TY - JOUR A1 - Hofmann, D. A1 - Wartig, K.-A. A1 - Thomann, R. A1 - Dittrich, Bettina A1 - Schartel, Bernhard A1 - Mülhaupt, R. T1 - Functionalized graphene and carbon materials as additives for melt-extruded flame retardant polypropylene N2 - Functionalized graphene nanosheets TRGO and MLG 250, prepared from thermally reduced graphite oxide, represent attractive carbon additives for improving the performance of flame retardant polypropylene (PP-FR). The influence of carbon nanofiller type and content on morphology, thermal, mechanical, and electrical properties as well as the fire behavior of melt-extruded PP-FR is investigated. In contrast to conventional nano- and micron-sized carbon fillers such as expanded graphite (EG 40), nano-scaled carbon black (CB), and multiwall carbon nanotubes (CNT), only TRGO and MLG 250 afford uniform dispersion combined with simultaneously improved stiffness (+80%), electrical conductivity (3 × 10-5 S · cm-1) and enhanced flame retardancy of PP-FR, as expressed by lower peak heat release rate (-76%). KW - Extrusion KW - Flame retardance KW - Graphene KW - Nanocomposite KW - Polypropylene PY - 2013 DO - https://doi.org/10.1002/mame.201200433 SN - 1438-7492 SN - 1439-2054 VL - 298 IS - 12 SP - 1322 EP - 1334 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-29817 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schartel, Bernhard A1 - Damerau, Thomas A1 - Hennecke, Manfred T1 - Photo- and thermo-oxidative stability of aromatic spiro-linked bichromophoric cross-shaped molecules N2 - An extensive investigation of the photostability and the thermo-oxidative stability is presented for 2,2,7,7-tetrakis(biphenyl-4-yl)-9,9-spirobifluorene and 2,2,4,4,7,7-hexakis(biphenyl-4-yl)-9,9-spirobifluorene. Both compounds are conjugated fully aromatic systems that are being discussed as active functional materials for a variety of advanced applications. The effect of atmosphere, sample thickness and preparation procedure on photo-oxidative degradation are investigated in detail by absorption and fluorescence spectroscopy. Distinct mechanisms are described in terms of relevant parameters such as the quantum yields of the photo-oxidation and the fluorescence. No oxidative degradation could be detected under nitrogen. In ambient air a strong decrease of the fluorescence performance is found due to effective quenching by defective chromophores. Chemiluminescence investigations were performed to characterise the thermo-oxidative behaviour in the temperature region between 300 and 450 K. It becomes clear that even a stable chemical structure such as the investigated aromatic system does not guarantee sufficient photostability with regard to light emitting properties. About this Journal PY - 2000 DO - https://doi.org/10.1039/b004931j SN - 1463-9076 SN - 1463-9084 VL - 2 IS - 20 SP - 4690 EP - 4696 PB - The Royal Soc. of Chemistry CY - Cambridge AN - OPUS4-1002 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schartel, Bernhard A1 - Krüger, Simone A1 - Wachtendorf, Volker A1 - Hennecke, Manfred T1 - Excitation energy transfer of a bichromophoric cross-shaped molecule investigated by polarized fluorescence spectroscopy N2 - The excitation energy transfer (EET) of a bichromophoric cross-shaped molecule was investigated by stationary polarized fluorescence spectroscopy in the solid state. For this purpose 2,2[prime],7,7[prime]-tetrakis(biphenyl-4-yl)-9,9[prime]-spirobifluorene was embedded in a polymeric bisphenol-A-polycarbonate (PC) matrix. The dependence of the fluorescence on concentration and wavelength was determined. The role of the intermolecular and intramolecular EET is dealt with separately and discussed by means of the degree of polarization. The intermolecular excitation energy transfer is described in terms of a Förster transfer mechanism. The intramolecular transfer is prevented for the zero-point vibrational levels by the molecular cross-shaped structure, but is found for a wide range of wavelength, presumably based on vibrationally excited states. PY - 2000 DO - https://doi.org/10.1063/1.481620 SN - 0021-9606 SN - 1089-7690 VL - 112 IS - 22 SP - 9822 EP - 9827 PB - American Institute of Physics CY - Melville, NY AN - OPUS4-1038 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schartel, Bernhard A1 - Kunze, Ralf A1 - Neubert, Dietmar A1 - Tidjani, Adams T1 - ZnS as fire retardant in plasticised PVC N2 - The flame retardant effect of zinc sulphide (ZnS) in plasticised poly(vinyl chloride) (PVC-P) materials was investigated. PVC-P containing different combinations of additives such as 5% ZnS, 5% of antimony oxide (Sb2O3) and 5% of mixtures based on Sb2O3 and ZnS were compared. The thermal degradation and the combustion behaviour were studied using thermogravimetry (TG), coupled with FTIR (TG-FTIR) or with mass spectroscopy (TG-MS), and a cone calorimeter, respectively. A detailed and unambiguous understanding of the decomposition and release of the pyrolysis products was obtained using both TG-MS and TG-FTIR. The influence of ZnS, Sb2O3 and the corresponding mixtures on the thermal decomposition of PVC-P was demonstrated. Synergism was observed for the combination of the two additives. The combustion behaviour (time to ignition, heat release, smoke production, mass loss, CO production) was monitored versus external heat fluxes between 30 and 75 kW m-2 with the cone calorimeter. Adding 5% of ZnS has no significant influence on the fire behaviour of PVC-P materials beyond a dilution effect, whereas Sb2O3 works as an effective fire retardant. Synergism of ZnS and Sb2O3 allows the possibility of replacing half of Sb2O3 by ZnS to reach equivalent fire retardancy. KW - PVC KW - ZnS KW - Fire retardancy KW - TG-FTIR KW - Cone calorimeter PY - 2002 DO - https://doi.org/10.1002/pi.845 SN - 0959-8103 SN - 1097-0126 SN - 0007-1641 VL - 51 IS - 3 SP - 213 EP - 222 PB - Wiley InterScience CY - Chichester, West Sussex AN - OPUS4-1291 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schartel, Bernhard A1 - Kunze, Ralf A1 - Neubert, Dietmar T1 - Red Phosphorus-Controlled Decomposition for Fire Retardant PA 66 N2 - The thermal degradation and the combustion behavior of glass fiber-reinforced PA 66 materials containing red phosphorus were investigated. Thermogravimetry (TG), TG coupled with FTIR, and TG coupled with mass spectroscopy were used to investigate the thermal decomposition. The flame retardant red phosphorus was investigated with respect to the decomposition kinetics and the release of volatile products. The combustion behavior was characterized using a cone calorimeter. Fire risks and fire hazards were monitored versus external heat fluxes between 30 and 75 kW/m2. Red phosphorus acts in the solid phase and its efficiency depends on the external heat flux. The use of red phosphorus results in an increased amount of residue and in a corresponding decrease in total heat release. The decrease of the mass loss rate peak results in a corresponding decrease of the peak heat release. With increasing external heat flux applied the first effect on the total heat release decreases linearly, whereas the second effect on the peak heat release expands linearly. The investigation provides insight into the mechanisms of how the fire retardant PA 66 is achieved by red phosphorus controlling the degradation kinetics. Taking into account that a decrease of the volatile products also leads to a decrease of heat production in the flame zone and that the char acts as heat transfer barrier, a reduced pyrolysis temperature is suggested as a further feedback effect. T2 - 8th European Conference on fire retardant polymers CY - Alessandria, Italy DA - 2001-06-24 KW - PA 66 KW - Red phosphorus KW - Fire retardancy KW - TG-FTIR KW - Cone calorimeter PY - 2002 DO - https://doi.org/10.1002/app.10144 SN - 0021-8995 SN - 1097-4628 VL - 83 IS - 10 SP - 2060 EP - 2071 PB - Wiley InterScience CY - Hoboken, NJ AN - OPUS4-1234 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schartel, Bernhard A1 - Kühn, Gerhard A1 - Mix, Renate A1 - Friedrich, Jörg Florian T1 - Surface Controlled Fire Retardancy of Polymers Using Plasma Polymerisation N2 - Communication: Fire retardant coatings are deposited on polyamide-66 using plasma polymerisation. Chemical composition and thickness of deposits are adjusted varying the plasma treatment based on hexamethydisiloxane mixed with oxygen. The fire retardancy performances are evaluated using a cone calorimeter. The correlation between fire retardancy and thickness as well as chemical composition is discussed. KW - Cone calorimeter KW - Flame retardance KW - Heat release KW - Plasma polymerization KW - Polyamides PY - 2002 DO - https://doi.org/10.1002/1439-2054(20020901)287:9<579::AID-MAME579>3.0.CO;2-6 SN - 1438-7492 SN - 1439-2054 VL - 287 IS - 9 SP - 579 EP - 582 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-1537 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Lehmann, M. A1 - Schartel, Bernhard A1 - Hennecke, Manfred A1 - Meier, H. T1 - Dendrimers consisting of stilbene or distyrylbenzene building blocks synthesis and stability N2 - On the basis of Wittig-Horner reactions and protection group techniques compound 7 for the core and the components 9a-c and 11a-c for the dendrons were prepared and linked in the final step. The convergent synthesis yielded constitutionally and configurationally pure dendrimers (2a-c, 2a'-c') which consist of distyrylbenzene units. Their thermo-oxidative stability in the presence of air was studied by chemiluminescence and compared to the dendrimers 1 consisting of stilbene units. KW - Chemiluminescence KW - Dendrimers KW - Diphenylethylenderivate KW - Oxidation KW - Wittig reactions PY - 1999 DO - https://doi.org/10.1016/S0040-4020(99)00823-6 SN - 0040-4020 SN - 1464-5416 VL - 55 IS - 47 SP - 13377 EP - 13394 PB - Elsevier Science CY - Kidlington AN - OPUS4-1539 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Xu, C. A1 - Battig, Alexander A1 - Schartel, Bernhard A1 - Siegel, R. A1 - Senker, J. A1 - von der Forst, I. A1 - Unverzagt, C. A1 - Agarwal, S. A1 - Möglich, A. A1 - Greiner, A. T1 - Investigation of the Thermal Stability of Proteinase K for the Melt Processing of Poly(L‑lactide) N2 - The enzymatic degradation of aliphatic polyesters offers unique opportunities for various use cases in materials science. Although evidently desirable, the implementation of enzymes in technical applications of polyesters is generally challenging due to the thermal lability of enzymes. To prospectively overcome this intrinsic limitation, we here explored the thermal stability of proteinase K at conditions applicable for polymer melt processing, given that this hydrolytic enzyme is well established for its ability to degrade poly(L-lactide) (PLLA). Using assorted spectroscopic methods and enzymatic assays, we investigated the effects of high temperatures on the structure and specific activity of proteinase K. Whereas in solution, irreversible unfolding occurred at temperatures above 75−80 °C, in the dry, bulk state, proteinase K withstood prolonged incubation at elevated temperatures. Unexpectedly little activity loss occurred during incubation at up to 130 °C, and intermediate levels of catalytic activity were preserved at up to 150 °C. The resistance of bulk proteinase K to thermal treatment was slightly enhanced by absorption into polyacrylamide (PAM) particles. Under these conditions, after 5 min at a temperature of 200 °C, which is required for the melt processing of PLLA, proteinase K was not completely denatured but retained around 2% enzymatic activity. Our findings reveal that the thermal processing of proteinase K in the dry state is principally feasible, but equally, they also identify needs and prospects for improvement. The experimental pipeline we establish for proteinase K analysis stands to benefit efforts directed to this end. More broadly, our work sheds light on enzymatically degradable polymers and the thermal processing of enzymes, which are of increasing economical and societal relevance. KW - Enzymatic degradation KW - Poly(L‑lactide) KW - Polyesters KW - biodegradation PY - 2022 DO - https://doi.org/10.1021/acs.biomac.2c01008 SN - 1525-7797 SN - 1526-4602 VL - 23 IS - 11 SP - 4841 EP - 4850 PB - ACS Publications AN - OPUS4-56292 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Battig, Alexander A1 - Garfias González, Karla I. A1 - Schartel, Bernhard T1 - Valorizing “non-vegan” bio-fillers: Synergists for phosphorus flame retardants in epoxy resins N2 - Sustainable, biogenic flame retardant adjuvants for epoxy resins are receiving increased focus. Zoological products like insects, bone meal, and eggshells are available in large quantities, but remain uninvestigated as functional fillers to epoxy resins, although they are potential synergists to flame retardants. The efficacy and flame retardancy of “non-vegan” additives in combination with flame retardants is investigated and the fire behavior and thermal decomposition of bio-sourced epoxy resin composites is characterized. By comparing the fire performance of composites containing flame retardants or fillers at varying loadings (5, 10, and 20%), their role as synergists that enhance the function of organophosphorus flame retardants in bio-epoxy composites is identified and quantified. Peak heat release rates were 44% lower in composites containing both filler and flame retardant versus those containing only flame retardants, and fire loads were reduced by 44% versus the pure resin, highlighting the ability of “non-vegan” fillers to function as synergists. KW - Flame retardancy KW - Synergy KW - Bio-composite KW - Epoxy resin KW - Biogenic KW - Renewable PY - 2022 DO - https://doi.org/10.1016/j.polymdegradstab.2022.109875 SN - 0141-3910 VL - 198 SP - 109875 PB - Elsevier Ltd. AN - OPUS4-54438 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Strommer, Bettina A1 - Battig, Alexander A1 - Frasca, Daniele A1 - Schulze, Dietmar A1 - Huth, Christian A1 - Böhning, Martin A1 - Schartel, Bernhard T1 - Multifunctional Property Improvements by Combining Graphene and Conventional Fillers in Chlorosulfonated Polyethylene Rubber Composites N2 - The incorporation of nanoparticles like multilayer graphene (MLG) into elastomeric composites boosts their technical performance, such as their mechanical behavior and electrical conductivity. Common filler types (carbon black (CB) and aluminum trihydroxide (ATH)) generally fulfill single, specific purposes and are often used in high loadings. CB typically reinforces rubber mechanically, while ATH increases flame retardancy. Small amounts of MLG reduce these high filler contents and maintain the multifunctional characteristics of rubber composites. In chlorosulfonated polyethylene (CSM) + ATH, an intrinsically flame-retardant rubber was designed to achieve the highest standards such as maximum average of heat emission (MARHE) <90 kW m−2, 3 phrMLG was substituted for 15 phr CB and/or 3 phr ATH via an industrially applicable processing approach. Replacing either CB or ATH resulted in a property profile that was multifunctionally improved in terms of features such as mechanical performance, reduced sorption, and flame retardance. MLG nanocomposites are reported to show promise as an industrially utilizable route to obtain multifunctional high-performance rubbers. KW - Nanocomposites KW - Rubber KW - Multilayer graphene KW - Flame retardancy KW - Synergy KW - Nanoparticles KW - Elastomers PY - 2022 DO - https://doi.org/10.1021/acsapm.1c01469 SN - 2637-6105 VL - 4 IS - 2 SP - 1021 EP - 1034 PB - ACS Publ. CY - Washington, DC AN - OPUS4-54330 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -