fernando raffan , xi ding, stanislav stoliarov university of maryland, college park
DESCRIPTION
Flaming Combustion Calorimetry : A New Tool for Flammability Assessment of Mg-scale Pyrolyzable Solid Samples. Fernando Raffan , Xi Ding, Stanislav Stoliarov University of Maryland, College Park Roland Kraemer BASF. Brominated Flame Retardants. Introduction - PowerPoint PPT PresentationTRANSCRIPT
Flaming Combustion Calorimetry: A New Tool for Flammability Assessment of Mg-scale Pyrolyzable Solid Samples
Flaming Combustion Calorimetry: A New Tool for Flammability Assessment of Mg-scale Pyrolyzable Solid SamplesFernando Raffan, Xi Ding, Stanislav StoliarovUniversity of Maryland, College Park
Roland Kraemer BASFBrominated Flame RetardantsBrominated flame retardants (BFRs) are widespread in their use due to their relative low cost/high performanceRecently, BFRs have been found to accumulate in human tissues and persist in the environment1,2. Industry is moving towards suitable replacementsUnderstanding mechanisms of BFRs as gas phase combustion inhibitors can guide the research community towards a suitable replacementA small scale screening tool for BFR replacements is highly desirable as it will considerably drive down costs during product development
12/5/20137th Triennial International Aircraft Fire and Cabin Safety Research Conference 2IntroductionBrominated Flame RetardantsCurrent Test MethodsObjectives of Current WorkDevelopment of FCCDesign and CapabilitiesDiagnosticsParametric Testing andOperating ConditionsTest MatrixData Analysis
Experimental ResultsPolystyrene and BrominePBT and Al-DEPFlame Temperatures
Conclusions and Future Work
1. http://www.epa.gov/oppt/existingchemicals/pubs/actionplans/pbde.html2. http://www.nist.gov/el/fire_research/upload/1-Axelrad.pdf
Current Test MethodsCone CalorimetryCommonly used in fire testingLaminar-Transitional Diffusion flamesControlled incident heat fluxRequires samples on the order of grams (expensive for new materials)Micro Combustion Calorimetry (MCC)Laminar premixed reactor (no flame, complete combustion by design)Controlled pyrolysis (constant heating rate)Milligram sized samples12/5/20137th Triennial International Aircraft Fire and Cabin Safety Research Conference 3
Design and implement an apparatus that can study the flaming combustion of milligram scale solid samples in a well-controlled fashionCorrelate the measured gas-phase combustion efficiency with MCC and cone calorimetry resultsDevelop steps towards measurement of flame temperatures in polymers with/without flame retardantsThe FCCFlaming Combustion Calorimeter
Objective of Current Work12/5/20137th Triennial International Aircraft Fire and Cabin Safety Research Conference 4Design and Capabilities
12/5/20137th Triennial International Aircraft Fire and Cabin Safety Research Conference 5IntroductionBrominated Flame RetardantsCurrent Test MethodsObjectives of Current WorkDevelopment of FCCDesign and CapabilitiesDiagnosticsParametric Testing andOperating ConditionsTest MatrixData Analysis
Experimental ResultsPolystyrene and BrominePBT and Al-DEPFlame Temperatures
Conclusions and Future Work
Pyrolyzer6Purge gasCDS 5000Pyro-probe
Quartz tube12/5/20137th Triennial International Aircraft Fire and Cabin Safety Research Conference
Sample tubeBase12/5/20137th Triennial International Aircraft Fire and Cabin Safety Research Conference 7
Insert coflow and igniter hardwareHomogenize coflowSeal assembly
Combustion Chamber12/5/20137th Triennial International Aircraft Fire and Cabin Safety Research Conference 8Enclose combustion processProvide optical access to the flame for gaining information like flame height, flame structure, combustion timeGas Analyzing System12/5/20137th Triennial International Aircraft Fire and Cabin Safety Research Conference 9
DrieriteFlow meterO2 sensorHoodPressure gaugeSoot filter
CapabilitiesCo-flow0 - 6.32 SLPMO2 % in co-flow0-100%Purge gas0-100 SCCMHeating rate0-32 K/s12/5/20137th Triennial International Aircraft Fire and Cabin Safety Research Conference 10IntroductionBrominated Flame RetardantsCurrent Test MethodsObjectives of Current WorkDevelopment of FCCDesign and CapabilitiesDiagnosticsParametric Testing andOperating ConditionsTest MatrixData Analysis
Experimental ResultsPolystyrene and BrominePBT and Al-DEPFlame Temperatures
Conclusions and Future Work
DiagnosticsO2 consumption calorimetryHeat Release RateCombustion EfficiencySoot Yield2 color ratio pyrometryFlame Temperatures12/5/20137th Triennial International Aircraft Fire and Cabin Safety Research Conference 11IntroductionBrominated Flame RetardantsCurrent Test MethodsObjectives of Current WorkDevelopment of FCCDesign and CapabilitiesDiagnosticsParametric Testing andOperating ConditionsTest MatrixData Analysis
Experimental ResultsPolystyrene and BrominePBT and Al-DEPFlame Temperatures
Conclusions and Future Work
Huggetts empirical observation: for most fuels, a more or less constant net amount of heat is released per unit mass of oxygen consumed for complete combustion. This constant is E = 13.1 + 0.6 kJ/g-O2
O2 consumption calorimetry12/5/20137th Triennial International Aircraft Fire and Cabin Safety Research Conference 12
O2 consumption calorimetry12/5/20137th Triennial International Aircraft Fire and Cabin Safety Research Conference 13Method 1: VAIR[IN] = constant, [O2][IN] = constant
Method 2: VAIR[IN] = VAIR[out], [O2][IN] = constant
Co-Flow TestsAtmosphere composition testsHeating Rate testsPurge gas flowrate tests
12/5/20137th Triennial International Aircraft Fire and Cabin Safety Research Conference 14Co-flow4 SLPMO2 inlet concentration20-21% (Air)Heating rate10 K/sPurge gas (N2)100 SCCMOperating ConditionsIntroductionBrominated Flame RetardantsCurrent Test MethodsObjectives of Current WorkDevelopment of FCCDesign and CapabilitiesDiagnosticsParametric Testing andOperating ConditionsTest MatrixData Analysis
Experimental ResultsPolystyrene and BrominePBT and Al-DEPFlame Temperatures
Conclusions and Future Work
Repeatability12/5/20137th Triennial International Aircraft Fire and Cabin Safety Research Conference 15IntroductionBrominated Flame RetardantsCurrent Test MethodsObjectives of Current WorkDevelopment of FCCDesign and CapabilitiesDiagnosticsParametric Testing andOperating ConditionsTest MatrixData Analysis
Experimental ResultsPolystyrene and BrominePBT and Al-DEPFlame Temperatures
Conclusions and Future Work
5 PMMA Tests
Polystyrene Family12/5/20137th Triennial International Aircraft Fire and Cabin Safety Research Conference 16
IntroductionBrominated Flame RetardantsCurrent Test MethodsObjectives of Current WorkDevelopment of FCCDesign and CapabilitiesDiagnosticsParametric Testing andOperating ConditionsTest MatrixData Analysis
Experimental ResultsPolystyrene and BrominePBT and Al-DEPFlame Temperatures
Conclusions and Future Work
Results
1712/5/20137th Triennial International Aircraft Fire and Cabin Safety Research Conference IntroductionBrominated Flame RetardantsCurrent Test MethodsObjectives of Current WorkDevelopment of FCCDesign and CapabilitiesDiagnosticsParametric Testing andOperating ConditionsTest MatrixData Analysis
Experimental ResultsPolystyrene and BrominePBT and Al-DEPFlame Temperatures
Conclusions and Future Work
CE = measured O2 consumption / theoretical O2 consumption (assuming complete combustion)Results
1812/5/20137th Triennial International Aircraft Fire and Cabin Safety Research Conference IntroductionBrominated Flame RetardantsCurrent Test MethodsObjectives of Current WorkDevelopment of FCCDesign and CapabilitiesDiagnosticsParametric Testing andOperating ConditionsTest MatrixData Analysis
Experimental ResultsPolystyrene and BrominePBT and Al-DEPFlame Temperatures
Conclusions and Future Work
Results
190.850.790.790.750.560.5912/5/20137th Triennial International Aircraft Fire and Cabin Safety Research Conference IntroductionBrominated Flame RetardantsCurrent Test MethodsObjectives of Current WorkDevelopment of FCCDesign and CapabilitiesDiagnosticsParametric Testing andOperating ConditionsTest MatrixData Analysis
Experimental ResultsPolystyrene and BrominePBT and Al-DEPFlame Temperatures
Conclusions and Future Work
Analysis of FCC data
2012/5/20137th Triennial International Aircraft Fire and Cabin Safety Research Conference IntroductionBrominated Flame RetardantsCurrent Test MethodsObjectives of Current WorkDevelopment of FCCDesign and CapabilitiesDiagnosticsParametric Testing andOperating ConditionsTest MatrixData Analysis
Experimental ResultsPolystyrene and BrominePBT and Al-DEPFlame Temperatures
Conclusions and Future Work
FCC TheoreticalFCC Measured
Analysis of FCC data For PS-FR2 ( 27.4 wt.% Br)
21Gas phase combustion incompleteness:43%
Formation of sootFormation of CO and/or other incomplete combustion products32%11%CO. yld (wt.%): 39.3%12/5/20137th Triennial International Aircraft Fire and Cabin Safety Research Conference Phosphorated flame retardantsWe have also studied a family of PBT with the addition of diethylphosphinate Al (Al-DEP) as flame retardant
12/5/20137th Triennial International Aircraft Fire and Cabin Safety Research Conference 22PBT75% PBT25% GlassPBT-263% PBT12% Al-DEP25% GlassPBT-355% PBT,20% Al-DEP25% GlassIntroductionBrominated Flame RetardantsCurrent Test MethodsObjectives of Current WorkDevelopment of FCCDesign and CapabilitiesDiagnosticsParametric Testing andOperating ConditionsTest MatrixData Analysis
Experimental ResultsPolystyrene and BrominePBT and Al-DEPFlame Temperatures
Conclusions and Future Work
PBT12/5/20137th Triennial International Aircraft Fire and Cabin Safety Research Conference 23
IntroductionBrominated Flame RetardantsCurrent Test MethodsObjectives of Current WorkDevelopment of FCCDesign and CapabilitiesDiagnosticsParametric Testing andOperating ConditionsTest MatrixData Analysis
Experimental ResultsPolystyrene and BrominePBT and Al-DEPFlame Temperatures
Conclusions and Future Work
Flame Destabilization
12/5/20137th Triennial International Aircraft Fire and Cabin Safety Research Conference 24Baseline PBT (no flame retardant)Flame Destabilization12/5/20137th Triennial International Aircraft Fire and Cabin Safety Research Conference 2563% PBT, 12% Al-DEP
Flame Destabilization12/5/20137th Triennial International Aircraft Fire and Cabin Safety Research Conference 26
63% PBT, 12% Al-DEPFlame Destabilization12/5/20137th Triennial International Aircraft Fire and Cabin Safety Research Conference 2755% PBT, 20% Al-DEP
Flame TemperaturesIn a fire, flame temperature is an indicator of relative strength of heat feedback to solidTemperature measurements can guide us in determining how well can the flame sustain itselfWe have measured temperatures in propane flames as initial step towards actual polymer fueled flames12/5/20137th Triennial International Aircraft Fire and Cabin Safety Research Conference 28IntroductionBrominated Flame RetardantsCurrent Test MethodsObjectives of Current WorkDevelopment of FCCDesign and CapabilitiesDiagnosticsParametric Testing andOperating ConditionsTest MatrixData Analysis
Experimental ResultsPolystyrene and BrominePBT and Al-DEPFlame Temperatures
Conclusions and Future Work
Consumer DSLR camera modified to extend spectral response into NIRFlame images taken with narrow bandpass filters at 2 distinct wavelengths 1, 2Abel transform applied to images to recover radial intensity distribution S1, S2 from line of sight measurements2 Color Ratio Pyrometry12/5/20137th Triennial International Aircraft Fire and Cabin Safety Research Conference 29
h = Plancks constantc = Speed of light in a vacuumk = Boltzmanns constantC2/C1 = Calibration constant12/5/20137th Triennial International Aircraft Fire and Cabin Safety Research Conference 30IntroductionBrominated Flame RetardantsCurrent Test MethodsObjectives of Current WorkDevelopment of FCCDesign and CapabilitiesDiagnosticsParametric Testing andOperating ConditionsTest MatrixData Analysis
Experimental ResultsPolystyrene and BrominePBT and Al-DEPFlame Temperatures
Conclusions and Future Work
650 nm900 nm12/5/20137th Triennial International Aircraft Fire and Cabin Safety Research Conference 31IntroductionBrominated Flame RetardantsCurrent Test MethodsObjectives of Current WorkDevelopment of FCCDesign and CapabilitiesDiagnosticsParametric Testing andOperating ConditionsTest MatrixData Analysis
Experimental ResultsPolystyrene and BrominePBT and Al-DEPFlame Temperatures
Conclusions and Future Work
650 nm900 nm
ConclusionsWe have successfully developed a new tool to test the flammability of mg-scale pyrolyzable solids, the FCCThe FCC has shown sensitivity to Bromine and PhosphorusFCC versatility allows to operate beyond a simple screening tool. Fully instrumented research tool allows to explore several operating conditionsFirst steps have been made towards the non-intrusive measurement of flame temperatures from polymer fuels
12/5/20137th Triennial International Aircraft Fire and Cabin Safety Research Conference 32IntroductionBrominated Flame RetardantsCurrent Test MethodsObjectives of Current WorkDevelopment of FCCDesign and CapabilitiesDiagnosticsParametric Testing andOperating ConditionsTest MatrixData Analysis
Experimental ResultsPolystyrene and BrominePBT and Al-DEPFlame Temperatures
Conclusions and Future Work
Future WorkExplore additional polymers and flame retardantsInvestigate flame temperatures under unsteady conditions, using polymer fuels (are brominated flames cooler?)Iterate on FCC design to improve robustness and usability12/5/20137th Triennial International Aircraft Fire and Cabin Safety Research Conference 33IntroductionBrominated Flame RetardantsCurrent Test MethodsObjectives of Current WorkDevelopment of FCCDesign and CapabilitiesDiagnosticsParametric Testing andOperating ConditionsTest MatrixData Analysis
Experimental ResultsPolystyrene and BrominePBT and Al-DEPFlame Temperatures
Conclusions and Future Work
BASFDr. Richard Lyon (FAA)Richard Walters (FAA)Colleen Frances (UMD)Hai Qing Guo (UMD)Dr. Peter Sunderland (UMD)Acknowledgments12/5/20137th Triennial International Aircraft Fire and Cabin Safety Research Conference 34Thank you!
Questions?12/5/20137th Triennial International Aircraft Fire and Cabin Safety Research Conference 35Backup Slides12/5/20137th Triennial International Aircraft Fire and Cabin Safety Research Conference 36 Method 137Combustion ProcessFlowmeterO2SensorAir
Baseline VAIR signal before test startBaseline [O2] signal before test start
12/5/20137th Triennial International Aircraft Fire and Cabin Safety Research Conference Method 238Combustion ProcessFlowmeterO2SensorAir
Baseline [O2] signal before test start=
12/5/20137th Triennial International Aircraft Fire and Cabin Safety Research Conference According to Plancks law, the radiative emission of a body is a function of temperature, wavelength and emissivityManipulation of Plancks law shows that temperature can be expressed as a function of wavelength, emitted radiation and emissivityIf the relationship between emitted radiation and detected intensity of a camera is linear and known (through calibration), then the bodys temperature can be expressed as a function of detected intensity ratios, wavelengths and emissivities2 Color Ratio Pyrometry12/5/20137th Triennial International Aircraft Fire and Cabin Safety Research Conference 39Calculate Heat of complete combustion of each polymer assuming Huggetts principle Data analysis40PSPS-FR1 (6.85% Br)PS-FR2(27.4% Br)Chemical formula(C8H8)n(C8H7.892Br0.108)nC8H7.514Br0.486)n Hc(kJ/g)40.337.428.8
X 13.1 kJ/g-O2 12/5/20137th Triennial International Aircraft Fire and Cabin Safety Research Conference Chemical formula of PS: (C8H8)n,Chemical formula of Saytex HP 3010 flame retardant: (C8H5.3Br2.7)n.Calculate gas-phase combustion efficiency
THR is the measured heat release normalized by initial sample massHchar= 34.9 kJ/g, assuming char consists of pure carbonchar.yld is the char yield (char mass normalized by initial sample mass)Data analysis41
12/5/20137th Triennial International Aircraft Fire and Cabin Safety Research Conference
Soot yield is measured in FCC. Thus, theoretically the maximum combustion efficiency that can be measured in FCC is:
CEmax =
Hchar = Hsoot = 34.9 kJ/g, assuming both char and soot consist of pure carbon.Hc is the heat of complete combustion of a given material
Analysis of FCC data4212/5/20137th Triennial International Aircraft Fire and Cabin Safety Research Conference