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Leather is considered a luxury good when used in seating and upholstery. To improve safety, flame retardancy in leather is usually achieved through various finishing processes such as spray or roller coating. These treatments require processing steps that cost time and are laborintensive. One avenue to achieving flame retardancy in leather is to add flame retardants during the tanning process. However, the influence on flame retardancy exerted by specific intumescent additives specifically added during leather tanning has yet to be investigated. This work explores the roles played by intumescent additive compounds in flame retarding leather when they are added during tanning instead of applied as a coating. Via a systematic investigation of various compound mixtures, the flame retardant effects in the condensed and the gas phases are elucidated. The results show a strong impact of melamine in the gas phase and of polyphosphates in the condensed phase. Their impact was quantified in fire and smoke analysis, showing a 14% reduction in the peak of heat release rate, strongly reduced burning lengths, and a 20% reduction in total smoke release compared to nontreated leather. These results illuminate the key role played by specific compounds in the flame retardancy of leather, particularly when they are added specifically during the tanning process instead of being applied as a coating.
This method has great potential to reduce processing steps, lower costs, and improve material safety.
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.
Investigation of the Thermal Stability of Proteinase K for the Melt Processing of Poly(L‑lactide)
(2022)
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.
Valorizing “non-vegan” bio-fillers: Synergists for phosphorus flame retardants in epoxy resins
(2022)
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.
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.
Multifunctional Graphene in Flame Retarded Polybutadiene/ Chloroprene/ Carbon Black Composites
(2021)
Multilayer graphene is investigated as a multifunctional nanofiller to polybutadiene/ chloroprene rubbers (BR/CR) that partially substitutes carbon black (CB) and aluminum trihydroxide (ATH). Loadings of only 3 parts per hundred rubber (phr) MLG replaced 15 phr of CB and/or 3 phr of ATH in BR/CR nanocomposites. Mechanical and fire behavior were investigated, and results point to improved rheological, curing and mechanical properties of MLG-containing rubber composites.
A rigid aromatic phosphorus-containing hyperbranched flame retardant structure is synthesized from 10-(2,5 dihydroxyphenyl)-10H-9-oxa-
10-phosphaphenanthrene-10-oxide (DOPO-HQ), tris(4-hydroxyphenyl)phosphine oxide (THPPO), and 1,4-terephthaloyl chloride (TPC). The resulting poly-(DOPO-HQ/THPPO-terephthalate) (PDTT) is implemented as a flame retardant into an epoxy resin (EP) at a 10 wt% loading. The effects on EP are compared with those of the monomer DOPO-HQ and triphenylphosphine oxide (OPPh3) as low molar mass flame retardants. The glass transition temperature, thermal decomposition, flammability (reaction to small flame), and burning behavior of the thermosets are investigated using differential scanning calorimetry, thermogravimetric analysis, pyrolysis combustion flow calorimetry, UL 94-burning chamber testing, and cone calorimeter measurements.
Although P-contents are low at only 0.6 wt%, the study aims not at attaining V-0, but at presenting a proof of principle: Epoxy resinswith PDTT show promising fire performance, exhibiting a 25% reduction in total heat evolved (THE), a 30% reduction in peak heat release rate (PHRR) due to flame inhibition (21% reduction in effective heat of combustion (EHC)), and an increase in Tg at the same time. This study indicates that rigid aromatic hyperbranched polymeric structures offer a promising route toward multifunctional flame retardancy.
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.