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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.
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
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.
To curtail flammability risks and improve material properties, flame retardants (FRs) and fillers are mixed into rubbers. High loadings of aluminum trihydroxide (ATH) and carbon black (CB) are the most used FRs and reinforcing additive, respectively, in rubbers. To reduce loading without losing mechanical properties, partial substitution of ATH as well as CB by low amounts of multilayer graphene (MLG) nanoparticles is investigated. The high aspect ratio MLG is made of ten graphene sheets. In polybutadiene/chloroprene (BR/CR) nanocomposites 3 phr MLG replaced 15 phr CB and/or 3 phr ATH. Material and mechanical properties as well as fire behavior of the nanocomposites are compared to BR/CR with 20 phr CB both with and without 50 phr ATH. MLG appears as a promising nanofiller to improve the functional properties: replacement of CB improved rheological, curing, and mechanical properties; substitution of ATH improved nanocomposite properties without affecting flame retardancy.
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.
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.
Multilayer graphene/chlorine-isobutene-isoprene rubber nanocomposites: the effect of dispersion
(2016)
Multilayer graphene (MLG) is composed of approximately 10 sheets of graphene. It is a promising nanofiller just starting to become commercially available. The Dispersion of the nanofiller is essential to exploit the properties of the nanocomposites and is dependent on the preparation method. In this study, direct incorporation of 3 parts per hundred of rubber (phr) MLG into chlorine-isobutene- isoprene rubber (CIIR) on a two-roll mill did not result in substantial enhancement of the material properties. In contrast, by pre-mixing the MLG (3 phr) with CIIR using an ultrasonically assisted solution mixing procedure followed by two-roll milling, the properties (rheological, curing, and mechanical) were improved substantially compared with the MLG/CIIR nanocomposites mixed only on the mill. The Young’s moduli of the nanocomposites mixed in solution increased by 38%. The CIIR/MLG nanocomposites produced via solution showed superior durability against weathering exposure.
Multilayer Graphene (MLG), a nanoparticle with a specific surface of BET = 250 m²/g and thus made of only approximately 10 graphene sheets, is proposed as a nanofiller for rubbers. When homogenously dispersed, it works at low loadings enabling the replacement of carbon black (CB), increase in efficiency, or reduction in filler concentration. Actually the appropriate preparation yielded nanocomposites in which just 3 phr are sufficient to significantly improve the rheological, curing and 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). A mere 3 phr of MLG tripled the Young’s modulus of CIIR, an effect equivalent to 20 phr of carbon black. Similar equivalents are observed for MLG/CB mixtures. MLG reduces gas permeability, increases thermal and electrical conductivities, and retards fire behavior. The later shown by the reduction in heat release rate in the cone calorimeter. The higher the nanofiller concentration is (3 phr, 5 phr, and 10 phr was investigated), the greater the improvement in the properties of the nanocomposites. Moreover, the MLG nanocomposites improve stability of mechanical properties against weathering. An increase in UV-absorption as well as a pronounced radical scavenging are proposed and were proved experimentally. To sum up, MLG is interesting as a multifunctional nanofiller and seems to be quite ready for rubber development.