TY - JOUR A1 - Battig, Alexander A1 - Sanchez-Olivares, G. A1 - Rockel, Daniel A1 - Maldonado-Santoyo, M. A1 - Schartel, Bernhard T1 - Waste not, want not: The use of leather waste in flame retarded EVA N2 - Leather is among the most ancient, widely used materials worldwide. Industrial-scale leather production produces large quantities of organic waste attained during shaving and buffing steps during processing. In this study, leather wastes (LW) are used as fillers in flame retarded polymer composites. LW is investigated as a multifunctional bio-filler that enhances the fire performance of flame retarded poly(ethylene–vinyl acetate) (EVA) containing phosphorus flame retardants (P-FRs) ammonium polyphosphate (APP) or a melamine-encapsulated APP (eAPP). Using LW from tanneries as adjuvants to enhance P-FRs in EVA reduces industrial wastes that otherwise require costly waste management solutions. Materials are characterized multi-methodically via mechanical tests, electron microscopy, rheology, thermogravimetric analysis, evolved gas analysis, and condensed phase FTIR, also reaction-to-small-flames and cone calorimeter tests. EVA containing 10 wt-% LW and 20 wt-% P-FRs achieve 20% reductions in fire loads versus EVA, and up to 10% reduction in effective heats of combustion versus EVA with equal (30 wt-%) P-FR loadings. Enhanced char stabilization of EVA composites with LW and P-FRs lowered peaks of heat release rates up to 53% compared to EVA, and up to 40% compared to equal P-FRs loadings. Synergisms between LW and P-FRs in EVA are quantified. A chemical decomposition mechanism is proposed. KW - Leather waste KW - Tannery industry KW - EVA KW - Fire protection KW - Flame retardancy KW - Charring PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-532977 DO - https://doi.org/10.1016/j.matdes.2021.110100 SN - 0264-1275 VL - 210 SP - 1 EP - 16 PB - Elsevier CY - Amsterdam AN - OPUS4-53297 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wahab, M. A. A1 - Kebelmann, Katharina A1 - Schartel, Bernhard A1 - Griffiths, G. T1 - Valorization of macroalgae digestate into aromatic rich bio-oil and lipid rich microalgal biomass for enhanced algal biorefinery performance N2 - The valorization of macroalgae digestate as a secondary resource for high value chemicals and nutrients will promote the sustainability and circularity of anaerobic digestion based biorefinery. In this study, three digestates from A. nodosum C.linum and L. digitata were separated into liquid and solid fractions to investigate the production of high value added chemicals through pyrolysis using Pyrolysis Gas Chromatography Mass Spectroscopy (Py-GC/MS) while the filtered liquid fractions were tested as an alternative culture media to grow C. sorokiniana under mixotrophic conditions. The digestates showed different thermal degradation and an improvement of bio-oil profiles compared to the starter material. Pyrolyzates from raw macroalgae were characterized by a high anhydrosugar content in contrast to high aromatics observed in the case of their digestates. Toluene, benzofuran and vinylphenol, base chemicals for many industries, represented together 30–37% of the total chemicals produced during pyrolysis of the three macroalgae digestate. On the other hand, C. sorokiniana cultured on digestate-based media showed a higher lipid content with an increase in monounsaturated fatty acids and a lower poly-unsaturated fatty acid content in comparison to microalgae grown in standard tris-acetate-phosphate media. Thus, the acyl composition was shifted in a direction more suitable for biodiesel production by this process. In addition, the increase of Chemical Oxygen Demand and Volatile Fatty Acids concentration in the digestate was found to reduce ammonium toxicity. Finally, 94% of Chemical Oxygen Demand and 83% of ammonium were removed by microalgae from the digestate-based media which will reduce the pollution risk of the biorefinery. Overall, the results indicate that using macroalgae solid digestates can generate improvements in the quality of products obtained by pyrolysis and the liquid digestate can positively influence microalgae growth and its products. KW - Macroalgae KW - Anaerobic digestion KW - Aromatics KW - Microalgae culture KW - Biorefinery PY - 2022 DO - https://doi.org/10.1016/j.jclepro.2022.130925 SN - 0959-6526 VL - 341 SP - 1 EP - 10 PB - Elsevier Ltd. AN - OPUS4-54365 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schartel, Bernhard T1 - Non-vegan flame-retardant (adjuvants in) biocomposites N2 - Emanating from developing flame retarded biocomposites, we have proposed renewable natural fibers (including keratin) taken from industrial waste as an authentic sustainable approach. More recently, we have investigated non-vegan flame retardant approaches. This paper loves to give you an insight into our ongoing projects on biogenic industrial wastes like leather, bone meal, and insects. Materials were characterized multi-methodically, flame retardant modes of action quantified, decomposition mechanism proposed, and synergisms explained. Considering the large quantities of leather waste (LW) in industrial-scale production, we underline LW as multifunctional bio-adjuvants. LW enhances the flame retardancy of poly(ethylene-vinyl acetate) (EVA) containing phosphorus flame retardants (P-FR). Products/by-products of the invertebrate and vertebrate farming, respectively, are promising bio-based adjuvants in flame retarded bio-epoxy thermosets. While the addition of bone meal yields the formation of an inorganic shield, protein-based powders from insects provide an intumescent behavior. In combination with a P-FR superior charring and self-extinguishing are obtained. Acknowledgement: In part of this work was supported by the Volkswagen Foundation grant “Experiment!” No. 97437. T2 - Fire and Polymers, workshop, ACS Division of Polymer Chemistry CY - Napa, California, US DA - 05.06.2022 KW - Fire behaviour KW - Renewable KW - Circular economy KW - Biocomposite PY - 2022 AN - OPUS4-55025 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Gleuwitz, F. Robert A1 - Battig, Alexander A1 - Schartel, Bernhard T1 - Tenebrio molitor Beetle as a “Nonvegan” Adjuvant to Flame Retardants in Tannic Acid-Based Epoxy Thermosets N2 - Material solutions that meet both circular bioeconomy policies and high technical requirements have become a matter of particular interest. In this work, a prospectively abundant proteinrich waste resource for the manufacturing of flame-retardant epoxy biocomposites, as well as for the synthesis of biobased flame retardants or adjuvants, is introduced. Different biomass fillers sourced from the cultivation of the mealworm beetle Tenebrio molitor are embedded in a bioepoxy resin cured with tannic acid and investigated regarding the fire performance of the thermosets. By means of spectroscopic and thermal analysis (attenuated total reflectance FTIR spectroscopy, thermogravimetric analysis-coupled FTIR spectroscopy, and differential scanning calorimetry), the influence of the biomass microparticles on the curing and thermal degradation behavior is evaluated. The final performance of the biocomposites is assessed based on fire testing methodology (limited oxygen index, UL-94, and cone calorimetry). Providing a high charring efficiency in the specific tannic acid-based epoxy matrix, the protein-rich adult beetle is further investigated in combination with commercial environmentally benign flame retardants in view of its potential as an adjuvant. The results highlight a char forming effect of nonvegan fillers in the presence of tannic acid, particularly during thermal decomposition, and point toward the potential of protein-based flame retardants from industrial insect rearing for future formulations. KW - Tannic acid KW - Flame retardancy KW - Sustainable KW - Epoxy resin KW - Insects PY - 2022 DO - https://doi.org/10.1021/acssuschemeng.2c00746 SN - 2168-0485 VL - 10 IS - 19 SP - 6313 EP - 6324 PB - ACS AN - OPUS4-54845 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Chacon Castro, Jose Pablo A1 - Schneider, Rika A1 - Greiner, Andreas A1 - Schartel, Bernhard T1 - Flame retardant poly(limonene carbonate): material innovation as a game changer N2 - The global plastic industry relies on fossil-based materials, presenting environmental challenges. A sustainable polymer namely poly(limonene carbonate) (PLimC), made of limonene and CO2 as two monomers from non-food sources, shows advances in various applications where additives such as flame retardants (FRs) are crucial to comply with fire safety measures. The variety of FRs is wide, and therefore the approach involved conducting a comparative study of four different halogen-free flame retardant systems that are conventionally used in polycarbonates and polyolefins to understand which FR enhances the flame resistance of PLimC most effectively. The primary task of the project is to conduct experimental evaluations to analyze the thermal properties, flammability, and fire behavior of each system. This data will offer valuable insights towards the advancement of safer and more sustainable materials. T2 - Polymers for Sustainable Future 2024 CY - Prague, Czech Republic DA - 24.06.2024 KW - Poly(limonene carbonate) KW - Flame retardancy KW - Fire science PY - 2024 AN - OPUS4-60556 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Rockel, Daniel A1 - Sanchez Olivares, G. A1 - Schartel, Bernhard T1 - Improving the Flame Retardancy of Aluminium Trihydroxide in Thermoplastic Starch Biocomposites Using Waste Fibers and Silicon-Based Synergists N2 - The synergistic behavior of different silicon compounds is investigated in flame retardant biocomposites with aluminum trihydroxide (ATH) as the main flame retardant. The paper shows a new approach towards sustainable biocomposites through the implementation of thermoplastic starch (TPS), leather fibers from industrial waste streams, and non-hazardous flame retardants and synergists. In these multicomponent systems, the different components address different modes of action in the fire scenario. When ATH is partially substituted by glass frits or layered silicates, fire performance is enhanced without changing the total amount of filler in the polymer. In a biocomposite with 25 phr of fiber and 90 phr of ATH, substituting 5 phr of ATH for layered silicates increased the LOI from 31.5 vol % to 34.8 vol %, decreased the peak of heat release by 20%, and increased the UL 94 rating from V-1 to V-0. KW - Biocomposites KW - Sustainability KW - Waste streams KW - Flame retardancy KW - Synergism KW - Modes of action PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-605711 DO - https://doi.org/10.1021/acssusresmgt.4c00053 SN - 2837-1445 VL - 1 IS - 6 SP - 1131 EP - 1145 PB - ACS AN - OPUS4-60571 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Dudziak, Mateusz A1 - Bhatia, Riya A1 - Dey, Rohit A1 - Ullrich, Matthias S. A1 - Schartel, Bernhard T1 - Phosphor-enriched wastewater products as sustainable flame retardant in PLA N2 - Revolutionizing our polymer industry for adaption to a sustainable carbon circular economy has become one of today’s most demanding challenges. Exploiting renewable resources to replace fossil-fuel—based plastics with biopolymers such as poly(lactic acid) (PLA) is inevitable while using waste streams as a raw material resource at least is promising. When it comes to using PLA as technical polymer, its high flammability must be addressed by flame retardants compatible with the thermoplastic processing of PLA and its compostability. This study proposes microalgae enriched with phosphorus from wastewater (P-Algae) as an elegant way towards a kind of sustainable organophosphorus flame retardant. The concept is demonstrated by investigating the processing, pyrolysis, flammability, and fire behavior of PLA/P-Algae, while varying the P-Algae content and comparing P-Algae with four alternative bio-fillers (phosphorylated lignin, biochar, thermally treated sewage sludge, and metal phytate) with different P-contents as meaningful benchmarks. T2 - EcoFRam2024 CY - Valencia, Spain DA - 22.05.2024 KW - PLA KW - Flame retardancy KW - Phosphorylated algae KW - Wastewater flame retardants KW - Zink phytate KW - Phosphorylated lignin KW - Thermally treated sludge PY - 2024 AN - OPUS4-60142 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Dudziak, Mateusz A1 - Schartel, Bernhard T1 - Phosphor-enriched wastewater products as sustainable flame retardant in PLA N2 - Revolutionizing our polymer industry for adaption to a sustainable carbon circular economy has become one of today’s most demanding challenges. Exploiting renewable resources to replace fossil-fuel—based plastics with biopolymers such as poly(lactic acid) (PLA) is inevitable while using waste streams as a raw material resource at least is promising. When it comes to using PLA as technical polymer, its high flammability must be addressed by flame retardants compatible with the thermoplastic processing of PLA and its compostability. This study proposes microalgae enriched with phosphorus from wastewater (P-Algae) as an elegant way towards a kind of sustainable organophosphorus flame retardant. The concept is demonstrated by investigating the processing, pyrolysis, flammability, and fire behavior of PLA/P-Algae, while varying the P-Algae content and comparing P-Algae with four alternative bio-fillers (phosphorylated lignin, biochar, thermally treated sewage sludge, and metal phytate) with different P-contents as meaningful benchmarks. T2 - Polymers for Sustainable Future CY - Prague, Czech Republic DA - 24.06.2024 KW - PLA KW - Flame Retardancy KW - Thermally Treated Sludge KW - Phosphorylated Algae KW - Zink Phytate KW - Wastewater Flame Retardants KW - Phosphorylated Lignin PY - 2024 AN - OPUS4-60619 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Markwart, J. C. A1 - Battig, Alexander A1 - Urbaniak, T. A1 - Haag, K. A1 - Koschek, K. A1 - Schartel, Bernhard A1 - Wurm, F. R. T1 - Intrinsic flame retardant phosphonate-based vitrimers as a recyclable alternative for commodity polymers in composite materials N2 - Recycling of crosslinked fiber-reinforced polymers is difficult. Moreover, as they are often based on flammable resins, additional additives are needed. So-called “vitrimers” open the possibility of Recycling and reprocessing and repairing with dynamically crosslinked chemistries. To date, vitrimer-based composites still need flame retardant additives, such as organophosphates. An additive-free vitrimer composite has not been reported. Herein, we synthesized an intrinsic flame-retardant vitrimer, relying on vinylogous polyurethanes containing covalently installed phosphonates as flame-retardant units and prepared glassfiber-reinforced composites. We studied recycling and flame retardant properties and compared the data to phosphorus-free vitrimers and conventional epoxy resins (with and without additive flame retardant). Our phosphonate-based vitrimer proved in first tests, a flame retardant effect comparable to commercial flame retardant resins. The bending strength and bending modulus for the phosphorus-vitrimer glass fiber composites were comparable to glass fiber composites with permanently cross-linked epoxies. In summary, we were able to prove that the covalent installation of phosphonates into vitrimers allows the preparation of recyclable and intrinsic flame retardant composites that do not need flame retardant additives. We believe this concept can be expanded to other polymer networks and additives to generate recyclable and sustainable high-performance materials. KW - Vitrimer KW - Flame retardant KW - Recyclable KW - Organophosphonate KW - Polyurethane PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-510889 DO - https://doi.org/10.1039/d0py00275e VL - 11 IS - 30 SP - 4933 EP - 4941 AN - OPUS4-51088 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schartel, Bernhard T1 - Bio, Waste, Non-vegan – Fun, Food for Thought, or Future N2 - Overview of the state of the art and current trends with the main topics: - renewable sources in flame retardant polymers (flame retarded bio-polymers and biocomposites; bio-flame retardants, renewable adjuvants from industrial waste) - flame retardancy meets sustainability - concepts between analogy and out-of-the-box. T2 - 18th SKZ International Conference on Trends in Fire Safety and InnovativeRFlame retardants for Plastics CY - Würzburg/Rottendorf, Germany DA - 27.09.2022 KW - Bio-polymer KW - Bio-composite KW - Renewable source KW - Renewable adjuvants KW - Vitrimer KW - Bio-flame retardant PY - 2022 AN - OPUS4-55840 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 - CONF A1 - Schartel, Bernhard T1 - Flame Retardancy Features Sustainability Food for Thought, Fake Fiction, and Future N2 - Sustainability (environmental conservation for the economic welfare and prosperity for all) would revolutionise the plastics industry were it to become predominant practice as a linear, fossil-fuel–based economy is switched to a carbon circular one. Hence, the innovative field of flame-retardant polymeric materials should lend its strength to drive this challenge. Visionary solutions are proposed to inspire us, while the implementation of economically feasible concepts take us forward into the future. A critical overview of current trends is presented, using examples from the literature and our own recent projects. The examples lead from the use of natural materials with some intrinsic flame retardancy, via biocomposites, to using renewable sources for flame retardants. Natural flame retardants and adjuvants are highlighted, motivating our vision. Some of the visionary approaches such as flame-retardant poly(limonene carbonate) or wastewater phosphorus enriched micro algae as a sustainable flame retardant are rather innovative. Further, natural material streams find their way into polymer mass production as fillers, adjuvants, or renewable educt sources; industrial waste streams open the door to sustainable solutions, because they avoid competition for land with farming or virgin forests. Remarks will address recycling, flame retardant vitrimers are potential materials for recyclable thermosets. Only convincing property profiles will prevail both for exploiting renewable sources and circular design; sustainability must not be merely tolerated as an additional demand but should instead be recognized as a solution ensuring our economic welfare now and in the future. Acknowledgement: Funding: BMBF WTZ 01DN16040, DFG Scha 730/19 u. 20, VW-Stiftung: Experiment 97437, BMBF KMU Innovativ 031B1289B. People: A Battig, R Bhatia, J Chacon Castro, M Dudziak, SF Falkenhagen, FR Gleuwitz, a.o. (BAM) and G Sánchez Olivares (CIATEC), R Dey (Constructor University), A Greiner (Bayreuth), a.o. T2 - 19th Bayreuth Polymer Symposium CY - Bayreuth, Germany DA - 21.09.2025 KW - Poly(limonene carbonate) KW - Flame retardant biocomposites KW - Wastewater phosphorus enriched micro algae KW - Non-vegan flame retardant KW - Flame retardant vitrimers KW - Bio-based flame retardant PY - 2025 AN - OPUS4-64204 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Rockel, Daniel A1 - Sanchez Olivares, G. A1 - Calderas, F. A1 - Schartel, Bernhard T1 - It’s not waste, it’s a resource: Utilizing industrial waste fibers/mineral fillers to attain flame retardant biocomposites N2 - Integrating natural fibers derived from local industrial waste streams into thermoplastic starch (TPS) proves to be a promising approach towards sustainable flame retardant biocomposites. Initially, three types of waste fibers from the agave, coconut, and leather industries were evaluated for their flame retardant properties in combination with aluminum trihydroxide (ATH), an environmental friendly flame retardant. Leather fiber (BLF) exhibited the best flame retardant performance and were further investigated along with ATH and varying amounts of bentonite nanoclay to enhance the residual protective layer. The combination of multiple components shows improvement in performance while reducing the total load of filler. The images of the fire residues revealed that a more enclosed surface correlates with a reduction in the peak of heat release rate. Whereas higher amounts of bentonite does not deliver further inprovements, only 1 phr nanoclay in the novel multicomponent system of TPS, ATH, BLF, and bentonite synergistically improved the UL-94 rating from HB to V1. The proposed system brings together the different approaches using a renewable biopolymer, natural waste fibres, and envirnmentally friendly flame retardancy and thus, is striking for its combination of outstanding sustainablity, instant feasability, and sufficient fire performance. KW - Biocomposites KW - Flame retardancy KW - Residue analysis KW - Sustainability KW - Waste streams PY - 2025 DO - https://doi.org/10.1177/08927057241297083 SN - 0892-7057 SN - 1530-7980 VL - 38 IS - 6 SP - 2225 EP - 2252 PB - Sage AN - OPUS4-63431 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -