TY - CHAP A1 - Pikacz, E. A1 - Seefeldt, Henrik A1 - Schartel, Bernhard A1 - Braun, Ulrike A1 - Karrasch, Andrea A1 - Jäger, Christian T1 - Flame retardancy in PC/Silicone rubber blends using BDP and additional additives T2 - 20th Annual conference on recent advances in flame retardancy of polymeric materials CY - Stamford, CT, USA DA - 2009-06-01 KW - Flame retardancy KW - PC blend KW - Aryl phosphate PY - 2009 SN - 1-59623-509-8 VL - 20 IS - Chapter IV-B SP - 236 EP - 246 CY - Wellesley, MA, USA AN - OPUS4-20703 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wawrzyn, Eliza A1 - Schartel, Bernhard A1 - Seefeldt, Henrik A1 - Karrasch, Andrea A1 - Jäger, Christian T1 - What reacts with what in bisphenol A polycarbonate/silicon rubber/bisphenol A bis(diphenyl phosphate) during pyrolysis and fire behavior? N2 - The pyrolysis and flame retardancy of a bisphenol A polycarbonate/silicon rubber/bisphenol A bis(diphenyl phosphate) (PC/SiR/BDP) blend were investigated and compared to those of PC/BDP and PC/SiR. The impact modifier SiR consists mainly of poly(dimethylsiloxane) (PDMS > 80 wt %). The pyrolysis of PC/SiR/BDP was studied by thermogravimetry (TG), TG–FTIR to analyze the evolved gases, and a Linkam hot stage cell within FTIR as well as 29Si NMR and 31P NMR to analyze the solid residue. The fire performance was determined by PCFC, LOI, UL 94, and a cone calorimeter under different external irradiations. The fire residues were studied by using ATR-FTIR as well as the additional binary systems PC + PDMS, PC + BDP, and BDP + PDMS, focusing on the specific chemical interactions. The decomposition pathways are revealed, focusing on the competing interaction between the components. Fire retardancy in PC/SiR/BDP is caused by both flame inhibition in the gas phase and inorganic-carbonaceous residue formation in the condensed phase. The PC/SiR/BDP does not work as well superimposing the PC/SiR and PC/BDP performances. PDMS reacts with PC and BDP, decreasing BDP's mode of action. Nevertheless, the flammability (LOI > 37%, UL 94 V-0) of PC/SiR/BDP equals the high level of PC/BDP. Indeed, SiR in PC/SiR/BDP is underlined as a promising impact modifier in flame-retarded PC/impact modifier blends as an alternative to highly flammable impact modifiers such as acrylonitrile–butadiene–styrene (ABS), taking into account that the chosen SiR leads to PC blends with a similar mechanical performance. KW - PC KW - BDP KW - PDMS KW - Flame retardancy KW - Flammability KW - Decomposition KW - Pyrolysis PY - 2012 DO - https://doi.org/10.1021/ie201908s SN - 0888-5885 SN - 1520-5045 VL - 51 IS - 3 SP - 1244 EP - 1255 PB - American Chemical Society CY - Washington, DC AN - OPUS4-25460 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wawrzyn, Eliza A1 - Schartel, Bernhard A1 - Karrasch, Andrea A1 - Jäger, Christian T1 - Flame-retarded bisphenol A polycarbonate/silicon rubber/bisphenol A bis(diphenyl phosphate): Adding inorganic additives N2 - Various inorganic additives belonging to four different groups: layered materials, metal hydroxides, metal oxides/carbonate and metal borates are investigated in bisphenol A polycarbonate/silicon rubber/bisphenol A bis(diphenyl phosphate) (PC/SiR/BDP) to improve flame retardancy. The pyrolysis, reaction to small flame and fire behaviour of the blends are characterised and structure–property relationships discussed. Among the added layered materials, talc functions as an inert filler with potential for commercialisation, whereas organically modified montmorillonite (LS) enhances decomposition. PC/SiR/BDP + talc and PC/SiR/BDP + LS reinforce the char and induce a flow limit. The different dispersion and location of boehmite (AlO(OH)) nano-particles and Mg(OH)2 micro-particles determine the impact on performance. PC/SiR/BDP + Mg(OH)2 shows additional hydrolysis and thus reduced flame retardancy. AlO(OH) is embedded in SiR and thus behaves as an inert filler. Both additives worked as smoke suppressants. Using selective filling with nano-particles is proposed as an interesting route for flame retardancy in PC/SiR blends. Adding metal oxides and carbonate (MgO, CaCO3 and SiO2) changes the decomposition pathways of PC/SiR/BDP, worsening the fire performance of PC/SiR/BDP. CaCO3 harbours the potential to intumescence, even though an early collapse of the char structure occurred. Adding hydrated metal borates, CaB, MgB and ZnB, changes the pyrolysis and flame retardancy action. Smoke suppression occurs; LOI is improved as well as UL 94 classification. ZnB performs better than MgB and CaB. The comprehensive study, also based on systematic material variation, delivers valuable guidelines for future development of flame-retarded multi-component PC blends. KW - Flame retardancy KW - Polycarbonate blends KW - Aryl phosphate KW - Inorganic fillers PY - 2014 DO - https://doi.org/10.1016/j.polymdegradstab.2013.08.006 SN - 0141-3910 SN - 1873-2321 VL - 106 SP - 74 EP - 87 PB - Applied Science Publ. CY - London AN - OPUS4-30952 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Karrasch, Andrea A1 - Wawrzyn, Eliza A1 - Schartel, Bernhard A1 - Jäger, Christian T1 - Solid-state NMR on thermal and fire residues of bisphenol A polycarbonate/silicone acrylate rubber/bisphenol A bis(diphenyl-phosphate)/(PC(SiR/BDP) and PC/SiR/BDP/zinc borate (PC/SiR/BDP/ZnB) - Part 1: PC charring and the impact of BDP and ZnB N2 - Structural changes in the condensed phase of bisphenol A polycarbonate (containing 0.45 wt% poly (tetrafluoroethylene))/silicone acrylate rubber/bisphenol A bis(diphenyl-phosphate) (PC/SiR/BDP) and PC/SiR/BDP/zinc borate (PC/SiR/BDP/ZnB) during thermal treatment in nitrogen atmosphere and in fire residues were investigated by solid-state NMR. H-1, B-11, C-13 and P-31 NMR experiments using direct excitation with a single pulse and H-1-P-31 cross-polarization (CP) were carried out including 31P(1 H) and C-13{P-31}double-resonance techniques (REDOR: Rotational Echo Double Resonance) on a series of heat-treated samples (580 K-850 K). Because many amorphous phases occur in the solid residues, and solid-state NMR spectroscopy addresses the most important sites carbon, phosphorus and boron, this paper is the key analytical approach for understanding the pyrolysis and flame retarding phenomenon in the condensed phase of PC/SiR/BDP and PC/SiR/BDP/ZnB. For the system PC/SiR/BDP it is shown that (i) at temperatures around 750-770 K (main decomposition step) carbonaceous charring of PC occurs and arylphosphate structures are still present, reacted in part with the decomposing PC; (ii) for higher temperatures from 770 K the phosphorus remaining in the solid phase increasingly converts to amorphous phosphonates and inorganic orthophosphates with a minor amount of crystalline orthophosphates; and (iii) H-1-P-31{H-1} CP REDOR and H-1-C-13{P-31} CP REDOR NMR experiments suggest that the phosphates and phosphonates are bound via oxygen to aromatic carbons, indicating the interaction with the carbonaceous char. When ZnB is added to the system PC/SiR/BDP, (i) ZnB leads to a slightly enhanced PC decomposition for temperatures below 750 K; (ii) alpha-Zn-3(PO4)(2) and borophosphate (BPO4) are formed in small amounts at high temperatures suggesting a reaction between BDP and ZnB during thermal decomposition; and (iii) most of the borate remains in the solid residues, forming an amorphous pure borate network, with the BO3/BO4 ratio increasing with higher temperatures. The NMR data of thermal and fire residues are highly correlated, underlining the importance of this work for understanding the pyrolysis and flame retardancy mechanisms in the condensed phase during the burning of the PC/SiR blends. (C) 2010 Elsevier Ltd. All rights reserved. KW - Flame retardance KW - NMR KW - Polycarbonate (PC) blends KW - Bisphenol-A bis(diphenyl)phosphate (BDP) KW - Zinc borate PY - 2010 DO - https://doi.org/10.1016/j.polymdegradstab.2010.07.034 SN - 0141-3910 SN - 1873-2321 VL - 95 IS - 12 SP - 2525 EP - 2533 PB - Applied Science Publ. CY - London AN - OPUS4-22647 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Karrasch, Andrea A1 - Wawrzyn, Eliza A1 - Schartel, Bernhard A1 - Jäger, Christian T1 - Solid-state NMR on thermal and fire residues of bisphenol A polycarbonate/silicone acrylate rubber/bisphenol A bis(diphenyl-phosphate)/(PC(SiR/BDP) and PC/SiR/BDP/zinc borate (PC/SiR/BDP/ZnB) - Part II: The influence of SiR N2 - Solid residues of bisphenol A polycarbonate (containing 0.45 wt% poly(tetrafluoroethylene))/silicone acrylate rubber/bisphenol A bis(diphenyl-phosphate) (PC/SiR/BDP) and PC/SiR/BDP/zinc borate (PC/SiR/BDP/ZnB) after thermal treatment were investigated by solid-state and liquid-state NMR, focusing on the role and interaction of SiR with the other components of the polymer blend. In PC/SiR/BDP, part of the SiR reacts to an amorphous silicate network rather than being completely released in the gas phase. The silicate network consists of Q4 and Q3 groups formed via intermediate D and T groups. The D groups are formed by a reaction of SiR with bisphenol-A units as well as phenyl groups of PC and BDP. In addition a small amount of silicon diphosphate was observed after thermal treatment at temperatures higher than 810 K. The same decomposition products (without SiP2O7) occur in the solid residues of PC/SiR/BDP/ZnB samples. The formation of intermediate D and T groups occurs earlier, at slightly lower temperatures. Any formation of a borosilicate network was excluded. The results also apply for the fire residues of PC/SiR/BDP and PC/SiR/BDP/ZnB and are thus valuable for understanding the impact of SiR on pyrolysis and flame retardancy mechanisms in the condensed phase during the burning of PC/SiR/BDP blends. SiR was found to influence the pyrolysis and the char formed. Beyond the replacement of highly combustible mechanical modifiers, SiR harbours the potential to enhance flame retardancy. KW - Flame retardance KW - 29Si NMR KW - Polycarbonate (PC) blends KW - Bisphenol A bis(diphenyl)phosphate (BDP) KW - Silicone rubber PY - 2010 DO - https://doi.org/10.1016/j.polymdegradstab.2010.07.030 SN - 0141-3910 SN - 1873-2321 VL - 95 IS - 12 SP - 2534 EP - 2540 PB - Applied Science Publ. CY - London AN - OPUS4-22648 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -