/substrate interface there is a loss of adhesion. An additional mode of failure for concrete is osmotic blistering. Osmotic blistering is where the water migrates through the concrete to the concrete / coating interface and if this water is trapped and there is a loss of adhesion, then the coating will blister. 22

23 Basic principles for Osmotic blistering Blister, filled with water Pores in the concrete Impermeable Topcoat Primer Scheme of a water filled blister Failure by osmotic blistering 23

24 Osmosis Resistant EP Primers Basic principles Two types of systems are used in the industry and were studied: 1. Solvent free systems: Systems which use a specially designed primer which can resist mechanically the development of blisters and will keep a superior adhesion in all instances 2. Waterborne systems: «Open» or so-called «Porous» Systems which allow the free water to pass through h the interlayer and prevent the development of localized li pressure 24

25 Osmosis Blister Testing Test procedure Tests according global standard DIN EN Application to dry concrete plates with a prolonged testing period 45 days typical, up to 9 months. Afterwards, adhesion Pull-off tests are performed after one month recovery. Tests were stopped when blisters were observed. Dry concrete plates, 30 x 30cm x 6cm - Blister rating - Primer or sealer coat 450 g/m2 - Enamel coating direct to concrete - Self leveling flooring 25

26 Blister Resistance Testing 26

27 Osmotic Blistering Results Test Block No. Formulations Applied Wt. Results Pull off adhesion 1 Bis-F LER / New WB Amine Curing Agent 40 g No Blisters at 56 days 493 psi 2 WB benchmark primer (2K WB epoxy) Bis-F LER / New WB Amine Curing Agent 40 g 100 g No Blisters at 56 days 406 psi 3 Bis-F LER / New WB Amine Curing Agent Mid coat (2K WB epoxy) Top Coat (2K solvent free epoxy system) 40 g 500 g 200 g No Blisters at 56 days 479 psi 4 (Control) WB benchmark primer (2K WB epoxy) 40 g No Blisters at 56 days 450 psi 5 (Control) WB benchmark primer (2K WB epoxy) Mid coat (2K WB epoxy) Top Coat (2K solvent free epoxy system) 40 g 500 g 200 g No Blisters at 56 days 479 psi Pull off adhesion was performed after the blocks were allowed to recover for 28 days 27

28 Water Vapor Transmission of Organic Coating Films (ASTM D ) New WB Amine Curing Agent / Bis-F LER (@ 0.9:1.0 Epoxy equiv. : Amine equiv.) ht Loss (gra ams) Weig New WB Amine Curing Agent / Bis-F LER (@ 1.1:1.0 Epoxy equiv. : Amine equiv.) Control ( Bis-A LER/ Cycloaliphatic Amine) Time (days) These WB systems exhibit 5 times greater water permeability vs. the solvent less system 28

29 Osmotic blister and water vapor transmission Conclusions and Ongoing g Work Based on Adhesion and Water Vapor transmission data, this NEW Waterbased Amine curing agent has the potential for the development of osmotic blister resistant flooring systems Coating on the concrete blocks exhibit excellent adhesion Superior water vapor transmission results This offers formulators broad latitude for optimization of other properties (i.e. solvent resistance and chemical resistance) Further work under consideration: Formulation development of self leveling flooring systems Development of formulation guidelines (do s and don ts) Assist with specific customer opportunities Reminder- The water vapor transmission testing was performed with free films. These free films do not include any substrate effects. (i.e. any surface contamination, residual cleaners and contaminates,especially acids from the surface preparation of the concrete block, or surface contouring). 29

30 New WB Amine Curing agent for Concrete Concluding Benefits: Excellent product stability Easy product handling and application Successful field trial at 55º F No co-solvent Easier to Formulate Ultra-Low and Zero VOC is now possible Easy water clean-up Excellent penetration and adhesion 100% Cohesive failure of cement Superior clarity Clear films Clear solution to < 25% N.V. Low Curing Agent Demand (64 PHR) 30

31 New WB Curing Agent Outperforms Competitive Products in Side-by-Side Testing Property New WB Comp. Curing Comp. Curing Curing Agent Agent A Agent B Low Viscosity and Water clean-up Easy to Handle Easy to Apply Performance Coating Appearance Cost in Use + = = 31

32 EPIKURE Curing Agent 8547-W-60 New Curing agent for Concrete coatings 60% solids in water No cosolvent TSCA Listed Not Corrosive, Not Toxic, by D.O.T. Regulations Property Conditions Value Clear to Slightly Hazy solution Solids ºC 59-61% Viscosity Color Gardner 9 max. Amine Value BoS Amine Equiv wt BoS

33 Summary High Performance, Ultra-Low VOC epoxy coatings for concrete can be developed with this new WB Amine Curing Agent EPIKURE Curing Agent 8547-W-60 33

34 Special Thanks and Recognition C. Ash J. Elmore D. Weinmann D. Woodcock A. Bernard J. Hite P. Deudon V. Maksymowsk C. Medlock 34

35 Are there any Questions? Contact information David Fernee Sample requests or your local Hexion epoxy distributor 35