1. ULTRA FIRE RESISTANT THERMOSET POLYMERS Richard E. Lyon Fire Research Program Fire Safety Section AAR-440 FEDERAL AVIATION ADMINISTRATION W.J. Hughes Technical Center Atlantic City International Airport, NJ 08405

2. ULTRA FIRE RESISTANT THERMOSET POLYMERS OUTLINE OF TALK FAA Fire Resistant Materials Program Background of Bisphenol-C Polymers New Bisphenol-C Polymers Fire & Flammability Results Conclusions

3. FAA PROGRAM OBJECTIVE:

4. PROGRAM DELIVERABLES

5. A VERSATILE BUILDING BLOCK IS NEEDED ThermoplasticsThermosets

6. BACKGROUND: Bisphenol-C Polymers 1874: Chloral-phenol condensation reaction product (I) first reported. 1874: Dehydrochlorination to 1,1-dichloro, 2,2-bis(4-hydroxyphenyl) ethylene (bisphenol-C, BPC) first reported.

7. 1964: Polycarbonate from BPC first reported. 1965: “Self-Extinguishing Epoxies” from BPC first reported in Poland. BACKGROUND: Bisphenol-C Polymers

8. GE begins research to obtain non-burning (XB) plastics. Investigates bisphenol-C, etherimide, and acetylenic polymers. 1970’s: BACKGROUND: Bisphenol-C Polymers Acetylenic groups increase char yield in flame. Too many acetylenes increase flammability (decrease LOI) C.B. Quinn, 1967

9. 1970’s: BACKGROUND: Bisphenol-C Polymers GE develops and patents industrial process chemistry to make BPC-polycarbonate (XB-1) and polyetherimide (XB-2). GE downselects to XB-2 (ULTEM™) because of fire (UL) and high temperature (TEM) capability. XB-2 XB-1

10. 1980’s – 1990’s: Research in chloral condensation polymers continues in Poland and Russia but not in U.S.A. Fire testing limited to flame tests (flammability). High LOI (50-60) and “self-extinguishing” behavior attributed to chlorine content. No commercial activity. BACKGROUND: Bisphenol-C Polymers 1994: Comprehensive review: Condensation Polymers Based on Chloral And Its Derivatives, A.L. Rusanov, Progress In Polymer Science, Vol. 19, pp. 589- 662 (1994)

11. BACKGROUND: Flaming Heat Release Rate Measured 1997: FAA measures flaming heat release rate of BPC polycarbonate in OSU fire calorimeter.

12. BACKGROUND: New Flammability Screening Test 1998: FAA develops milligram-scale heat release rate test to accelerate search for new polymers Forced Nonflaming Combustion

13. TEST METHOD REPRODUCES FLAMING COMBUSTION

14. slope = 1 kg-K/m 2 -s HEAT RELEASE CAPACITY PREDICTS FIRE RESPONSE (as per 1-D burning model) Provides new capability for rapid screening of research polymers for fire resistance.

15. BACKGROUND: Flammability Screening Yields Results 1998: FAA collaborates with Ciba Specialty Chemicals/Vantico Performance Polymers Division, Brewster, NY to develop ultra fire resistant cyanate ester thermoset resins for aircraft interiors BPC cyanate ester identified as having lowest heat release capacity of any thermoset tested to date BPC cyanate ester patent filed by Ciba/Vanitco BPC cyanate ester scaled-up and prepregged for bench scale fire calorimetry testing 1999-present: University (UMASS, Rice) research continues on BPC copolymers and blends.

16. 2000:“Thermal Decomposition Mechanism of…”, M. Ramirez, DOT/FAA/AR-00/42, and A. Factor, GE Plastics BACKGROUND: Thermal Degradation Mechanism Identified 350-450°C – 80 kJ/mole

17. 2001: FAA Scales up BPC polycarbonate chemistry with Dow Chemical, Freeport TX 2002:U.S. Navy tests and approves BPC cyanate ester composites for use in submarines. 2003: VANTICO obtains composition of matter patent for BPC cyanate ester. 2004:NAVY awards SBIR programs to develop BPC thermoset process chemistry for large shipboard structures BACKGROUND: Technology Transfer

18. BPC THERMOSET POLYMERS Epoxy Cyanate Ester Epoxy-Cyanate Ester Blends

19. EPOXY

20. EPOXIES: Synthesis as per DGEBA

21. EPOXY FORMULATIONS: Hardeners Examined EMI-24 (2 phr) TETA (14 phr) MDA (58 phr) BPC (78 phr DGEBC) Cyanate ester of BPC (53 phr DBEBC) BPA (66 phr DGEBA)

22. “R” group for epoxy has relatively high fuel value. Dichloroethylidene (DCE) group has zero fuel value, but… FIRE RESISTANCE OF BPC EPOXY LIMITED BY HIGH FUEL VALUE OF GLYCIDYL ETHER “R” Heat of combustion, h c = 7 kJ/g-polymer (theoretical) = 11 kJ/g-polymer (measured)

23. EPOXY HEAT RELEASE CAPACITIES DGEBC DGEBA UL 94 V-0 (typically)

24. EPOXY FIRE CALORIMETRY: Peak HRR DGEBC DGEBA Glass fabric lamina FAR 25.853 (a-1) FAA Maximum

25. EPOXY FIRE CALORIMETRY: Total Heat Release DGEBC DGEBA FAA Maximum Glass fabric lamina FAR 25.853 (a-1) (2-min, flaming)

26. GLASS TRANSITION TEMPERATURE STIFFNESS STRENGTH MECHANICALS: BPA () vs. BPC () Epoxy HEAT OF POLYMERIZATION

27. CYANATE ESTERS

28. CYANATE ESTER: Polymerization Reaction 200°C BPC triazine thermoset polymer BPC cyanate ester monomer

29. EFFECT OF BISPHENOL ON HEAT RELEASE RATE OF CYANATE ESTERS ASTM 1354, cone calorimeter at 50 kW/m 2 heat flux, neat resin, 1/4-inch thick

30. BPC CYANATE ESTER: FAA Heat Release Rate Test glass fabric lamina 1/8-in NOMEX honeycomb

31. STRUCTURAL COMPOSITES FOR NAVY SUBMARINES Fire Test/CharacteristicRequirement (MIL-STD-2031) BPC-CE Time to ignition (s) at irradiance: 100 kW/m 2 75 kW/m 2 50 kW/m 2 25 kW/m 2 Peak/Average Heat Release Rate (kW/m 2 ) at irradiance: Smoke Obscuration, D max /D s (avg): 100 kW/m 2 75 kW/m 2 50 kW/m 2 25 kW/m 2 > 300 > 150 > 90 > 60 < 50/50 < 65/50 < 100/100 < 150/120 Composite Resin Phthalo- nitrile Silicone Combustion Gas Toxicity (CO/CO 2 /HCN/HCl): Mechanical Properties pass good pass N/A good pass poor < 200/100 Only 3 resins pass fire performance requirements as glass composites: J. Koo, et. al., SAMPE 2001 Cure Temperature< 200°C> 375°CN/A

32. CYANATE ESTER-EPOXY BLENDS

33. 0 100 200 300 400 500 600 0 5 10 15 20 25 30 35 40 00.20.40.60.81 Heat Release Capacity of Blend, J/g-K (Baseline Corrected) OSU Peak HRR, kW/m 2 Mole Fraction BPC-Epoxy in Blend FIRE PERFORMANCE OF BPC(CE-EP) BLENDS

34. CONCLUSIONS: Comparing Properties Fire Hazard Potential (  c ): Fire Hazard (HRR): Glass Transition Temperature, K: Modulus: Yield Strength: Yield Strain: BPC / BPA – 90 % – 60 % + 3 % + 10 % Average Change (5-7 polymers)

35. ACKNOWLEDGEMENTS Jennifer Stewart, Huiquing Zhang, UMASS Lauren Castelli, Mike Ramirez, FAA Arnie Factor, Mike MacLaury, GE Plastics Borsheng Lin, Mike Amone, Ciba Specialty Chemicals Richard Walters, Galaxy Scientific Gary Green, Pacific Epoxy