7.5 Technische Eigenschaften von Polymerwerkstoffen
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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.
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.
In den letzten Jahrzehnten wurde die Degradation der polymeren Matrix von flammgeschützten Polymeren eingehend untersucht. Erst in den letzten Jahren jedoch hat sich die Frage der Lebensdauer der Funktionalität des Flammschutzes selbst als wichtige Fragestellung herauskristallisiert, z.B. bei Kabeln. Deshalb sollte diese Fragestellung durch systematisch-variierte künstliche Klima- und Bewitterungstests an flammgeschützten Polymerwerkstoffen untersucht werden.
Tailored crosslinking in elastomers is crucial for their technical applications. The incorporation of nanoparticles with high surface-to-volume ratios not only leads to the formation of physical networks and influences the ultimate performance of nanocomposites, but it also affects the chemical crosslinking reactions. The influence of few-layer graphene (FLG) on the crosslinking behavior of natural rubber is investigated. Four different curing systems, two sulfur-based with different accelerator-to-sulfur ratios, and two peroxide-based with different peroxide concentrations, are combined with different FLG contents. Using differential scanning calorimetry (DSC), vulcametry (MDR) and swelling measurements, the results show an accelerating effect of FLG on the kinetics of the sulfur-based curing systems, with an exothermic reaction peak in DSC shifted to lower temperatures and lower scorch and curing times in the MDR. While a higher accelerator-to-sulfur ratio in combination with FLG leads to reduced crosslinking densities, the peroxide crosslinkers are hardly affected by the presence of FLG. The good agreement of crosslink densities obtained from the swelling behavior confirms the suitability of vulcameter measurements for monitoring the complex vulcanization process of such nanocomposite systems in a simple and efficient way. The reinforcing effect of FLG shows the highest relative improvements in weakly crosslinked nanocomposites.
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.
Im Rahmen des Forschungsprojektes IGF 20470N wurden Untersuchungen zum Alterungsverhalten von reaktiven Brandschutzsystemen (RBS) auf Stahlbauteilen durchgeführt. Mithilfe der Ergebnisse einer umfangreichen Literaturrecherche sowie experimentellen und numerischen Untersuchungen sollte ein Vorschlag für ein Prüfkonzept zum Nachweis einer Nutzungsdauer von RBS von mehr als 10 Jahren auf Basis von Kurzzeitversuchen abgeleitet werden. Dabei setzt die Bewertung des Alterungsverhaltens von RBS voraus, dass die Mechanismen der Alterung hinreichend bekannt sind.
Dafür wurden zunächst systematisch Daten von Kurz- und Langzeitversuchen von nationalen Zulassungsprüfungen der letzten Jahrzehnte ausgewertet. Anschließend wurden umfangreiche experimentelle Untersuchungen an einer wasserbasierten sowie einer epoxidharzbasierten Richtrezeptur durchgeführt. Da aus der Literatur bekannt ist, dass die Einflüsse der Bewitterung zu einer Veränderung der Konzentration der Bestandteile innerhalb der Beschichtung führen können, wurden Untersuchungen mit Mangelrezepturen durchgeführt, wobei systematisch einzelne Bestandteile reduziert wurden. Neben optischen Untersuchungen wurden thermoanalytische Verfahren (DSC-TG-, ATR-FTIR-, Elementar-, Farbanalyse) angewandt sowie Brandversuche an beschichteten Stahlplatten durchgeführt. Des Weiteren wurden die Richtrezepturen den beschleunigten Kurzzeitversuchen gemäß EAD 350402-00-1106 (2017) unterzogen, welche die Zulassung von Produkten auf europäischer Ebene regelt. Für die wasserbasierte Richtrezeptur wurden die Bewitterung für den feuchten Innenraum (Typ Z1) mehrfach wiederholt (1x, 3x, 6x). Für die epoxidharzbasierte Richtrezeptur entsprach die Bewitterung dem Zyklus für die Außenanwendung (Typ X). In Brandversuchen sowie thermoanalytischen und optischen Untersuchungen wurde das Alterungsverhalten sowie die thermische Schutzwirkung analysiert.
Anschließend wurden numerische Simulationen von Stahlbauteilen mit gealterten RBS durchgeführt und anhand der experimentellen Untersuchungen validiert. Mithilfe der numerischen Modelle kann eine Bewertung der thermischen Schutzwirkung von Stahlbauteilen mit gealterten RBS vorgenommen werden.
Mithilfe der gesammelten Erkenntnisse wurde ein Vorschlag für ein Prüfkonzept für den Nachweis einer Nutzungsdauer von mehr als 10 Jahren abgeleitet. Das Prüfkonzept besteht dabei aus einem Katalog von Möglichkeiten, die aktuellen Zulassungsprüfungen auf europäischer Ebene für eine Nutzungsdauer von 10 Jahren auf einen längeren Zeitraum zu erweitern.
The important take home message of this chapter: When multicomponent flame retardant systems are applied to polymeric materials, it becomes possible to address multiple fire properties, increase efficiency, and minimize flame retardant use to maximize polymer property balance. Flame retardants are combined or used together with adjuvants or synergists; fibers and fillers make a crucial contribution to their fire properties. Multicomponent systems are discussed in their capacity as an overall powerful strategy for achieving and optimizing non-halogenated flame-retardant polymeric materials.
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.
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.
A few layer/multilayer graphene (MLG) with a specific surface area of BET=250 m2/g is proposed as an efficient multifunctional nanofiller for rubbers. The preparation method, i.e., ultrasonically-assisted solution mixing of master batches followed by two-roll milling, strongly influences the dispersion in the elastomeric matrix and is fundamental for the final properties. When homogenously dispersed, single stacks of only approximately 10 graphene sheets, with an aspect ratio of 34, work at low loadings, enabling the replacement of large amounts of carbon black (CB), an increase in efficiency, and a reduction in filler load. The appropriate preparation yielded nanocomposites in which just 3 phr are sufficient to significantly improve the rheological, curing, gas barrier properties, electrical and thermal conductivity, as well as mechanical properties of different rubbers, as shown for chlorine-Isobutylene-Isoprene rubber (CIIR), nitrile-butadiene rubber (NBR), natural rubber (NR), and styrene-butadiene rubber (SBR). 3 phr of MLG tripled the Young’s modulus of CIIR, an effect equivalent to 20 phr of CB. The stronger interactions between MLG and NR or SBR also resulted in a reduction in the elongation at break by 20% and 50%, respectively, while the same parameter was hardly changed for CIIR/MLG and NBR/MLG. CIIR/MLG and NBR/MLG were stiffer but just as defomable than CIIR and NBR. The strong reinforcing effect of 3 phr MLG was confirmed by the increase of greater than 10 Shore A in hardness. MLG reduces gas permeability, increases thermal and electrical conductivities, and retards flammability, the latter shown by the reduction in heat release rate in the cone calorimeter. We investigated MLG also as a synergist for reducing the aluminium trihydrate loading in flame retardant hydrogenated acrylonitrile-butadiene (HNBR), polybutadiene chloroprene (BR/CR), and chlorosulfonated polyethylene rubber(CSM). The higher the nanofiller concentration is, the greater the improvement in the properties. For instance, the permeability decreased by 30% at 3 phr of MLG, 50% at 5 phr and 60% at 10 phr, respectively. Moreover, the MLG nanocomposites improve stability of mechanical properties against the effects of weathering. In key experiments an increase in UV-absorption and a pronounced radical scavenging were proved as stabilizing mechanisms. In a nutshell, MLG is an efficient multifunctional nanofiller ready to be used for innovative rubber development.