Flame Retardants as a Tool to Prevent Ignition and Mitigate Flame Spread Hazard in Mass Transportation A. Ben-Zvi, M. Leifer, J. Lison, S. Levchik Beer Sheva, Israel Tarrytown, New York
ICL-IP Market Leadership ICL-IP is Industrial Products business unit of ICL ICL is a global chemical company 2016 sales ICL - $5.4 billion ICL-IP about $1 billion (18%) Product lines are based on 4 chemistries omine Phosphorus Magnesium Nitrogen Number 1 Market Positions #1 in Flame Retardants #1 in omine capacity #1 in omine Iso-tank fleet #1 in ominated biocides #1 in Phosphorus FRs #1 in Clear ine Fluids #1 Self-extinguishing Hydraulic fluids We are not bias to any chemistry as long as it is sustainable and serves customer needs 1
Geographical Coverage and Production Sites IPE ICL Japan BF IPT IPA GF Tarrytown Beer-Sheva IMI SBCL LYG DSB BCL Zhapu Plant ICL India R&D ICL azil ICL Shanghai Sales office ICL Hong Kong ICL Korea 2
ICL-IP Product Supply Chains Dead Sea omine compounds plants: Israel Netherlands China Customers Purchased Phosphorus compounds plants: Germany USA 3
Flame Retardancy Mode of Action HEAT Because combustion is a selfsustaining free-radicals branching process, flames are difficult to extinguish FIRE There is no commercial Flame Retardant which provides just one mode of action FUEL (Resin) Mixing of fuel and air AIR Flame Retardants provide passive fire protection Flame Retardants can be applied at different steps of manufacturing Polymer synthesis Thermosetting Additives Coatings
temperature Designing Flame Retardants Ignition is the most important event in the course of a fire (no ignition: no fire) Ignition handbook, Vyto Babrauskas Prevent ignition primary purpose Reduce the rate of flame spread: avoid or delay flashover Resist large existing Fire... Not usually start of fire flash over time Flame retardancy involves disruption of the burning process at one or more stages, so that ignition is prevented, or the process is terminated within an acceptable period of time, or slowed down sufficiently to give time for evacuation
Combustion of Hydrocarbons Initiation Propagation anching Energy Termination
Flame inhibition efficiency Premixed CH 4 /O 2 /N 2 flame. Effectiveness relative to CH 3 V. Babushok and W. Tsang, Combust. Flame, 124(2000)488
Halogens The high energy OH radicals responsible for energy and H radicals responsible for chain branching are removed at first the FR breaks down RX R + X halogen radical reacts with the polymer X + RH R + HX hydrogen halides interfere with radical chain HX + H --> H 2 + X HX + OH --> H 2 O + X Significant condensed phase action typically overlooked
Fire testing- Standards- EN 45545 EN ISO 4589-2, LOI* ISO 5658-2, lateral flame spread ISO 5660-1, heat release, smoke, mass loss* EN ISO 9239-1: radiant panel EN ISO 11925-2: ignition to direct flame ISO/TR 9705-2: furniture calorimeter vandalized seat ISO 12952-2: textiles, bedding ignitability, match flame* ISO 2592: flash & fire points EN 60332-1-2: cables, vertical flame, single wire* EN 60332-3-24: cables, vertical flame, bunched wires EN 50305:2002: cables, special performances EN ISO 5659-2: smoke/optical density EN ISO 5659-2: gas analysis, FTIR NF X70-100-1,2: gas analysis EN 61034-2: cables, smoke density EN-13501: reaction to fire tests EN 60695-2-11: glow wire* EN 60695-11-10: vertical small flame* 9
Poly(pentabromobenzyl acrylate), FR-1025 Polymeric BFR with content 71% High thermal stability, 5% weight loss is at 330 С CH 2 CH C O O CH 3 Softening temperature is reasonably low, 190-220 С Main application is in thermoplastics Improves compatibility with glass fibers
Endcapped brominated epoxy, F-3000 Epoxy Mw content, % Softening temperature С Main application F-3014 1400 60 87-105 ABS, HIPS F-3020 2000 56 105-120 ABS, HIPS F-3516 1600 54 130-150 ABS, HIPS F-3100 15000 53 180-220 PBT, PET, polyamides OH CH 3 OH CH 3 OH O CH 2 CH CH 2 O C O CH 2 CH CH 3 CH 2 O C O CH 2 CH CH 2 n CH 3 O
R24, R25, R26 Polyamide 6 Magnesium hydroxide surface treatment EN45545 unit Aminosilane Polymeric coating Polymer added Set Limit 1 2 3 4 5 Polyamide 6 % 43.5 48.7 43.5 48.7 48.7 Glass fibers % 15 15 15 15 15 Magnesium hydroxide % 20 20 20 20 20 ominated polyacrylate % 15.5 15.5 15.5 ominated epoxy polymer % 20.8 20.8 Heat stabilizer % 0.2 0.2 0.2 0.2 0.2 Processing aid % 0.3 0.3 0.3 0.3 0.3 Ca- stearate % 0.3 0.3 0.3 0.3 0.3 UL-94 V R26 Rating [1.6mm] R26 V0 V0 V0 V0 V0 V0 Rating [0.8mm] R26 V0 V2 V2 V2 V0 V0 LOI R24 28-32 % 53 39 53 48 49 GWIT R25 850 C 875 875 900 875 875 Izod nothed impact J/m 46 59 57 76 71 Tensile strength N/mmz 102 96 92 90 90 elongation at break % 2.1 2.5 2.4 2.8 2.8 Tensile modulus N/mmz 8030 7180 6980 6270 6500 CTI V 325 300 425 400 375 HDT C 125 160 124 146 148 12
R24, R25, R26 Polyamide 6.6 Magnesium hydroxide surface treatment Stearic acid Aminosilane Proprietary coating 1% Proprietary coating 2% unit 1 2 3 4 Polyamide 6.6 % 43.5 43.5 43.5 43.5 Glass-fibers % 15 15 15 15 Magnesium hydroxide % 20 20 20 20 ominated epoxy (F-3100) % 20.8 20.8 20.8 20.8 Heat stabilizer % 0.2 0.2 0.2 0.2 Processing aid % 0.3 0.3 0.3 0.3 Calcium stearate % 0.3 0.3 0.3 0.3 UL-94 V (1.6 mm) V0 V0 V0 V0 LOI % 52 52 54 57 GWIT of 3.2 mm thickness o C 930 930 930 930 13
R25, R26 Polyester (PBT) Units 1 2 3 4 5 6 7 8 9 10 Polyester (PBT) % 51.1 51.5 51.8 52.2 52.5 47.3 47.6 48 48.3 48.7 GF for PBT ex % 30 30 30 30 30 30 30 30 30 30 ominated polyacrylate (FR- 1025) % 11.3 11.3 11.3 11.3 11.3 ominated epoxy (F-3100) 15.1 15.1 15.1 15.1 15.1 Calcium borate (FR-1120) % 1.43 2.85 4.28 5.7 1.43 2.85 4.28 5.7 Antimony trioxide (80 % MB) % 7.1 5.3 3.6 1.8 0 7.1 5.3 3.6 1.8 0 Antidrip, PTFE % 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Heat stabilizer % 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 UL-94V @ 1.6mm V-0 V-0 V-0 V-0 V-1 V-0 V-0 V-0 V-0 V-1 GWIT ºC 750 775 800 825 930 775 775 800 825 930 HDT ºC 183 180 181 183 185 181 182 174 176 182 Izod notched impact J/m 91 80 69 60 59 74 65 58 57 54 Tensile strength MPa 113 111 110 105 103 122 119 115 113 111 Elongation at break % 3.7 2.6 2.5 2.5 1.9 3.15 2.9 2.7 2.4 3.3 Tensile modulus GPa 10.2 1.05 10.2 10.2 10.5 10.2 9.9 10.3 10.5 10.7 14
R24, R25, R26 Styrenic Polymers FR-Grade 1 2 3 HIPS % 78.0 77.5 77.5 ominated epoxy (F-3014) % 16.7 17.2 17.2 Antimony trioxide (80% MB) % 5 5 5 PTFE % 0.1 0.1 0.1 Antioxidant % 0.2 0.2 0.2 UL-94V @ 1.6mm V-0 V-1 V-1 GWFI C 960 960 960 LOI % 23 24 24 HDT as molded C 66 66 65 Izod notched impact J/m 66 61 65 Tensile strength MPa 25.6 25.2 24.7 Elongation at break % 45 43 39 Tensile modulus MPa 1970 1966 1890 FR grade 1 2 3 ABS % 76.9 77.3 77.3 ominated epoxy (F-3020) % 17.9 17.5 17.5 Antimony trioxide (80% MB) % 5 5 5 Antioxidant % 0.2 0.2 0.2 UL-94V @ 1.6mm V-2 V-0 V-2 GWFI C 960 960 960 LOI % 26 28 26 HDT as molded C 76 77 76 Izod notched impact J/m 100 96 100 Tensile strength MPa 45.3 44.8 44.22 Elongation at break % 3.1 2.9 2.9 Tensile modulus MPa 2205 2250 2280
Metal hydroxides-mode of action Released water significantly decreases temperature of the flame 2 Al(OH) 3 --> Al 2 O 3 + 3 H 2 O 1127 J/g Mg(OH) 2 --> MgO + H 2 O 1244 J/g High heat capacity of Al 2 O 3 and MgO White color of the oxides reflects IR radiated heat
Time to ignition (sec) Cone calorimeter PVC vs. Polyolefins, 50 kw/m 2 Heat Release Rate kw/m 2 1000 800 600 400 200 Avg. Heat Release Rate Peak Heat Release Rate Time to ignition 80 70 60 50 40 30 20 10 0 PVC + 50phr CaCO3+ 6phr FR- 1120 PVC + 50phr CaCO3 + 6phr ZnB PP + 30% MDH PP + 25% MDH+5% FR-1120 Sample EVA + 60% FR-20 + 5%FR-1120 EVA + 65% FR-20 0 17
Smoke Release Cone calorimeter PVC vs. Polyolefins 3000 Total smoke release 2500 2000 1500 1000 500 0 PVC + 50phr CaCO3+ 6phr FR-1120 PVC + 50phr CaCO3 + 6phr ZnB PP + 30% MDH PP + 25% MDH+5% FR-1120 EVA + 60% FR-20 + 5%FR-1120 EVA + 65% FR-20 Sample 18
Optical density, DM PP-Smoke Obscuration 1000 800 600 32% FR-1025 + 11% Sb2O3 (no FR-20) 15% FR-1025 + 5%Sb2O3 + 20 % FR-20 65% FR-20 (no FR) Ref no FR 400 200 0 0 2 4 6 8 10 12 14 Time, min 19
Cone calorimeter PP magnesium hydroxide 20
MARHE kw/m² Smoke Parameter Cone calorimeter PP magnesium hydroxide 50 kw/m 2 600 644.4 MARHE Smoke Parameter 700 500 600 400 416.8 500 400 300 300 200 214.3 200 100 0 90.1 42.8 11.1 452.0 490.0 265.3 171.1 117.7 101.0 Neat PP PP + 20% FR-20 PP + 40% FR-20 PP + 60% FR-20 PP + 70% FR-20 PP + 75% FR-20 Sample 100 0 21
MARHE kw/m² Smoke Parameter Polypropylene - MDH 25 kw/m 2 200 160 24.8 MARHE Smoke Parameter 30 25 120 20 15 80 10 40 0 2.1 91.4 66.5 PP + 60% FR-20 25kw PP + 70% FR-20 25kw Sample 5 0 22
Phosphorus can contribute to all three mechanisms, sometimes synergistically. Poisoning free-radical reactions in the flame (suffocating flame) Decreasing fuel supply from the solid material Mass and heat transfer barrier on the interface of solid phase and flame char Phosphorus Flame Retardants
High char low heat and smoke Most polymers produce turbostratic char. Intermediate stage between amorphous carbon and graphite Contains H, O, N, P Viscous liquid at the temperature of combustion Char is not flammable in typical medium size flames Surface T = 400-600 C Char can be oxidized (glowing, smoldering) Carbon fuel remains in the condensed phase. Flame is smaller, easier to extinguish Hu Y. et al., Progr. Org. Coat., 70(2011)59
Heat Release Rate (kw/m²) Time to ignition (sec) Polycarbonate, 50 kw/m 2 700 600 Avg. Heat Release Rate Peak Heat Release Rate Time to ignition 80 70 500 60 400 300 50 40 30 200 20 100 10 0 Neat PC Commercial FR PC PC + 30% GF PC + 30% GF + 5% SolDP Sample 0 25
MARHE Smoke Parameter Polycarbonate, 50 kw/m 2 250 532 MARHE Smoke Parameter 600 200 451 500 150 358 400 100 247 300 200 50 100 0 214 148 189 159 Neat PC Commercila FR PC PC + 30% GF PC + 30% GF + 5% SolDP Sample 0 26
Conclusions Flame retardants affect combustion process at different steps. Predominant mechanism depends on FR chemistry. Flame retardant are most efficient to prevent ignition- no ignition no fire. Flame retardants help with decreasing heat release rate (flame spread) and smoke. Combination of different FRs from available toolbox can give right solution even for the most demanding requirements of EN 45545 27
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