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Elastomers are usually mechanically reinforced with high loadings of carbon black (CB) to achieve the properties demanded; high amounts of mineral flame retardants are used to fulfill fire safety requirements. In this study, multilayer graphene (MLG), a nanoparticle made of only 10 graphene sheets, is applied in low loadings, 3 parts per hundred rubber (phr) to reduce the total amount of filler or boost performance in hydrogenated acrylonitrilebutadiene rubber (HNBR). In the HNBR/MLG nanocomposites, 3 phr MLG replaced 15 phr CB, 3 phr aluminum trihydroxide (ATH), or 15 phr CB + 3 phr ATH. The nanocomposites were prepared via master batch by ultrasonically assisted solution mixing and subsequent conventional two-roll milling. A comprehensive study is presented, illustrating the impact of MLG on curing and mechanical properties; e.g. replacing 2.5 phr ATH with 3 phr MLG increased the Young's modulus by over 60% and hardness by 10%, while improving flame retardancy, and reducing the total heat evolved by 10%. MLG is a multifunctional filler, as demonstrated by various enhancements in terms of the mechanical and flame retardancy properties of the rubber composites.
Ethylene propylene diene monomer (EPDM) Rubbers with the flame retardants tris(2-ethylhexyl)phosphate, ammonium polyphosphate, polyaniline, and aluminum trihydroxide were prepared and analyzed in this study. The homogenous dispersion of the fillers in the rubber matrix was confirmed by scanning electron microscope. To investigate the interplay of the different flame retardants, the flame retardants were varied systematically. The comprehensive study sought combinations of flame retardants that allow high loadings of flame retardants without deterioration of the physical and mechanical properties of the EPDM rubber. The eight EPDM rubbers were investigated via thermogravimetric analysis and pyrolysis gas chromatography coupled with a mass spectrometer (Py GC/MS) to investigate the potential synergistic effects. In the Py-GC/MS experiments, 27 pyrolysis products were identified. Furthermore, UL 94, limiting oxygen index, FMVSS 302, glow wire tests, and cone calorimeter tests were carried out. In the cone calorimeter test the EPDM rubbers R-1AP and R-1/2P achieved an increase in residue at flameout of 76% and a reduction in total heat evolved of about 35%. Furthermore, the compounds R-1AP and R-1/2P achieved a reduction in MARHE to about 150 kW m−1, a reduction of over 50% compared to the unprotected rubber R.
The impact of polyaniline in phosphorus flame retardant ethylene-propylene-diene-rubber (EPDM)
(2019)
Usually elastomers are loaded with high amounts of flame retardants to fulfill fire safety requirements. In this study the potential char precursor polyaniline (PANI) and the established fire retardant pentaerythritol (PER) were implemented in ethylene-propylene-diene monomer rubber (EPDM). PANI and PER were used in low loadings (7 phr) and combined with two phosphorous flame retardants, Ammonium polyphosphate (APP) and a piperazine-pyrophosphate/phosphoric acid compound (FP), to boost their performance. A comprehensive study is presented, explaining the impact of PANI on curing and mechanical properties, including compensation for the plasticizer-like effect of APP in EPDM, and improved flame retardancy. In the cone calorimeter test, the combination of EPDM/FP/PANI reduced the effective heat of combustion by 20%. All nine EPDM rubber compounds were investigated with the LOI and UL 94 tests, cone calorimeter, FMVSS 302 and glow wire testing to quantify fire performance. The PANI containing EPDM rubbers, EPDM/APP/PANI and EPDM/FP/PANI outperformed the corresponding PER containing, EPDM/APP/PER and EPDM/FP/PER rubbers in various tests. Moreover, the study investigated the impact of PANI and PER on the mode of action of the phosphorus species and showed that the addition of PANI increased the amount of phosphorus in the condensed phase. To receive a broader understanding of the flame retardant mode of action of PANI in combination with APP and FP, calculations were carried out to estimate the impact of PANI on the protective layer effect.
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.
Scientific publications addressing the durability of the flame retardance of cables during their long-term application are rare and our understanding lacks. Three commercial flame retardants, aluminum hydroxide, aluminum diethyl phosphinate (AlPi-Et), and intumescent flame retardant based on ammonium polyphosphate, applied in ethylene-vinyl acetate copolymer (EVA) model cables, are investigated. Different artificial aging scenarios were applied: accelerated weathering (UV-irradiation/temperature/rain phases), humidity exposure (elevated temperature/humidity), and salt spray exposure. The deterioration of cables’ surface and flame retardancy were monitored through imaging, color measurements, attenuated total reflectance Fourier transform infrared spectroscopy, and cone calorimeter investigations. Significant degradation of the materials’ surface occurred. The flame retardant EVA cables are most sensitive to humidity exposure; the cable with AlPi-Et is the most sensitive to the artificial aging scenarios. Nevertheless, substantial flame retardance persisted after being subjected for 2000 h, which indicates that the equivalent influence of natural exposure is limited for several years, but less so for long-term use.
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.
In the processing of nanocomposites, high shear stresses at elevated tempera-tures orient two-dimensional nanoparticles like graphene. This orientationleads to anisotropic mechanical, thermal or barrier properties of the nanocom-posite. This anisotropy is addressed in this study by comparing graphene (few-layer graphene, FLG) with a nanoscaled carbon black (nCB) at a filler contentof 3 phr, by varying the vulcanization, and by comparing different FLG con-tents. Transmission electron microscopy gives insight into the qualitative ori-entation in the nanocomposite with FLG or nCB. The storage moduli paralleland normal to the orientation reveal the direction dependency of reinforce-ment through dynamic mechanical analysis (DMA). Dimensional swellingmeasurements show a restriction of the expansion parallel to the FLG orienta-tion, and an increased expansion normal to the orientation. The vulcanizationsystem and crosslinking determine the respective level of property values, andhigher crosslinking densities increase the anisotropy in DMA resulting invalues of up to 2.9 for the quantified anisotropy factor. With increasing FLGcontent, the anisotropy increases. A comparison of the results reveals swellingmeasurements as the most suitable method for the determination of anisot-ropy. Compared to recent literature, the presented processing induces higheranisotropy, leading to higher reinforcing effects in the direction of orientation
The addition of nanoparticles as reinforcing fillers in elastomers yields nanocomposites with unique property profiles, which opens the door for various new application fields. Major factors influencing the performance of nanocomposites are studied by varying the type and shape of nanoparticles and their dispersion in the natural rubber matrix. The industrial applicability of these nanocomposites is put into focus using two types of graphene and a nanoscale carbon black, all commercially available, and scalable processing techniques in the form of a highly filled masterbatch production via latex premixing by simple stirring or ultrasonically assisted dispersing with surfactant followed by conventional two-roll milling and hot pressing. Different processing and measurement methods reveal the potential for possible improvements: rheology, curing behavior, static and dynamic mechanical properties, swelling, and fire behavior. The aspect ratio of the nanoparticles and their interaction with the surrounding matrix prove to be crucial for the development of superior nanocomposites. An enhanced dispersing method enables the utilization of the improvement potential at low filler loadings (3 parts per hundred of rubber [phr]) and yields multifunctional rubber nanocomposites: two-dimensional layered particles (graphene) result in anisotropic material behavior with strong reinforcement in the in-plane direction (157% increase in the Young's modulus). The peak heat release rate in the cone calorimeter is reduced by 55% by incorporating 3 phr of few-layer graphene via an optimized dispersing process.
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.
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.