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Office of Aviation Research Washington, D.C. 20591
Combustibility of Cyanate Ester Resins
June 2002 Final Report
This document is available to the U.S. public through the National Technical Information Service (NTIS), Springfield, Virginia 22161.
U.S. Department of Transportation Federal Aviation Administration
NOTICE This document is disseminated under the sponsorship of the U.S. Department of Transportation in the interest of information exchange. The United States Government assumes no liability for the contents or use thereof. The United States Government does not endorse products or manufacturers. Trade or manufacturer's names appear herein solely because they are considered essential to the objective of this report. This document does not constitute FAA certification policy. Consult your local FAA aircraft certification office as to its use.
This report is available at the Federal Aviation Administration William J. Hughes Technical Center’s Full-Text Technical Reports page: actlibrary.tc.faa.gov in Adobe Acrobat portable document form (PDF).
Flammability. 17. Gandhi* 9. No.Technical Report Documentation Page 1. Thermoset polymer 19. Security Classif. DOT/FAA/AR-02/44 4. Springfield. (of this page) Unclassified Form DOT F1700. Richard E. Type of Report and Period Covered U. Distribution Statement Polycyanurate. Hughes Technical Center COTR is Richard Lyon. Heats of complete combustion of the polymer and fuel gases were determined by oxygen bomb calorimetry and pyrolysis-combustion flow calorimetry. yet produced significantly less smoke and comparable levels of carbon monoxide and soot. the rate of heat release. Report No. NJ 08405 12. 3. Report Date COMBUSTIBILITY OF CYANATE ESTER RESINS June 2002 6. Richard Walters* and S.7 (8-72) Unclassified Reproduction of completed page authorized 26 . Department of Transportation Federal Aviation Administration Office of Aviation Research Washington. Author(s) 8. Lyon. Fire response parameters derived from the data include the thermal inertia. Work Unit No. Fire calorimetry experiments were conducted to measure the heat released. Contract or Grant No. C Fire Safety Branch Egg Harbor Township. (of this report) This document is available to the public through the National Technical Information Service (NTIS). Security Classif. Title and Subtitle 5. Performing Organization Code 7. Halogen-containing polycyanurates exhibited extremely low heat release rate in flaming combustion compared to the hydrocarbon resins. Price 20. Key Words 18. Supplementary Notes Final Report 14. Sponsoring Agency Code AIR-120 The FAA William J.S. DC 20591 15. 13. 2. char-forming thermoset polymers. Virginia 22161. Performing Organization Report No. Research and Development Division 2500 English Creek Ave. NJ 08234 Atlantic City International Airport. and combustion efficiency. Sponsoring Agency Name and Address 11. 16. Performing Organization Name and Address 10.. effective heat of combustion. of Pages 22. Abstract Flaming and nonflaming combustion studies were conducted on a series of polycyanurates to examine the effect of chemical composition and physical properties on the fire behavior of these cross-linked. Hughes Technical Center Airport and Aircraft Safety *Galaxy Scientific Corp. respectively. and the smoke generation in flaming combustion. 21. (TRAIS) Federal Aviation Administration William J. heat of gasification. Government Accession No. Fire. Cyanate ester. Bldg. Recipient's Catalog No.
TABLE OF CONTENTS Page EXECUTIVE SUMMARY INTRODUCTION EXPERIMENTAL MATERIALS METHODS Oxygen Bomb Calorimetry Pyrolysis Combustion Flow Calorimetry Fire Calorimetry RESULTS AND DISCUSSION NONFLAMING COMBUSTION FLAMING COMBUSTION Ignitability Heat Release Rate Combustion Products CONCLUSION REFERENCES APPENDIX A—HEAT RELEASE HISTORIES OF POLYCYANURATES AT INDICATED HEAT FLUXES v 1 1 1 3 3 3 4 5 5 7 9 10 12 15 15 iii .
and Char Fraction for Polycyanurates Fire Behavior of Polycyanurates in Cone Calorimeter Ignition Properties of Polycyanurates Cone Calorimeter Data for Smoke Obscuration and Combustion Products Yields Page 2 6 8 10 13 iv . Specific Heat Release. Heat Release Capacity.LIST OF FIGURES Figure 1 2 3 4 5 Cyanate Ester Polymerization and Thermal Degradation Reactions Pyrolysis-Combustion Data for Polycyanurates Time-to-Ignition Data for B-10 Polycyanurate Heat Release Rate Histories of Polycyanurates at 50 kW/m2 Heat Flux in Cone Calorimeter Soot Yield and CO/CO2 Ratio Versus Combustion Efficiency in Flame for Cyanate Esters at Irradiances Tested in Study Page 1 7 10 11 14 LIST OF TABLES Table 1 2 3 4 5 Trade Names and Chemical Structure of the Cyanate Ester Monomers Net Heat of Complete Combustion.
heat of gasification. Halogen-containing polycyanurates exhibited extremely low heat release rate in flaming combustion compared to the hydrocarbon resins. respectively. the rate of heat release. Fire calorimetry experiments were conducted to measure the heat released. char-forming thermoset polymers. and the smoke generation in flaming combustion. Heats of complete combustion of the polymer and fuel gases were determined by oxygen bomb calorimetry and pyrolysis-combustion flow calorimetry. and combustion efficiency. Fire response parameters derived from the data include the thermal inertia. effective heat of combustion. yet produced significantly less smoke and comparable levels of carbon monoxide and soot. v/vi .EXECUTIVE SUMMARY Flaming and nonflaming combustion studies were conducted on a series of polycyanurates to examine the effect of chemical composition and physical properties on the fire behavior of these cross-linked.
The present flaming and nonflaming combustion studies are an attempt to correlate the fire behavior of polycyanurates with their chemical structure. and chemical structure are shown in table 1. flammability . M-10. at 450° ±8°C. The amount of char formed in the thermal degradation process ranges from 30% to 60% in rough proportion to the aromatic content of the polycyanurate backbone. atomic formula. XU-366. 1 . chemical structure. The chemistry and properties . A list of the cyanate ester monomers along with their trade name. Cyanate Ester + H O R 3 C N Volatiles R O C N R + 200°C ∆ O C N O N R O N Polycyanurate R ∆ 450°C N O O N N O Char R O Polymerization Thermal Degradation FIGURE 1. CYANATE ESTER POLYMERIZATION AND THERMAL DEGRADATION REACTIONS EXPERIMENTAL M AT E R I A L S . Because the thermal decomposition (ignition) temperature and heat transport properties of the polycyanurates are relatively independent of the backbone. the fire behavior of these materials will depend only on their fuel value. Recent work by the Federal Aviation Administration (FAA)  shows that aromatic polycyanurates thermally decompose by a common mechanism which begins with thermolytic cleavage of the resin backbone between 300°–450°C. nitrogen. The char contains carbon. F-10. and culminates with decyclization of the cyanurate rings. L-10.INTRODUCTION Polycyanurates are thermoset polymers that are cross-linked through the cyclotrimerization reaction of three cyanate ester (–O–C≡ N) groups to form oxygen-linked triazine rings (cyanurates). and oxygen in the approximate atomic ratio C/H/O/N = 15/4/2/1 as indicated in figure 1. so that void-free castings and fiber reinforced composites with good surface finish can be obtained. and fire behavior [3-6] of cyanate esters have been reviewed in detail. to produce a variety of volatile fuel species as shown schematically in figure 1. char yield. hydrogen. and char properties. Polymerization (curing) occurs via a thermally-activated addition reaction which produces no volatiles. The cyanate ester resins AroCy B-10.
] Bisphenol-A Cyanate Ester [1156-51-0] Hexafluorobisphenol-A Cyanate Ester [32728-27-1] Bisphenol-E Cyanate Ester [47073-92-7] Tetramethylbisphenol-F Cyanate Ester [101657-77-6] Bisphenol-M Cyanate Ester [127667-44-1] Phenol Novolac Cyanate Ester [P88-1591] Formula C17H14O2N2 C17H8O2N2F6 C16H12O2N2 NCO Structure CH3 C CH3 CF3 NCO C CF3 CH3 NCO H 3C OCN OCN C H OCN CH3 AroCy M-10 C19H18O2N2 NCO H 3C CH2 OCN CH3 AroCy XU-366 C26H24O2N2 CH3 NCO C CH3 CH 3 C CH 3 OCN OCN OCN CH2 Cl C Cl C OCN CH2 AroCy XU-371 C23H15O3N3 AroCy RD98-228 AroCy XU-71787. Performance Polymers Division.02L were provided by Y.02L. TABLE 1. Cured plaques of resin XU-71787. commercial (or precommercial) samples which were used as received without further purification or catalysts. No. NJ.02L Primaset PT-30 PT-60 PT-90 Bisphenol-C Cyanate Ester C16H8N2O2Cl2 BPC = [14868-03-2] Dicyclopentadienylbisphenol Cyanate Ester [119505-06-5] Novolac Cyanate Ester n = 1 [Ass. 160817] n = 7 [153191-90-3] NCO OCN OCN C17H17NO OCN OCN CH2 CH2 n OCN C23H15O3N3 C47H30N6O6 C71H45N9O9 2 . PT-60. No. and PT-90 are produced by Lonza Incorporated. TRADE NAMES AND CHEMICAL STRUCTURE OF THE CYANATE ESTER MONOMERS Trade Name AroCy B-10 AroCy F-10 AroCy L-10 Chemical Designation [CAS Reg. No. All of the cyanate ester monomers in this study were one-part. Incorporated. Fairlawn. Brewster. 100% solids. Benecia. XU-71787. CA.A. The phenol novolac-based cyanate ester resins Primaset PT-30. and RD98-228 were produced by Ciba Specialty Chemicals. 160817] n = 4 [Ass.XU-371.L. NY (currently Vantico).
water. which is typically a few degrees Kelvin. in units of kJ. Specific heat release.c1 . and the initial mass m0 (g) according to h0 c . >99. The net heat of complete combustion h0 c . Methane. oxygen. removed from the mold. Carbon dioxide. ME T HODS .x 10. PCFC. were measured in a PCFC developed by the FAA  for heat release rate (HRR). A sample weighing 1. The bomb is then sealed. s (net) is calculated from the gross heat of complete combustion in kJ/g according to equation 2. where oxygen is added to effect complete (nonflaming) combustion of the volatile fuel.96 kJ/g) (2) where wH is the weight fraction of hydrogen in the sample. The fully cured samples were 10.1 mg is heated in a nitrogen stream at 4K/s to force anaerobic pyrolysis at heating rates comparable to those at a solid surface during steady flaming combustion. and pressurized to 20 atmospheres with pure oxygen. and ˙ (W/g). Upon thermal equilibration of the system at ambient temperature. 4 hours at 200°C. pyrolysis-combustion flow calorimetry (PCFC). and (if necessary) 3 . OXYGEN BOMB CALORIMETRY. The sealed bomb is then placed inside a 2-liter water bath which is inside an adiabatic container. Approximately 1 gram of sample is placed inside a sample cup in a pressure vessel (oxygen bomb) which is in contact with an ignition wire connected to two electrodes. Q c studying the molecular-level fire response of materials. the calibration factor C (J/°K).Samples for oxygen bomb calorimetry. the sample is ignited and completely combusted. The net heat of combustion accounts for the fact that at fire temperatures (≈ 1000°C). purged. degassing under vacuum at 50°C.c2)/m0 (1) where c1 and c2 are the correction factors for the heat of combustion of the ignition wire and the heat of formation of acids.99% purity grades obtained from Matheson Gas Products. PYROLYSIS COMBUSTION FLOW CALORIMETRY. and postcured free-standing at 300°C for an additional 15 minutes.64-cm solid plaques that were semitransparent and amber or dark brown in color. s (gross) – (wH)(21. and TGA. respectively. and then curing in a convection oven for 18 hours at 150°C. and nitrogen gases used for calibration and testing were dry. and 4 hours at 250°C. The volatile decomposition products are purged to a high temperature (900°C) combustion furnace. and thermogravimetric analysis (TGA) were made by pouring the warmed (50°C) liquid resins into Teflon-coated aluminum molds. fire (cone) calorimetry. s (gross) = (C∆T .x 0. Qc (J/g). The solid samples were then cooled to room temperature. The gross heat of combustion of the sample at room temperature is calculated from the temperature rise of the water bath ∆T (°K). s (net) = h c .  0 h0 c . water is in the gaseous state so that its heat of vaporization/condensation must be subtracted from the gross (room temperature) heat of combustion. Values for the gross heat of combustion were obtained with an oxygen bomb calorimeter (Parr Instrument Model 1341) using the American Society for Testing and Materials (ASTM) standard test method D 2382-88 . These polycyanurate samples were used directly for fire calorimetry or cut into samples for oxygen bomb calorimetry.0 ±0.
mass loss rate (MLR). The empirical proportionality constant E = 13.v 0 (1 – µ)E a eRTp 2 (6) The heat release capacity ηc as measured. Therefore. e is the natural number.v m0 m0 max = h c. is the mass loss rate of the pyrolyzing solid sample 0 and h c. Dividing equation 5 by β yields a derived the temperature at maximum mass loss rate.1 ±0. released by combustion per unit initial mass of solid is obtained from equation 3 as the time integral of the oxygen consumption rate after the experiment when the baseline returns to zero (t = ∞) Qc = E m0 ∞ 0 ∆m O 2(t) dt = 1 m0 ∞ 0 h c.acid gases are removed from the sample stream using Drierite™ and Ascarite™ scrubbers. and combustion gases were measured in a fire calorimeter (Cone2a. The HRR.6 kJ/g-O2 is the amount of heat liberated on average per gram of diatomic oxygen consumed by combustion. the amount of heat liberated by complete combustion of typical hydrocarbon fuels is proportional to the mass of oxygen consumed in the oxidation reactions. and Tp (K) is max ˙s (g/s). FIRE CALORIMETRY. µ (g/g) is the char fraction. v (t) is the instantaneous net heat of complete combustion of the volatile pyrolysis products per unit mass. where m s . m quantity containing only material properties and having the units (J/g-K) and significance of a heat (release) capacity. According to the principle of oxygen consumption calorimetry [11 and 12]. for example.v 0 βE a(1 – µ) eRTp 2 (5) where β (K/s) is the constant heating rate.v(t) m s(t) dt 0 (4) It has been shown  that the maximum value of the specific heat release rate measured in the PCFC has an analytic form in a constant heating rate experiment Q max c ms E max 0 = ∆m O 2 = h c. v m s . smoke density. Ea (J/mole-K) is the global activation energy for pyrolysis.v(t) E Q c(t) = ∆m O 2(t) = m s(t) m0 m0 0 (3) The total heat. Dividing the heat release rate by the initial sample weight mo gives the ˙ in units of W/g. the rate of heat released by combustion of the pyrolysis (fuel) gases ˙ O2 = h0 ˙ ˙ in the PCFC is E ∆m c . R is the gas constant. specific heat release rate Q c h c. is a molecular level fire property that is proportional to the heat release rate per unit area in steady flaming combustion  and is calculable from additive molar group contributions . Qc. Atlas Electric) operating on the oxygen 4 . in the PCFC. ηc Qc = β max = h c.
consumption principle according to ASTM E1354 . as described in detail by Babrauskas . and 100 kW/m2 using a Schmidt-Boelter heat flux gage. µ 1– µ (7) 5 . Square samples (100 x 100 x 6.4 mm) of each material were tested in a horizontal orientation with the retainer edge frame. with higher extinction area causing greater attenuation of the laser beam intensity in the test and. as per ASTM E1354 . Instantaneous smoke production rate (SPR). total heat release (THR). v . (m2/s). The smoke extinction coefficient k (1/m) was calculated from attenuation of the He-Ne laser beam intensity (I/I0) over path length L (m) in the exhaust duct as. p is. The cold wall external radiant heat flux was set at 35. The disparity between the heats of combustion of the polymer and its fuel gases is the result of partitioning of degradation products into nitrogen (N) and oxygen (O) enriched volatile fuel and N. the net heats of combustion fall within the relatively narrow range 28. tends to track the heat release rate fairly closely. and effective heat of combustion (EHC) were measured for each material at each external irradiance level. v is related to the heat of 0 0 combustion of the polymer h c. is calculated during the test from the volumetric flow rate in the exhaust duct Vf (m3/s). µ as 0 hc .5 cm above the sample surface was kept in place until stable flaming combustion was observed. The heat of combustion of the volatile fuel gases h c . about 20% greater than the 0 net heat of combustion of the volatile degradation products. F-10 and RD98228. in principle. and mass loss rate of the sample as SEA = kVf / m Extinction area is related to the number and size of smoke particles produced. 75. the extinction coefficient k (1/m). O depleted carbonaceous char during thermal degradation (see 0 figure 1). The mass of soot generated per unit mass of burned sample (kg/kg) was measured for the entire duration of the test by diverting 0. The smoke production rate. RESULTS AND DISCUSSION N O N F L A M I N G CO M B U S T I O N . The time to sustained ignition (tig). MLR. A spark igniter located 2. p – µh c . like the mass loss rate. The gross and net heats of complete combustion of the polycyanurates from oxygen bomb calorimetry are listed in table 2. The net 0 heat of complete combustion of the polycyanurate h c . Excluding the halogen-containing polymers. ˙ s. on average. for materials with tendency for swelling. greater obscuration in a fire. h c . determined by pyrolysis combustion flow calorimetry. k = (1/L) ln (I/I0). is calculated as the product of the extinction coefficient and the volumetric flow rate in the exhaust duct divided by the sample surface area A. SPR = kVf /A. Yields of carbon monoxide and carbon dioxide per unit mass loss during flaming combustion (kg-COx/kg-mass loss) were calculated from the instantaneous mass flow rates of the gases ˙ s (kg/s).v = 0 0 hc .2% of the exhaust duct flow through a 47-mm-diameter microfiberglass collection filter (Whatman #1820047) using a mass flow controller and weighing the filter before and after the test. p and its char h c.4 kJ/g. Specific smoke extinction area (SEA) (kg/s) divided by the sample mass loss rate m 2 (m /kg). HRR. 50.6-34.
39 28.1 39.6 35.6 9.The last column of table 2 are the net heats of complete combustion of the char calculated with 0 0 0 equation 7 from h c .72 Figure 2 shows specific heat release rate data for the polycyanurates obtained in the pyrolysiscombustion flow calorimeter. v kJ/g 27.64 30.1 9. TABLE 2.25 18.3 26.9 30.7 32.6 21.6 20.5 9.9 4.0 31.0 33.4 22. HEAT RELEASE CAPACITY.43 0.6 8. Polycyanurates with the highest heat release capacity and total heat release (XU-71787 and XU-366) had the highest aliphatic hydrocarbon content and fuel value.9 27.0 0 Calculated 0 h c.92 28. p (net) kJ/g kJ/g 29.59 0.77 32. SPECIFIC HEAT RELEASE.52 0. µ increases with the carbon/hydrogen content of the polymer (see table 1).9 43.1 20.36 0.4 31. AND CHAR FRACTION FOR POLYCYANURATES Oxygen Bomb 0 h c.35 0. PT. p (gross) h c .65 22.27 0.6 14. 6 .14 29.81 0 Material B-10 F-10 L-10 M-10 XU-366 XU-371 XU-71787 PT-30 RD98-228 Qc kJ/g 17.2 PCFC Char ηc J/g-K Fraction 283 62 316 280 239 88 493 122 24 0. µ kJ/g 31. lower heat release capacity.81 21. v .94 33. NET HEAT OF COMPLETE COMBUSTION.76 33. The pyrolysis residue is in reasonable agreement with the char yield after flaming combustion measured in the cone calorimeter (compare table 4). L-10.3 K/s) to compute the heat release capacity listed in table 2 along with the total heat release (area under the curve) and the char residue after the test. and lower total heat release in accordance with equations 4 and 5. v and therefore (see equation 6) had the lowest heat release capacity and total heat release.6 38. and XU-371 resulted in increased char yield. The halogen-containing polycyanurates F-10 and RD98-228 0 exhibit high char yield and low heat of combustion of the fuel gases h c .38 29.06 27. The data have been horizontally shifted from the reference XU71787 data in 200-second increments for clarity. p . M-10.0 18.7 17.25 28.42 0. It is seen that h c.1 25. and µ for each polycyanurate. h c . The maximum value of the heat release rate for each polycyanurate was divided by the sample heating rate (4.23 34.71 29. Increasing aromatic hydrocarbon content over the series B-10.6 4.53 h c.26 0.38 31. The char fraction or pyrolysis residue increases from 27% to 65% in rough proportion to the aromatic content of the monomer backbone as predicted from group contributions to the char forming tendency of polymers .
the exposed face of the material began gasifying soon after exposure to the radiant heat flux. and the development of porosity. the maximum heat release rate at ignition. heat flux data pairs in table 3. the first peak in the HRR curves (HRRpk). Complete heat release rate histories for all of the polymers and heat fluxes tested are contained in appendix A. is obtained from the reciprocal slope of a plot of peak mass loss rate versus external heat flux. there was no sustained ignition at 35 or 50 kW/m2. the peak mass loss rate (MLRpk). Listed in table 3 are the time-to-ignition (tign). Table 3 lists flaming combustion parameters extracted from the data in the appendix for the polycyanurates. 7 .2000 Heat Release Rate (W/g) XU-71787 1500 L-10 B-10 M-10 XU-366 1000 PT-30 500 XU-371 PT-90 PT-60 F-10 RD98-228 0 0 0 0 300 600 900 1200 1500 1800 2100 Time (seconds) FIGURE 2. see column 8 of table 3. Values of Lg in parentheses are the result of only two peak mass loss rate. The times to ignition for the polycyanurates were comparable at a particular heat flux with the exception of the halogenated F-10 and RD98-228 cyanate esters which were significantly longer. PYROLYSIS-COMBUSTION DATA FOR POLYCYANURATES (Horizontally shifted for clarity) F L A M I N G CO M B U S T I O N . Ignition of gaseous fuel emerging from the exposed surface occurred 1-2 minutes into the test followed by surface charring. and the effective heat of combustion (EHC) at each of the incident heat fluxes. In the case of the fluorinated polycyanurate F-10. The heat of gasification per unit mass of volatile fuel (Lg).. char cracking. During the cone calorimeter tests. i. the average heat release rate (HRRav) and the total heat released (THR) over the entire 20-minute duration of the test.e.
1 — 11.6 26.8 35.3 28.2 20.8 20 17.7 32 Lg (MJ/kg) EHC (MJ/kg) 25.9) 4.1 24.0 (2.5 24.3 8 .1 3.6 35.5 20.6 20.9 9.1 3.5 — 20.98 16.6 27.9 21.2 26.0 22.5 26.0 4.6 18.8 27.8 20.1 19.4 29. FIRE BEHAVIOR OF POLYCYANURATES IN CONE CALORIMETER Heat Flux (kW/m2) 35 50 B10 75 100 35 50 F10 75 100 35 50 L10 75 100 35 50 M10 75 100 35 50 PT30 75 100 35 50 XU366 75 100 35 50 XU371 75 100 35 50 XU71787 75 100 35 50 RD98-228 75 100 Material tig HRRpk HRRav THR (s) (kW/m2) (kW/m2) (MJ/m2) 171 166 92 93 98 195 111 118 40 246 157 160 26 272 150 101 NI — — — (90) — — — 41 53 60 82 27 78 45 53 151 96 65 56 88 149 104 102 40 183 139 126 22 204 145 100 159 305 117 97 69 251 125 117 24 280 169 133 19 338 173 112 202 179 71 46 96 166 88 78 40 118 112 83 19 138 126 74 — — — — 69 202 149 152 32 279 229 186 — — — — 203 204 68 42 93 210 99 83 41 231 123 79 23 248 127 76 167 244 55 51 67 304 113 96 32 378 172 165 20 415 166 126 294 57 19 5.9 28.8 25.4 189 124 45 13 139 177 67 16 129 186 57 19 MLRpk (g/m2-s) 8.4 5.7 3.2) (2.0 12.4 22.3 17.6 34.5 5.23 24.0 27.2 — — 16.4 24.2 — 28.5 19.3 11.3 10.7 10.9 27.1 4.3 — 17.3 25.0 (3.6 — — 16.0 25.0 27.1 26.9 24.5 19.1 21.9 26.0) 5.TABLE 3.0 17.5 4.0 27.2 28.2 7.7 21.6 20.
ignition source. q ˙ ext . kρc ≈ 1.e. the time-toignition (tign ) for a semi-infinite thickness of material having ignition temperature Tign ˙ net is experiencing a net heat flux q t ign Tign – T0 π = kρc 4 q net 2 (8) where k. then kρc can be computed from the measured TRP. The exceptions are the halogen-containing polycyanurates F-10 and RD98-228 which should have similar thermal properties to the other polycyanurates but instead exhibit experimental kρc values that are significantly higher. ρ . ˙ net .0 ±0. where TRP = (TignT0)(kρc)1/2 is referred to as the thermal response parameter (TRP). Table 4 lists the measured TRP and ignition (onset decomposition) temperature for each of the polycyanurates along with the thermal inertia (kρc) calculated from these data. are valid for use with equation 10. fire calorimeter data for time-toignition for the polycyanurates at the higher external heat fluxes can be analyzed to extract an average value of the product kρc that represents the thermal resistance (inertia) of a material to external heating over the temperature range from ambient to ignition. The net heat flux. The TRP values are at the high end of the range reported for common polymers 200–700 kW-s1/2-m–2  because of the relatively high decomposition temperature of the polycyanurates . is equal to the external radiant heat flux. q q net = q ext – q loss (9) In practice. density. heat of combustion of the fuel value of the gases. measured in laboratory thermogravimetric analyses . most of the kρ c values of the polycyanurates are in the range of common.. If the ignition temperatures of the polycyanurates are equal to their decomposition temperatures. 9 . heat lost to the environment at temperature T0 by reradiation and convection. and heat capacity of the material. From equations 8 and 9 1 t ign = – q loss π kρc Tign – T0 4 + q ext π kρc Tign – T0 4 (10) Equation 10 applies if L > 2(αtign)1/2. The reciprocal slope of the line in figure 3 equals (Tign-T 0)($kρc/4)1/2 = ($/4)1/2 TRP. and c are the thermal conductivity. q ˙ loss .IGNITABILITY. According to the thermal (heat transfer limited) theory of ignition. Values have been tabulated for many common polymers and composites .. Thus. In the present study L = 6. when Tign is accounted for in the calculation of the thermal inertia. where L is the sample thickness and α = k/ρc is the thermal diffusivity.4 mm and α = 10–7 m2/s (typically).2 kJ2/m4-s-K4 . Figure 3 is the ignition data from table 3 for the B-10 polycyanurate plotted according to equation 10. minus the respectively. the ignition time is found to depend on the ventilation conditions. unfilled polymers. equation 10). etc. perhaps due to gas phase combustion inhibition not considered in the thermal (heat transfer limited) criterion for ignition (i.e. However. so ignition times. tign ≤ L2/4α ≈ 2 minutes. i.
6 2 HEAT RELEASE RATE.3 2.2 1.5 1. The heat release rate curves are vertically shifted for clarity. The top four curves shown in figure 4 are data for the polycyanurates of monomers containing more than two reactive cyanate ester groups (i.2 1.15 0. f > 2) PT-30/60/90 and XU-371. kW/m2 FIGURE 3.1 1. These f > 2 polycyanurates showed an initial peak in heat release rate at ignition followed by a decrease in HRR as the char 10 . with the exception of F-10 which did not sustain burning at that flux.0.10 0. functionality. TIME-TO-IGNITION DATA FOR B-10 POLYCYANURATE TABLE 4..1 1. Figure 4 shows heat release rate histories for all of the polycyanurates at an external flux of 50 kW/m2.8 2. IGNITION PROPERTIES OF POLYCYANURATES Material B-10 F-10 L-10 M-10 PT-30 XU-366 XU-371 XU-7178 RD98-228 Tign °C 468 465 479 471 462 482 461 463 461 TRP kW-s1/2/m2 596 649 553 469 463 500 531 508 705 kρc kJ /m4-s-K4 1. s -1/2 0.20 1/√tign.25 0.e.05 0 0 20 40 60 80 100 120 External Heat Flux.5 1.
200 kW/m2 PT-90 PT-60 Heat Release Rate at 50 kW/m2 (kW/m2) XU-371 PT-30 L-10 B-10 M-10 XU-366 XU-71787 RD98-228 0 200 400 600 800 1000 1200 Time (seconds) FIGURE 4.layer forms and increases in thickness preventing the escape of pyrolysis (fuel) gases generated below the surface. A second heat release rate peak is observed for f > 2 polycyanurates about a minute after the ignition peak that corresponds to a catastrophic fracture of the charred surface and the instantaneous release of pressurized pyrolysis gases formed at depth . HEAT RELEASE RATE HISTORIES OF POLYCYANURATES AT 50 kW/m2 HEAT FLUX IN CONE CALORIMETER 11 .
and vaporize the resulting fuel fragments. typical of synthetic polymers . M-10. COMBUSTION PRODUCTS. The absence of catastrophic char fracture during the burning of polycyanurates from f = 2 monomers may be due to their lower char yield (35 ±7%) compared to the multifunctional resins (56 ±5%) and/or greater char permeability to pyrolysis gases. The data in table 4 (with the exception of F-10) for soot yield.. Product yields are per unit mass of sample consumed. 50. XU-71787. The broad secondary HRR peak of the f = 2 polycyanurates corresponds to char swelling and the generation of numerous small fissures in the char surface that gradually release the pyrolysis gases formed at depth.7 kJ/g. and CO2 (the latter quantities expressed as the ratio CO/CO2) are plotted versus combustion efficiency in figure 5. and heats of vaporization of the degradation products that comprise hg are similar for these polycyanurates. The char yields µ and Lg in table 3 can be used to calculate the heat of gasification per unit mass of polycyanurate. These f = 2 polycyanurates show the same initial heat release rate peak at ignition as does the polycyanurates from the f > 2 monomers. The reported values for the combustion efficiency and combustion products are cumulative values for the entire test duration. and the residual mass (char) fraction after the test.The heat release rate histories of the polycyanurates of the difunctional (f = 2) cyanate ester monomers L-10. Table 5 lists data at 35. is the heat per unit mass ˙ ′′ ) of volatile fuel and it is obtained as the reciprocal slope of a plot of the peak mass loss rate ( m ˙ ′′ versus external heat flux ( q ) assuming ext m = " qn q ext + q fl – q rr = Lg Lg (11) ˙" ˙" where q fl is the flame heat flux back to the surface and q rr is the heat lost from the surface due to reradiation. i. The f > 2 polycyanurates have a lower molecular weight between cyanurate rings (higher cross-link density)  than those from f = 2 resins. hg = (1-µ )Lg = 2. the smoke yield in terms of specific extinction area.v in table 2). The heat of gasification determined from mass loss rate measurements. as would be expected based on their similar chemical composition and thermal degradation temperature. XU-366. bond breaking energies. However. and RD98-228 are the lower six curves in figure 4. χ = EHC/h0c. 12 . This is the heat of gasification per unit mass of solid polymer.e.v. which could explain their higher char yield and the brittle fracture of their char during burning. hg. carbon monoxide (CO) and carbon dioxide (CO2) yields. B-10. Char yield is expressed per unit initial mass of sample. break primary chemical bonds in the polymer to make fuel fragments. Lg in table 3.e.. 75. The narrow range of hg indicates that the latent heats. with the exception of RD98-228. soot yield. Solid materials generate gaseous fuel when the total heat absorbed by the solid is sufficient to raise the temperature of the material to the thermal decomposition temperature (latent heat). the secondary heat release rate peak is broad and lower than the peak at ignition and occurs much later in the heat release history.5 ±0. i. and 100 kW/m2 radiant heat flux for the products of flaming combustion. The combustion efficiency in the flame χ is calculated as the ratio of the effective heat of flaming combustion (EHC in table 3) to the heat of complete combustion of the fuel gases (h0c. CO.
376 0.8 54.077 0.1 22.44 0.02 0.3 53.039 0.20 1.05 1.0 30.04 0.7 353.092 0.9 452.00 1.078 0.TABLE 5.02 0.07 1.93 0.6 709.00 0.5 683.2 723.110 0.7 61.170 0.0 70.80 1.5 70.134 0.01 0.039 0.2 50.93 0.98 0.00 0.94 1.250 Soot Yield kg/kg 0.04 1.7 395.80 1.030 0.90 0.17 0.033 0.95 1.2 56.00 0.15 1.00 0.86 1.0 27.087 0.5 33.02 0.93 2.2 0.11 0.6 705.04 1.03 0.1 906.10 0. CONE CALORIMETER DATA FOR SMOKE OBSCURATION AND COMBUSTION PRODUCTS YIELDS Heat Flux 2 Material B10 kW/m 35 50 75 100 75 100 35 50 75 100 35 50 75 100 35 50 75 100 35 50 75 100 50 75 35 50 75 100 35 50 75 100 SEA m2/kg 583.90 1.61 1.033 0.8 20.94 1.038 0.14 0.85 0.0 46.426 0.95 0.02 1.03 0.12 0.08 0.92 0.02 0.84 0.3 312.7 233.65 1.040 0.065 0.041 0.91 1.96 1.039 0.035 0.6 863.49 0.027 Combustion Efficiency.055 0.32 767.10 1.10 0.01 0.0 222.8 19.39 0.07 0.4 70.04 0.7 440.34 0.2 53.72 627.00 1.036 0.98 0.2 54.7 24.05 0.6 771.0 73 58 28 43 62.0 97.91 1.94 0.6 960.3 305.123 0.93 2.173 0.036 0.00 1.100 0.01 0.2 783.5 540.15 0.8 F10 L10 M10 PT30 XU371 XU366 XU71787 RD98-228 0.3 924.01 0.00 0.17 747.46 13 .04 0.8 522.03 1.9 320.025 CO2 kg/kg 1.9 17.01 0.085 0.240 0.0 23.96 0.98 2.72 123.024 0.6 77.41 1.033 0.80 0.8 50.3 CO kg/kg 0.162 0.59 0.78 2.87 1.036 0.6 345.6 35.9 53.89 2.03 0.02 0.01 0.3 29.0 55.1 1.030 0.052 0.5 16.61 1.0 32.58 1.047 0.93 1.071 0.8 235. χ Char % w/w 48.039 0.040 0.0 48.71 0.
2 1. listed in table 4.6 0.15 Soot Yield. is consistent with the extremely low concentrations of hydrogen cyanide (3 ppm). so their CO and soot yields as well as the specific extinction area for these halogen-containing polymers are comparable to. the CO/CO2 ratio increases as the combustion efficiency decreases as would be expected for well-ventilated flaming combustion. χ = 0. However. being highest for the polycyanurates with pendent methyl (–CH3) groups B-10. The anomalous combustion efficiencies calculated for the fluorinated cyanate ester F-10 (χ > 1) suggest that the effective heat of combustion. or lower than.93 ±0. the F-10 and RD98-228 polycyanurates barely support flaming combustion.10 0. and NOx (3 ppm) in fire gases measured for these materials in fire calorimeters  and the low smoke evolution (Ds = 1. The data in table 5 (plotted in figure 5) show that.8 1. It is seen that χ. M-10.20 0. in general.3.4 0. if they burn vigorously.10 0. such as CO and soot. soot yield appears to be largely independent of the combustion efficiency in the flame and depends instead on the chemical structure of the polymer. However.15 CO/CO2 Ratio 0. kg/kg 0. and the CO/CO2 ratio are relatively independent of the applied external heat flux. the soot yields.4 Combustion Efficiency. The apparent 14 . and XU-366. The high average flaming combustion efficiency for the polycyanurates calculated from all of the test data. carbon monoxide (207 ppm). SOOT YIELD AND CO/CO2 RATIO VERSUS COMBUSTION EFFICIENCY IN FLAME FOR CYANATE ESTERS AT IRRADIANCES TESTED IN STUDY High soot yield and CO/CO2 ratios are usually indicative of incomplete combustion in the flame.0.05 0 0. may include nonflaming heat of char oxidation (smoldering) which dominates the latter portion of the test after flame extinction. Halogen-containing polymers usually exhibit relatively high levels of incomplete combustion products. χ FIGURE 5.7) . the other polycyanurates because of the absence of gas phase combustion.2 0 0.05 0.20 Soot CO/CO2 0.0 1.
1989. Granville. Ising and D.E. Arnold. “Flammability of Cyanate Ester Resins.” Proceedings 34th International SAMPE Symposium.A.” DOT/FAA/AR-01/32. S. HOCN. The halogen-containing polycyanurates were difficult to ignite and had extremely low heat release rates. “Flammability Resistance of Non-Brominated Cyanate Ester Resins. Ramirez. Gaithersburg. MD. burning behavior. 1326-1334. Standard Test Method for Heat of Combustion of Hydrocarbon Fuels by Bomb Calorimeter (High Precision Method). 7. R. and R. and B. ed. Crystal City. D2382-88. November 15-17.N. Lyon. Plast. Jr. which produces small amounts of low. when used as a matrix resin for structural composites. May 8-11. 8.and noncombustible gases (HCl. 6. Chemistry and Technology of Cyanate Ester Resins. 1994. CO. S. The effects of chemical composition were evidenced in the ignitability. “Fire Properties of a New Cyanate Ester Polymer Designed for Aircraft Applications. 3rd Edition. I. D. 1998. Mod. ASTM Fire Test Standards.” NIST Annual Conference on Fire Research. 1990. MD. Hughes Technical Center. and R. REFERENCES 1. S. Savitski. 1995. Philadelphia. NIST.P. is the only conventionally-processed thermosetting polymer reported [22 and 23] to have passed all of the fire performance requirements for use on Navy submarines . 1990.E. and CO2) and a large amount of char during pyrolysis . Das.” 50th Calorimetery Conference. Shimp. American Society for Testing and Materials. and R. Prevorsek.. the hydrocarbon materials. Hamerton.E. Gaithersburg. FAA William J. VA. DeBona. pp. July 23-28.” 4th International Fire and Materials Conference.E.. PA.J. CONCLUSION The combustibility of polycyanurates derived from a variety of cyanate ester monomers was studied in an attempt to correlate the chemical structure of these materials with their fire behavior. Arnold. London. A. November 2-5. while soot production and carbon monoxide yields were comparable to. Rodriguez-Arnold. 15 . and R. or lower than. F. 2. 5. Gandhi. September 2002. 4. Walters.. Lyon.C. “Thermal Decomposition of Cyanate Ester Resins. Walters.E. “Combustion Behavior of Triazine Resins. T. The RD98-228 polycyanurate. F.contradiction between combustion product yields and combustion efficiency for RD98-228 is in fact consistent with the thermal degradation mechanism of this polycyanurate. J. M. E. 1995. R. Lyon. Blackie Academic & Professional (Chapman & Hall). E. 3.M. and combustion efficiency in the flame. Lyon.N.
“Generation of Heat and Chemical Compounds in Fires. Babrauskas and S. Lyon and R..N. eds. Hughes Technical Center. A. Babrauskas. “Development of Cone Calorimeter . “Molar Group Contributions to Polymer Flammability. Lyon. N.” Proceedings 42nd International SAMPE Symposium and Exhibition.” J. 4 (2). Mag. “A Microscale Combustion Calorimeter for Determining Flammability Parameters of Materials. 207223. 649-652. 33. Babrauskas.N. Parker. 1985.. “Development of a Model for the Heat Release Rate of Wood. Quintiere and Harkleroad. February 2002. 14. Walters. Grayson. 16. V. “Solid State Thermochemistry of Flaming Combustion. 21.” in Fire Retardancy of Polymeric Materials. C. 2000. 17.E.” NBISR 85-3163. 11. 1984. W.” American Society for Testing and Materials. Washington. Elsevier Science. Hugget. 1995.M. 1995. Walters and R. A. DC. 1992. “Properties of Polymers. 15. PA. Tewarson. pp. Fire and Materials. Marcel Dekker. Inc. 13. “Standard Test Method for Heat and Visible Smoke Release Rates for Materials and Products Using the Oxygen Consumption Calorimeter. M. pp. Fire Science. Walters and R. 20. New York. (eds. August 20-24. Lyon. 1980. Wilkie.W.J. “A Microscale Combustion Calorimeter. 1990. National Bureau of Standards. E. 1997. Boston. J. D. “Heat of Combustion and Potential Heat.. 1917. Philos.). Lyon. Van Krevelen. 18. V. ASTM E1354. Elsevier Applied Science. R. 81. FAA William J. 12. The Netherlands.G.” NBSIR 84-2943.9. 1984.” Third Edition. MA. DC 20234. V.” in Heat Release in Fires. 42(2). “New Concepts for Measuring Flame Spread Properties. 196.F Grand and C. 1335-1344. 19. 2000.” Society of Fire Protection Engineers. R. Fire and Polymers Symposium.A Bench-Scale Heat Release Apparatus Based on Oxygen Consumption. Chapters 3-4. 10. 2nd Edition. “Estimation of Rate of Heat Release by Means of Oxygen Consumption Measurements. R. Thornton. W. Washington. NY. 16 . 391-447. 2.” DOT/FAA/AR01/117. pp.” Center for Fire Research. in SFPE Handbook of Fire Protection Engineering.” Proceedings ACS National Meeting.A.E. R. Philadelphia. E.
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APPENDIX A—HEAT RELEASE HISTORIES OF POLYCYANURATES AT INDICATED HEAT FLUXES B-10 1200 CH3 NCO C CH3 OCN F-10 250 CF3 NCO 200 100 kW/m 2 C CF3 OCN 1000 Heat Release Rate (kW/m ) Heat Release Rate (kW/m 2) 2 800 100 kW/m 2 150 600 75 kW/m2 100 400 50 kW/m2 75 kW/m2 50 200 35 kW/m2 0 0 200 400 600 800 1000 1200 0 0 250 500 750 1000 1250 1500 Time (seconds) Time (seconds) L-10 1000 1200 M-10 CH3 NCO C H 100 kW/m 2 H3 C OCN 1000 CH3 CH2 OCN CH3 100 kW/m 2 NCO H3 C 800 Heat Release Rate (kW/m ) Heat Release Rate (kW/m ) 2 2 800 600 75 kW/m2 400 50 kW/m2 200 600 75 kW/m2 400 50 kW/m2 200 35 kW/m2 0 0 200 400 600 800 1000 1200 0 0 200 400 600 800 35 kW/m2 1000 1200 Time (seconds) Time (seconds) FIGURE A-1. L-10 AND M-10 POLYCYANURATES AT INDICATED HEAT FLUXES A-1 . F-10. HEAT RELEASE RATE HISTORIES FOR B-10.
PT-60.PT-30 1400 OCN OCN CH 2 CH 2 OCN PT-60 1200 OCN 1000 CH2 OCN CH2 4 100 kW/m 2 OCN 1200 Heat Release Rate (kW/m 2) 1000 100 kW/m 2 Heat Release Rate (kW/m ) 2 800 800 75 kW/m2 600 600 75 kW/m2 400 50 kW/m2 200 400 50 kW/m2 200 35 kW/m2 0 0 300 600 900 35 kW/m2 0 0 100 200 300 400 500 600 700 Time (seconds) Time (seconds) PT-90 2000 800 XU-366 CH3 CH3 C CH3 OCN OCN CH2 OCN CH2 7 OCN 700 600 NCO C CH3 Heat Release Rate (kW/m ) Heat Release Rate (kW/m 2 ) 1500 2 100 kW/m 2 1000 75 kW/m2 500 400 75 kW/m2 300 500 50 kW/m2 200 100 50 kW/m2 35 kW/m2 0 0 100 200 300 400 500 600 0 0 200 400 600 800 1000 1200 Time (seconds) Time (seconds) FIGURE A-2. PT-90. AND XU-366 POLYCYANURATES AT INDICATED HEAT FLUXES A-2 . HEAT RELEASE RATE HISTORIES FOR PT-30.
XU-71787. AND RD98-228 POLYCYANURATES AT INDICATED HEAT FLUXES A-3/A-4 . HEAT RELEASE RATE HISTORIES FOR XU-371.XU-371 1200 1200 XU-71787 OCN OCN OCN OCN 1000 1000 CH2 CH2 Heat Release Rate (kW/m ) Heat Release Rate (kW/m 2) 800 100 kW/m 2 100 kW/m2 800 2 600 75 kW/m2 600 75 kW/m2 400 50 kW/m2 200 35 kW/m2 0 0 150 300 450 600 750 900 400 50 kW/m2 200 35 kW/m2 0 0 200 400 600 800 1000 Time (seconds) Time (seconds) RD98-228 800 Cl 700 NCO 600 100 kW/m2 500 400 75 kW/m2 300 50 kW/m2 C C OCN Cl Heat Release Rate (kW/m ) 2 200 100 35 kW/m2 0 0 100 200 300 400 500 600 Time (seconds) FIGURE A-3.