Design and Study of Novel Composites Based on EPDM Rubber Containing Bismuth (III) Oxide and Graphene Nanoplatelets for Gamma Radiation Shielding.

The mechanical, thermal and gamma radiation attenuation properties of ethylene-propylene-diene monomer (EPDM)-based composites containing graphene nanoplatelets (GNs) and bismuth (III) oxide nanoparticles (B) were investigated. The use of polyethylene glycol (PEG) as a compatibilizer to improve the dispersion of the fillers was also investigated. The results showed that the combined use of these fillers resulted in a drastic increase in mechanical properties, reaching 123% and 83% of tensile strength and elongation at break, respectively, compared to those of EPDM. In contrast, the addition of PEG to composites containing EPDM GNs and B resulted in composites with lower values of mechanical properties compared to the EPDM/B/GN-based composite. However, the presence of PEG leads to obtaining a composite (EPDM/B/GNP) with a mass attenuation coefficient to gamma radiation (137Cs, 662 keV) superior to that composite without PEG. In addition, the composite EPDM, B and PEG exhibited an elongation at break 153% superior to unfilled EPDM. Moreover, the binary filler system consisting of 100 phr of bismuth (III) oxide and 10 phr of GN leads to reaching 61% of the linear damping coefficient of the EPDM composite compared to that value of the unfilled EPDM. The study of the morphology and the state of filler dispersion in the polymer matrix, obtained using scanning electron microscopy and energy-dispersive X-ray spectroscopy, respectively, provides a useful background for understanding the factors affecting the gamma radiation attenuation properties. Finally, the results also indicated that by adjusting the formulation, it is possible to tune the mechanical and thermal properties of EPDM composites reinforced with bismuth oxide and graphene nanoplatelets.

Poly(methyl methacrylate) as Healing Agent for Carbon Fibre Reinforced Epoxy Composites.

Self-healing materials offer a potential solution to the problem of damage to fibre-reinforced plastics (FRPs) by allowing for the in-service repair of composite materials at a lower cost, in less time, and with improved mechanical properties compared to traditional repair methods. This study investigates for the first time the use of poly(methyl methacrylate) (PMMA) as a self-healing agent in FRPs and evaluates its effectiveness both when blended with the matrix and when applied as a coating to carbon fibres. The self-healing properties of the material are evaluated using double cantilever beam (DCB) tests for up to three healing cycles. The blending strategy does not impart a healing capacity to the FRP due to its discrete and confined morphology; meanwhile, coating the fibres with the PMMA results in healing efficiencies of up to 53% in terms of fracture toughness recovery. This efficiency remains constant, with a slight decrease over three subsequent healing cycles. It has been demonstrated that spray coating is a simple and scalable method of incorporating a thermoplastic agent into an FRP. This study also compares the healing efficiency of specimens with and without a transesterification catalyst and finds that the catalyst does not increase the healing efficiency, but it does improve the interlaminar properties of the material.

Development of Sustainable, Mechanically Strong, and Self-Healing Bio-Thermoplastic Elastomers Reinforced with Alginates.

New bio-thermoplastic elastomer composites with self-healing capacities based on epoxidized natural rubber and polycaprolactone blends reinforced with alginates were developed. This group of salts act as natural reinforcing fillers, increasing the tensile strength of the unfilled rubber from 5.6 MPa to 11.5 MPa without affecting the elongation at break (~1000% strain). In addition, the presence of ionic interactions and hydrogen bonds between the components provides the material with a thermally assisted self-healing capacity, as it is able to restore its catastrophic damages and recover diverse mechanical properties up to ~100%. With the results of this research, an important and definitive step is planned toward the circularity of elastomeric materials.

Understanding the Molecular Dynamics of Dual Crosslinked Networks by Dielectric Spectroscopy.

The combination of vulcanizing agents is an adequate strategy to develop multiple networks that consolidate the best of different systems. In this research, sulfur (S), and zinc oxide ( ZnO) were combined as vulcanizing agents in a matrix of carboxylated nitrile rubber (XNBR). The resulting dual network improved the abrasion resistance of up to ~15% compared to a pure ionically crosslinked network, and up to ~115% compared to a pure sulfur-based covalent network. Additionally, the already good chemical resistance of XNBR in non-polar fluids, such as toluene and gasoline, was further improved with a reduction of up to ~26% of the solvent uptake. A comprehensive study of the molecular dynamics was performed by means of broadband dielectric spectroscopy (BDS) to complete the existing knowledge on dual networks in XNBR. Such analysis showed that the synergistic behavior that prevails over purely ionic vulcanization networks is related to the restricted motions of rubber chain segments, as well as of the trapped chains within the ionic clusters that converts the vulcanizate into a stiffer and less solvent-penetrable material, improving abrasion resistance and chemical resistance, respectively. This combined network strategy will enable the production of elastomeric materials with improved performance and properties on demand.

Sustainable mobility: The route of tires through the circular economy model.

Until nowadays, the concept of the 3Rs (Reduce, Reuse, Recycle) has tried to develop responsible consumption habits. Nonetheless, the rise of ecological thinking has generated the appearance of four new Rs in addition to these basic 3Rs; the currently 7Rs (Reduce, Reuse, Recycle, Redesign, Renew, Repair and Recover) which refer to the actions necessary to achieve the change towards a circular economy (CE) model. This model aims at extending the lifetime of the resources through their rational and efficient use to generate value repeatedly, reducing costs and waste. In this review, we examine the route followed by tires from the CE perspective, analyzing end-of-life strategies that aim to improve the circular flow of tire rubber materials. We discuss the most relevant studies on the "7Rs" concepts applied to tires, comparing different scientific approaches, as well as their industrial and commercial implementation. We also illustrate the drawbacks and feasibility of each of the R-hierarchy strategies. From the early stages of production to the post-consumption step, the path that tires trail within this CE model evidences the commitment and efforts towards the development of effective management schemes for achieving a real sustainable mobility.

Setting Relationships between Structure and Devulcanization of Ground Tire Rubber and Their Effect on Self-Healing Elastomers.

The use of devulcanized tire powder as an effective reinforcement in self-healing styrene-butadiene rubber (SBR) compounds has been investigated for the first time in this work. For this purpose, the evolution of the microstructure of the rubber from end-of-life tires (ELTs) was studied during granulation, grinding and devulcanization through an exhaustive characterization work in order to relate the final microstructure with the mechanical response of the repaired systems. Different morphologies (particle size distribution and specific surface area) obtained by cryogenic and water jet grinding processes, as well as different devulcanization techniques (thermo-mechanical, microwave, and thermo-chemical), were analyzed. The results demonstrated the key influence of the morphology of the ground tire rubber (GTR) on the obtained devulcanized products (dGTR). The predictions of the Horikx curves regarding the selectivity of the applied devulcanization processes were validated, thereby; a model of the microstructure of these materials was defined. This model made it possible to relate the morphology of GTR and dGTR with their activity as reinforcement in self-healing formulations. In this sense, higher specific surface area and percentage of free surface polymeric chains resulted in better mechanical performance and more effective healing. Such a strategy enabled an overall healing efficiency of more than 80% in terms of a real mechanical recovery (tensile strength and elongation at break), when adding 30 phr of dGTR. These results open a great opportunity to find the desired balance between the mechanical properties before and after self-repair, thus providing a high technological valorization to waste tires.

Electrical Properties of Poly(Monomethyl Itaconate)/Few-Layer Functionalized Graphene Oxide/Lithium Ion Nanocomposites.

Poly(monomethyl itaconate) is outstanding because it is a glassy and dielectric polymer obtained from sustainable feedstock. Consequently, the study of the properties of its nanocomposites has gained importance. Herein, the electrical properties of nanocomposites based on poly(monomethyl itaconate) and functionalized few-layer graphene oxide (FGO) in the presence and absence of lithium ions (Li+) are studied. Not only did the electrical conductivities of the nanocomposites present values as high as 10-5 Scm-1, but also the dielectric permittivity of nanocomposites with (FGO) content lower than the percolation threshold was twice that of the pristine polymer, without presenting a drastic increase of the loss tangent. By contrast, nanocomposites containing Li+ ions presented significant increases of the permittivity with concomitant increases of the loss tangent. Moreover, it was determined that the presence of Li+ ions influenced the charge transport in the composites because of its ionic nature.

Design of Rubber Composites with Autonomous Self-Healing Capability.

The development of self-healing rubbers is currently under investigation as a strategy to promote their reuse and, hence, reduce their waste. However, autonomous, multicycle self-healing rubbers with good mechanical properties have so far proven difficult to achieve. Here, mechanically robust composites based on epoxidized natural rubber (ENR) and thermally reduced graphene oxide (TRGO) were successfully designed and prepared with a high healing efficiency of up to 85% at room temperature without applying external stimuli. The incorporation of TRGO not only improves the mechanical performance in more than 100% in relation to pristine ENR but also promotes the hydrogen bonding interactions with the rubber. This leads to a homogenous dispersion of TRGO within the ENR matrix, which further increases its self-healing capability.

Giving a Second Opportunity to Tire Waste: An Alternative Path for the Development of Sustainable Self-Healing Styrene-Butadiene Rubber Compounds Overcoming the Magic Triangle of Tires.

Current regulations demand tires with long lifetime and reduced fuel consumption without sacrificing car safety. However, tire technology still needs to reach a suitable balance between these three indicators. Here, we address them by developing a self-healing tire compound using styrene-butadiene rubber (SBR) as the matrix and reclaimed tire waste as the sustainable filler. The addition of ground tire rubber (GTR) to the matrix simultaneously improved the rolling resistance and maintained both wet grip and healing ability. We provide an in-depth analysis of the healing behavior of the material at a scale close to the relevant molecular processes through a systematic dynamic-mechanical and dielectric analysis. We found that SBR and SBR/GTR compounds show a complete recovery of stiffness and relaxation dynamics after being damaged by cyclic deformation, resulting in a heterogeneous repaired rubber network. This new development could well overcome the so-called magic triangle of tires, which is certainly one of the key objectives of the tire industry.

Understanding the Effect of the Dianhydride Structure on the Properties of Semiaromatic Polyimides Containing a Biobased Fatty Diamine.

In this work we report the effect of the hard block dianhydride structure on the overall properties of partially biobased semiaromatic polyimides. For the study, four polyimides were synthesized using aliphatic fatty dimer diamine (DD1) as the soft block and four different commercially available aromatic dianhydrides as the hard block: 4,4'-(4,4'-isopropylidenediphenoxy) bis(phthalic anhydride) (BPADA), 4,4'-oxidiphthalic anhydride (ODPA), 4,4'-(Hexafluoroisopropylidene) diphthalic anhydride (6FDA), and 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA). The polymers synthesized were fully organo-soluble thermoplastic branched polyimides with glass transition temperatures close to room temperature. The detailed analysis took into account several aspects of the dianhydrides structure (planarity, rigidity, bridging group between the phtalimides, and electronic properties) and related them to the results obtained by differential scanning calorimetry, rheology, fluorescence and broadband dielectric spectroscopy. Moreover, the effects of physical parameters (crystallization and electronic interactions) on the relaxation behavior are discussed. Despite the presence of the bulky branched soft block given by the dimer diamine, all polyimides showed intermolecular charge transfer complexes, whose extent depends on the electronic properties of the dianhydride hard block. Furthermore, the results showed that polyimides containing flexible and bulky hard blocks turned out fully amorphous while the more rigid dianhydride (BPDA) led to a nanophase separated morphology with low degree of crystallinity resulting in constrained segmental relaxation with high effect on its mechanical response with the annealing time. This work represents the first detailed report on the development and characterization of polyimides based on a biobased fatty dimer diamine. The results highlight the potential of polymer property design by controlled engineering of the aromatic dianhydride blocks.