Synergist: a miracle ingredient to reach fire safety?

Transcription

1 Corte, juin 2014 Synergist: a miracle ingredient to reach fire safety? Fabienne Samyn, Aurore Vannier, Sophie Duquesne, Serge Bourbigot R 2 FIRE@ISP/UMET UMR/CNRS 8207, ENSCL, Villeneuve d Ascq, France

2 Fire performances Introduction Why using synergist? Design of flame retarded formulation Synergist < 5% in substitution of the FR Enable to reach a high level of fire performances Main Flame retardant Synergist High Fulfil all the requirements Polymer Pass some tests but not all requirements Flame retarded formulation Low Fail to meet the requirements

3 Introduction Synergist nanoparticles metal oxides organoclay PSS Antimony trioxide Titanium oxide talc Zinc borate ATH MDH flame retardant How do the synergists work? Identification of the causes of the synergism = tricky task Dependant on: matrix main FR synergist (co-additives) Caused by: Modification of the dispersion of additives Chemical / physical interactions between the additives and polymer Combination of effects In this talk: cases study PET Zn phosphinate (ZnPi) M-PSS PA6 Al phosphinate (AlPi-MPP) rganoclay (o-mmt) 3

4 utline In this talk: cases study PET Zn phosphinate (ZnPi) M-PSS PA6 Al phosphinate (AlPi-MPP) rganoclay (o-mmt) Synergy (fire properties) Dispersion of the additives Mechanism of degradation Protective structures 4

5 HRR (kw/m²) HRR (kw/m²) Mechanism Structures Synergy CREPIM 600 PET LI=26% PET/ZnPi (90/10) LI=29% PA6 LI=25%, V2 PA6/AlPi-MPP (77/23) LI=26%, V PET/ZnPi/M-PSS (90/9/1) LI=36% PA6/AlPi-MPP/o-MMT (77/18/5) LI=31%, V Time (s) Time (s) With M-PSS: - Increase of LI - Decrease of phrr With o-mmt: - Increase of LI - V0 rating in UL-94 - Decrease second phrr Synergistic effect observed in both cases 5

6 Mechanism Structures Dispersion PET / 10% ZnPi (SEM) PET / 9% ZnPi / 1% M-PSS (EPMA) PET / 1% M-PSS (SEM) Polished sample, quantitative analysis 6

7 Mechanism Structures Dispersion PA6/AlPi-MPP (SEM) PA6/AlPi-MPP/o-MMT (SEM) PA6 / o-mmt (TEM) PA6/AlPi-MPP/o-MMT (TEM) Exfoliation Exfoliation 20nm 100nm 7

8 Mechanism Structures Dispersion PA6/AlPi-MPP/o-MMT (EPMA and TEM) 8

9 Structures Mechanisms Methodology used : systematic comparison of the decomposition products Additives, combination of additives Decomposition (air or N 2 ) polymer, Polymer/main FR, Polymer/synergist, Polymer/main FR/ synergist TVA Condensed phase Solid state NMR 31 P 29 Si 13 C 27 Al XRD Gas phase PET system TVA + GC-MS PA6 system TGA-FTIR 9

10 Structures Mechanisms PET/ZnPi/M-PSS Silicium T 3 Silicium Q 2 Silicium Q 3 Silicium Q 4 R R R Si Si Si Si Si Si Si Si R 29 Si NMR MPSS PET / ZnPi / M PSS Silica 500 C 300 C Ambiante Déplacement chimique (ppm)

11 31 P NMR Structures Mechanisms Acide Phosphonique Polyphosphates Phosphinates R 1 P - Zn 2+ Phosphonates R 1 P - rthophosphates Zn 2+ - P H Zn 2+ Pyrophosphates - P P - 2Zn 2+ R 1 P H H H P M + H n R H C C Acide phosphonique? 300 C Room T P PET + P950 + MPSS PET + P Déplacement chimique (ppm)

12 Structures Mechanisms Methodology used : systematic comparison of the decomposition products Additives, combination of additives Decomposition (air or N 2 ) polymer, Polymer/main FR, Polymer/synergist, Polymer/main FR/ synergist Condensed phase Gas phase PSS in PET/ZnPi Clay in PA6/AlPi-MPP No influence of the synergist on the decomposition pathway of the matrix or main FR: same products are detected Traces of ceramized silica Accumulation of platelets Volatilization of the PSS - 12

13 Protective structures CREPIM PET/ZnPi PET/ZnPi/M-PSS PA6/AlPi-MPP PA6/AlPi-MPP/o-MMT Before ignition After ignition phrr Thanks to the presence of M-PSS: - Higher expansion due to volatilization of PSS - More cells - Better insulation properties of the char Presence of clay change the morphology of the char: - More residue maintained, - Crust on the top instead of bubble, - Foam structure underneath with closed cells 13

14 Protective structures CREPIM PA6 PA6-o-MMT PA6/AlPi-MPP PA6/AlPi-MPP/o-MMT Resistance of the char In a parallel plate rheometer, - heating of the sample at 10 C/min until 500 C - Stay at 490 C during the compression of the sample Presence of clay change the morphology of the char: - More residue maintained, - Crust on the top instead of bubble, - Foam structure underneath with closed cells - Char highly resistant 14

15 Conclusion Two similar systems Engineering polymer / phosphinate / nanoparticle Synergistic effects cone, LI, UL-94 Modification of the dispersion in presence of nanoparticles No chemical interaction between the additives and polymer Condensed phase action of the synergist PSS = blowing agent More cells -MMT = nucleating agent Foam structure + accumulation of platelets