Flame Retardants as a Tool to Prevent Ignition and Mitigate Flame Spread Hazard in Mass Transportation A. Ben-Zvi, M. Leifer, J. Lison, S.

Transcription

1 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

2 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

3 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

4 ICL-IP Product Supply Chains Dead Sea omine compounds plants: Israel Netherlands China Customers Purchased Phosphorus compounds plants: Germany USA 3

5 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

6 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

7 Combustion of Hydrocarbons Initiation Propagation anching Energy Termination

8 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

9 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

10 Fire testing- Standards- EN EN ISO , LOI* ISO , lateral flame spread ISO , heat release, smoke, mass loss* EN ISO : radiant panel EN ISO : ignition to direct flame ISO/TR : furniture calorimeter vandalized seat ISO : textiles, bedding ignitability, match flame* ISO 2592: flash & fire points EN : cables, vertical flame, single wire* EN : cables, vertical flame, bunched wires EN 50305:2002: cables, special performances EN ISO : smoke/optical density EN ISO : gas analysis, FTIR NF X ,2: gas analysis EN : cables, smoke density EN-13501: reaction to fire tests EN : glow wire* EN : vertical small flame* 9

11 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, С Main application is in thermoplastics Improves compatibility with glass fibers

12 Endcapped brominated epoxy, F-3000 Epoxy Mw content, % Softening temperature С Main application F ABS, HIPS F ABS, HIPS F ABS, HIPS F 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

13 R24, R25, R26 Polyamide 6 Magnesium hydroxide surface treatment EN45545 unit Aminosilane Polymeric coating Polymer added Set Limit Polyamide 6 % Glass fibers % Magnesium hydroxide % ominated polyacrylate % ominated epoxy polymer % Heat stabilizer % Processing aid % Ca- stearate % 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 R % GWIT R C Izod nothed impact J/m Tensile strength N/mmz elongation at break % Tensile modulus N/mmz CTI V HDT C

14 R24, R25, R26 Polyamide 6.6 Magnesium hydroxide surface treatment Stearic acid Aminosilane Proprietary coating 1% Proprietary coating 2% unit Polyamide 6.6 % Glass-fibers % Magnesium hydroxide % ominated epoxy (F-3100) % Heat stabilizer % Processing aid % Calcium stearate % UL-94 V (1.6 mm) V0 V0 V0 V0 LOI % GWIT of 3.2 mm thickness o C

15 R25, R26 Polyester (PBT) Units Polyester (PBT) % GF for PBT ex % ominated polyacrylate (FR- 1025) % ominated epoxy (F-3100) Calcium borate (FR-1120) % Antimony trioxide (80 % MB) % Antidrip, PTFE % Heat stabilizer % mm V-0 V-0 V-0 V-0 V-1 V-0 V-0 V-0 V-0 V-1 GWIT ºC HDT ºC Izod notched impact J/m Tensile strength MPa Elongation at break % Tensile modulus GPa

16 R24, R25, R26 Styrenic Polymers FR-Grade HIPS % ominated epoxy (F-3014) % Antimony trioxide (80% MB) % PTFE % Antioxidant % mm V-0 V-1 V-1 GWFI C LOI % HDT as molded C Izod notched impact J/m Tensile strength MPa Elongation at break % Tensile modulus MPa FR grade ABS % ominated epoxy (F-3020) % Antimony trioxide (80% MB) % Antioxidant % mm V-2 V-0 V-2 GWFI C LOI % HDT as molded C Izod notched impact J/m Tensile strength MPa Elongation at break % Tensile modulus MPa

17 Metal hydroxides-mode of action Released water significantly decreases temperature of the flame 2 Al(OH) 3 --> Al 2 O 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

18 Time to ignition (sec) Cone calorimeter PVC vs. Polyolefins, 50 kw/m 2 Heat Release Rate kw/m Avg. Heat Release Rate Peak Heat Release Rate Time to ignition PVC + 50phr CaCO3+ 6phr FR PVC + 50phr CaCO3 + 6phr ZnB PP + 30% MDH PP + 25% MDH+5% FR-1120 Sample EVA + 60% FR %FR-1120 EVA + 65% FR

19 Smoke Release Cone calorimeter PVC vs. Polyolefins 3000 Total smoke release PVC + 50phr CaCO3+ 6phr FR-1120 PVC + 50phr CaCO3 + 6phr ZnB PP + 30% MDH PP + 25% MDH+5% FR-1120 EVA + 60% FR %FR-1120 EVA + 65% FR-20 Sample 18

20 Optical density, DM PP-Smoke Obscuration % FR % Sb2O3 (no FR-20) 15% FR %Sb2O % FR-20 65% FR-20 (no FR) Ref no FR Time, min 19

21 Cone calorimeter PP magnesium hydroxide 20

22 MARHE kw/m² Smoke Parameter Cone calorimeter PP magnesium hydroxide 50 kw/m MARHE Smoke Parameter Neat PP PP + 20% FR-20 PP + 40% FR-20 PP + 60% FR-20 PP + 70% FR-20 PP + 75% FR-20 Sample

23 MARHE kw/m² Smoke Parameter Polypropylene - MDH 25 kw/m MARHE Smoke Parameter PP + 60% FR-20 25kw PP + 70% FR-20 25kw Sample

24 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

25 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 = 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

26 Heat Release Rate (kw/m²) Time to ignition (sec) Polycarbonate, 50 kw/m Avg. Heat Release Rate Peak Heat Release Rate Time to ignition Neat PC Commercial FR PC PC + 30% GF PC + 30% GF + 5% SolDP Sample 0 25

27 MARHE Smoke Parameter Polycarbonate, 50 kw/m MARHE Smoke Parameter Neat PC Commercila FR PC PC + 30% GF PC + 30% GF + 5% SolDP Sample 0 26

28 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

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