powerpoint presentation - polymer flammability
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STANDARD TEST METHOD FOR FLAMMABILITY SCREENING OF AC MATERIALS
Fire Safety Branch AAR-440FEDERAL AVIATION ADMINISTRATION
William J. Hughes Technical CenterAtlantic City International Airport, NJ 08405
International Aircraft Materials Fire Test Working GroupTropicana Hotel-Casino, Atlantic City, NJ, March 20-21, 2006
WEB: www.fire.tc.faa.gov E-MAIL: [email protected]
Richard E. Lyon
OUTLINE
• FLAMMABILITY PROPERTIES FROM MICROCALORIMETRY
• MICROCALORIMETRY AND:
Ignitability (Radiant Panel Flame Spread)
Heat Release Rate (OSU and Intermediate Scale Tests)
Flame Resistance (Bunsen burner tests)
Research (Product Development)
• SUMMARY AND CONCLUSIONS
Standard Test Method for Flammability Screening of AC Materials
GOAL: PREDICT RESULTS OF AC FIRE TESTING
FLAMERESISTANCE
HEAT RELEASE
INTERMEDIATESCALE
FIRE TESTSPCFC
Semi-Empirical Correlation
CombustionPropertieshc, Tign, ηc
0
MilligramsKilograms
= 10 −6 = “Microscale”
OSU Hidden Materials
FLAME SPREAD
Radiant Panel
APPROACH: Simulated Flaming Combustion
Flaming Combustion
Microscale Combustion Calorimetry• Sample heated at constant rate in N2• Complete oxidation of fuel gases• Oxygen consumption calorimetry to
measure heat release rate
Pyrolysis
Combustion
Sample
Exhaust
DAQO2
GasScrubber Gas
Flow-meter
O2Meter
N2
APPARATUS CONSTRUCTION
Combustor
Pyrolyzer
Mixing Section
Sample Cup
ScrubberFlow MeterO2 Sensor
Exhaust
Purge Gas Inlet
Sample Post & Thermocouple
Oxygen Inlet
Q(t) =ρO2
Cm0
F[O2 ]{ }(t)
hc0 = Q(t)dt
0
∞∫
= 13 kJg
Br
Cl
Cl
( ) n
-50
0
50
100
150
200
250
300
0
100
200
300
400
500
600
700
0 100 200 300 400 500 600
Q (W
/g)
Temperature, C
elsius
Time, seconds
PCFC DATA: Example for Research Polymer
ηc = 260 W/ g1K / s
= 260 Jg −K
260 W/g
β = 1 K/s
Tmax
Tmax = 425 °C
MICRO HRR DATA FOR COMMON PLASTICS
200 300 400 500 600 700 800
0
500
1000
1500
2000
Temperature, °C
ABSPVDF
PVC
PP
POMPMMA
PET
PE
PC
Q/β
, J/g
-K
PPSPEI
PA66
FEP
MOTIVATION FOR MICRO SCALE TEST
Small Specimens (milligrams instead of kilograms)
Rapid Results (minutes instead of hours)
Reproducible (± 7%)
Repeatable (± 5%)
Fire Properties Measured (used with models to correlate other tests)
PROPERTIES RELATED TO FLAMMABILTIY
250 300 350 400 450 500 5500
100
200
300
400
500Qmax/β
Heat of Combustion
TmaxHea
t R
elea
se R
ate
(W/g
)
Temperature (°C)
PCFC Property
• Heat release rate• Flame resistance
(UL94 , LOI)
• Fire Load• Combustibility
• Ignitability (Tign, CHF)• Glow Wire Ignition
FlammabilityParameter
IGNITABILITY
IGNITION TEMPERATURE AND Tmax
200
300
400
500
600
700
200 300 400 500 600 700
Igni
tion
Tem
pera
ture
, �C
Tmax in PCFC, �C
40 Polymers
Tign ≈ Tmax(hydrocarbons)
CHF, kW/m2
Measured* σTmax4POLYMER
Tmax
(°C)
PMMA 401 � 8 11 - 12 6 - 23POM 409 �10 11 - 13 13HIPS 463 �10 15 - 17 15ABS 467 �12 16 - 18 9 - 15PET 471 �12 16 - 18 10 - 19PVC** 478 � 8 17 - 18 15 - 28
PP 493 �10 18 - 20 15 - 16
PE 514 �10 20 - 22 15 - 20PVDF** 510 � 2 21 30 - 50
PC 556 � 9 25 - 28 15 - 20PPS** 551 �18 24 - 28 35 - 38PEI 576 �10 28 - 31 25 - 40FEP 600 �10 31 - 34 38 - 50
PA66 482 17 - 19 15 - 21�11**Note poor agreement for halogen (Cl, F) and
heteroatom (S) polymers for which
Tign > Tmax
CRITICAL HEAT FLUX (CHF) FOR IGNITION FROM Tmax
*D. Drysdale, A. Tewarson, R.E. Lyon
0
10
20
30
40
50
60
0 10 20 30 40 50 60
Crit
ical
Hea
t Flu
x, k
W/m
2
81 2
3
45
7 11
13
14
6 9
1012
PMMAPOMHIPSABSPETPA66PVCPPPEPVDFPCPPSPEI
123456789
10111213
FEP14
σ 4Tmax, kW/m2
CRITICAL HEAT FLUX: Graphical Comparison
100
200
300
400
500
600
700
800
0 10 20 30 40 50
Tem
pera
ture
, °C
Distance From Igniter, cm
Tmax < Ts
Surface Temperature, Ts(From Panel Calibration)
Tmax > Ts
PERFORMANCE OF HIDDEN MATERIALS
Tmax (°C) Measured in
PCFC
Heat Resistance / Tmax is a Good Predictor of Flame Spread in FAA Radiant Panel Test
HEAT RELEASE RATE
HEAT RELEASE RATE: Macro / Micro
Slope = HRP ≡
HR
R (k
W/m
2 )
q″ext (kW/m2)0
hcLg
=hc / ΔTpLg / ΔTp
= ηcηg
Fire Calorimeter Data
HRR = HRR0 + ηc
ηg′ ′ q ext
Multiply by ΔTp / ΔTp
Intercept = HRR0
From PCFC
CONE HRR AND MICROCALORIMETER ηC
ConeCalorimeter
0
500
1000
1500
2000
0 500 1000 1500 2000
R = 0.93
PVC
Heat Release Capacity ηc (J/g-K)
PEIPPS
POM
PET
PVDFPC
PMMA
ABSPA66
HIPSPP
HDPE
50 kW/m2
FEP
Peak
HR
R in
Con
e C
alor
imet
er
(kW
/m2 )
HRR ≈ (q″ext/ηg) ηc = (50 kW/m2)/(50 kJ/kg-K) ηc
= (1 kg-K/m2-s) ηc
Slope = 1 kg-K/m2-s
ASTM E 906/OSURate of Heat
Release Apparatus
1
10
100
1000
1 10 100 1000Heat Release Capacity, J/g-K
Thermoplastic Sheet (1.6 mm) Thermoset Composites (single ply)
FAR 25.853(a-1) Maximum
OSU
Pea
k H
RR
, kW
/m2
OSU HRR AND MICROCALORIMETER ηC
THERMO ACOUSTIC INSULATION
Intermediate Scale and Micro Scale Results
PVF1 (120 J/g-K)
PUF block, Baseline
MPET (262 J/g-K)
PI-O (47 J/g-K)
PET1 (138 J/g-K)
PET3 (250 J/g-K)
PET00 (155 J/g-K)
Material (HRC)
Tem
pera
ture
, °F
TEMPERATURE RISE versus HRC
Intermediate Scale Test of Thermo-Acoustic Insulation
0
200
400
600
800
1000
1200
0 100 200 300
Max
imum
Tem
pera
ture
, °C
Heat Release Capacity, J/g-K
MPET
PET3
PET00PET1
PVF1
PI-0
FLAMERESISTANCE
FLAME RESISTANCE AND MICROSCALE HRR
Bunsen Burner Tests
Isolated flame / Unforced Combustion
Limiting Oxygen Index
Extinction in flame tests (q″ext = 0) when HRR0 ≤ HRR* ≈ 50-100 kW/m2,
HR
R (k
W/m
2 )
q″ext (kW/m2)
Slope = HRP = ηc/ ηg
Intercept = HRR0 = (q″flame- CHF) HRP = (q″flame- CHF) ηc/ ηg
0
FLAME RESISTANCE AND MICROCALORIMETRY
Cone Calorimeter Data
[O2∗ ] = CHF
a+
HRR∗ ηg / aηc
≈ 12% + 4000ηc
(%) ηc∗ ≤
HRR∗ ηg( ′ ′ q flame − CHF)
Limiting Oxygen Index = [O2*] UL 94 V Criterion
PCFC Data
q″flame ∝ [O2] = a [O2] = 1.4 kW/m2-%[O2]
Halogen containing
FLAME RESISTANCE (LOI) AND MICROCAL (ηC)
0
20
40
60
80
100
10 100 1,000 10,000
Lim
iting
Oxy
gen
Inde
x [O
2]*, %
v/v
Heat Release Capacity ηc, J/g-K
LOI = 12% + 4000ηc
(%)Predicted*
Halogencontaining
10 100 1000 10,000
HB
V2
V1
V0
Heat Release Capacity (ηc), J/g-K
UL 94Rating
Flam
mab
ility
ηc∗ ≤
HRR∗ ηg( ′ ′ q flame − CHF)200 J/g-K ≈
FLAME RESISTANCE (UL 94) AND MICROCAL (ηC)
FLAME RESISTANCE: FAR 25.853 AND 25.855
0
2
4
6
8
10
-2
0
2
4
6
8
10
0 100 200 300 400 500 600
Bur
n Le
ngth
(cm
)
Burn Tim
e (seconds)
HRC (J/g-K)
12 Second VerticalBurn Test-Aircraft Materials
Vertical FlameTest
Dripping
RESEARCH
FLAME RESISTANCE OF GFRP
ηc has maximum for non-charring plastics (PA6, PBT).
ηc decreases montonically for charring plastics (PC, PPS)
0
100
200
300
400
500
PA6
PC
PPS
Fiberglass Fraction, % w/w403020100
UL94-HB/V2
UL94-V0
FLAMERESISTANCE
PBT
Hea
t Rel
ease
Cap
acity
, J/g
-K
50
100
150
200
250
300
0 1 2 3 4 5 6
Hea
t Rel
ease
Cap
acity
, J/g
-K
Phosphorus Concentration, % w/w
Glycidylether phosphates (PO4)
Glycidylether phosphonates (PO3)
PHOSPHORUS-MODIFIED EPOXIES
Aminophosphineoxide (PO)
P-Compound (RPOx)
Efficacy Increases for Higher Oxides
Tetrabromobisphenol-A / DGEBATetrabromoDGEBA / DGEBA + EMI-24 (2 wt.%)
Heat of complete combustion of fuel gases is
independent of [Br] in epoxy
Heat Release Capacity
decreases with [Br] in epoxy
20
25
30
35
h c,v, k
J/g
0 5 10 15 20 25 30 35 40300400500600700800
Bromine Content, Wt. %
η c, J
/g-K
BROMINATED EPOXIES (Adjusted for Fuel Fraction)
No Gas Phase Activity
Condensed Phase Activity
SUMMARY
• Small (mg) Specimens = No Fabricated Products,Assemblies, Laminates.
• Physical Effects Not Captured in Test Results:
DrippingSwellingShrinkingCurlingIntumescenceBarrier (mass/heat) effectsetc.
• Complete Combustion Under Normal Operation= Limited Sensitivity to Gas Phase/Halogen FR.
CURRENT LIMITATIONS OF METHOD
Not So Important for FAA Tests(Which Tend to Be More Severe)
STATUS OF MICROCALORIMETRY: Commercial
• R&D 100 Award Submitted by FAA
• Two licensed manufacturers
The Govmark Organization, Farmingdale, NY.
Fire Testing Technology,East Grinstead, England.
• Over ten (>10) commercial units in operation in industry, government, academia.
ASTM Committee D20 (Plastics)
ISO Technical Committee TC 61 (Plastics)
FAA (?)
• “Screening Method” inFire Test Handbook?
• Adapt to AC Materials
STATUS OF MICROCALORIMETRY: Regulatory
Work Items Submitted forStandard Test Method in: