ULTRA FIRE RESISTANT THERMOSET POLYMERS

Ultra fire resistant thermoset polymers
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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

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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

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FAA PROGRAM OBJECTIVE:

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PROGRAM DELIVERABLES

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A VERSATILE BUILDING BLOCK IS NEEDED Thermoplastics Thermosets

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BACKGROUND: Bisphenol-C Polymers 1874 : Chloral-phenol buildup response item (I) first reported. 1874 : Dehydrochlorination to 1,1-dichloro, 2,2-bis(4-hydroxyphenyl) ethylene (bisphenol-C, BPC) initially reported.

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BACKGROUND: Bisphenol-C Polymers 1964 : Polycarbonate from BPC initially reported. 1965 : "Self-Extinguishing Epoxies" from BPC initially reported in Poland.

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BACKGROUND: Bisphenol-C Polymers 1970's: GE starts research to acquire non-blazing (XB) plastics. Examines bisphenol-C, etherimide, and acetylenic polymers. C.B. Quinn, 1967 • Acetylenic gatherings increment roast yield in fire. • Too numerous acetylenes increment combustibility (diminish LOI)

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BACKGROUND: Bisphenol-C Polymers 1970's: GE creates and licenses mechanical process science to make BPC-polycarbonate (XB-1) and polyetherimide (XB-2). XB-1 XB-2 GE downselects to XB-2 (ULTEM™) in light of flame (UL) and high temperature (TEM) capacity.

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BACKGROUND: Bisphenol-C Polymers 1980's – 1990's: Research in chloral buildup polymers continues in Poland and Russia yet not in U.S.A. • Fire testing constrained to fire tests (combustibility). • High LOI (50-60) and "self-quenching" conduct credited to chlorine content. • No business action. 1994: Comprehensive audit: Condensation Polymers Based on Chloral And Its Derivatives , A.L. Rusanov, Progress In Polymer Science, Vol. 19, pp. 589- 662 (1994)

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BACKGROUND: Flaming Heat Release Rate Measured 1997: FAA measures flaring warmth discharge rate of BPC polycarbonate in OSU fire calorimeter .

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BACKGROUND: New Flammability Screening Test 1998: FAA creates milligram-scale warm discharge rate test to quicken hunt down new polymers Forced Nonflaming Combustion

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TEST METHOD REPRODUCES FLAMING COMBUSTION

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HEAT RELEASE CAPACITY PREDICTS FIRE RESPONSE slant = 1 kg-K/m 2 - s (according to 1-D copying model) Provides new ability for fast screening of research polymers for imperviousness to fire.

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BACKGROUND: Flammability Screening Yields Results 1998: FAA teams up with Ciba Specialty Chemicals/Vantico Performance Polymers Division, Brewster, NY to create ultra fire safe cyanate ester thermoset saps for flying machine insides BPC cyanate ester distinguished as having least warmth discharge capacity of any thermoset tried to date BPC cyanate ester patent documented by Ciba/Vanitco BPC cyanate ester scaled-up and prepregged for seat scale fire calorimetry testing 1999-exhibit: University (UMASS, Rice) inquire about proceeds on BPC copolymers and mixes.

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

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BACKGROUND: Technology Transfer 2001: FAA Scales up BPC polycarbonate chemistry with Dow Chemical, Freeport TX 2002: U.S. Naval force tests and supports BPC cyanate ester composites for use in submarines. 2003: VANTICO gets piece of matter patent for BPC cyanate ester . 2004: NAVY honors SBIR projects to create BPC thermoset prepare science for expansive shipboard structures

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BPC THERMOSET POLYMERS Epoxy Cyanate Ester Epoxy-Cyanate Ester Blends

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EPOXY

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EPOXIES: Synthesis according to DGEBA

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

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FIRE RESISTANCE OF BPC EPOXY LIMITED BY HIGH FUEL VALUE OF GLYCIDYL ETHER Dichloroethylidene (DCE) aggregate has zero fuel esteem, yet… "R" assemble for epoxy has moderately high fuel esteem. "R" Heat of ignition , h c = 7 kJ/g-polymer (hypothetical) = 11 kJ/g-polymer (measured)

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EPOXY HEAT RELEASE CAPACITIES DGEBA DGEBC UL 94 V-0 (ordinarily)

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

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EPOXY FIRE CALORIMETRY: Total Heat Release Glass texture lamina FAR 25.853 (a-1) DGEBA DGEBC FAA Maximum (2-min, flaring)

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MECHANICALS: BPA ( ) versus BPC ( ) Epoxy STRENGTH STIFFNESS HEAT OF POLYMERIZATION GLASS TRANSITION TEMPERATURE

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CYANATE ESTERS

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

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EFFECT OF BISPHENOL ON HEAT RELEASE RATE OF CYANATE ESTERS ASTM 1354, cone calorimeter at 50 kW/m 2 warm flux, slick pitch, 1/4-creep thick

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

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

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CYANATE ESTER-EPOXY BLENDS

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FIRE PERFORMANCE OF BPC(CE-EP) BLENDS 600 40 35 500 30 400 25 Heat Release Capacity of Blend, J/g-K 20 300 (Baseline Corrected) OSU Peak HRR, kW/m 2 15 200 10 100 5 0 0.2 0.4 0.6 0.8 1 Mole Fraction BPC-Epoxy in Blend

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

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Acknowledgments 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

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