Anisotropic swelling of elastomers filled with aligned 2D materials

A comprehensive study has been undertaken on the dimensional swelling of graphene-reinforced elastomers in liquids. Anisotropic swelling was observed for samples reinforced with graphene nanoplatelets (GNPs), induced by the in-plane orientation of the GNPs. Upon the addition of the GNPs, the diameter swelling ratio of the nanocomposites was significantly reduced, whereas the thickness swelling ratio increased and was even greater than that of the unfilled elastomers. The swelling phenomenon has been analyzed in terms of a modification of the Flory-Rhener theory. The newly-derived equations proposed herein, can accurately predict the dependence of dimensional swelling (diameter and thickness) on volume swelling, independent of the type of elastomer and solvent. The anisotropic swelling of the samples was also studied in combination with the evaluation of the tensile properties of the filled elastomers. A novel theory that enables the assessment of volume swelling for GNP-reinforced elastomers, based on the filler geometry and volume fraction has been developed. It was found that the swelling of rubber nanocomposites induces a biaxial constraint from the graphene flakes

A New Era in Engineering Plastics: Compatibility and Perspectives of Sustainable Alipharomatic Poly(ethylene terephthalate)/Poly(ethylene 2,5-furandicarboxylate) Blends

The industrialisation of poly(ethylene 2,5-furandicarboxylate) for total replacement of poly(ethylene terephthalate) in the polyester market is under question. Preparation of high-performing polymer blends is a well-established strategy for tuning the properties of certain homopolymers and create tailor-made materials to meet the demands for a number of applications. In this work, the structure, thermal properties and the miscibility of a series of poly(ethylene terephthalate)/poly(ethylene 2,5-furandicarboxylate) (PET/PEF) blends have been studied. A number of thermal treatments were followed in order to examine the thermal transitions, their dynamic state and the miscibility characteristics for each blend composition. Based on their glass transition temperatures and melting behaviour the PET/PEF blends are miscible at high and low poly(ethylene terephthalate) (PET) contents, while partial miscibility was observed at intermediate compositions. The multiple melting was studied and their melting point depression was analysed with the Flory-Huggins theory. In an attempt to further improve miscibility, reactive blending was also investigated

The mechanics of reinforcement of polymers by graphene nanoplatelets

A detailed study has been undertaken of the mechanisms of stress transfer in polymeric matrices with different values of Young's modulus, Em, reinforced by graphene nanoplatelets (GNPs). For each material, the Young's modulus of the graphene filler, Ef, has been determined using the rule of mixtures and it is found to scale with the value of Em. Additionally stress-induced Raman bands shifts for the different polymer matrices show different levels of stress transfer from the polymer matrix to the GNPs, which again scale with Em. A theory has been developed to predict the stiffness of the bulk nanocomposites from the mechanics of stress transfer from the matrix to the GNP reinforcement based upon the shear-lag deformation of individual graphene nanoplatelets. Overall it is found that it is only possible to realise the theoretical Young's modulus of graphene of 1.05 TPa for discontinuous nanoplatelets as Em approaches 1 TPa; the effective modulus of the reinforcement will always be less for lower values of Em. For flexible polymeric matrices the level of reinforcement is independent of the graphene Young's modulus and, in general, the best reinforcement will be obtained in nanocomposites with strong graphene-polymer interfaces and aligned nanoplatelets with high aspect ratios

Graphene-Polyurethane Coatings for Deformable Conductors and Electromagnetic Interference Shielding

Electrically conductive, polymeric materials that maintain their conductivity even when under significant mechanical deformation are needed for actuator electrodes, conformable electromagnetic shielding, stretchable tactile sensors, and flexible energy storage. The challenge for these materials is that the percolated, electrically conductive networks tend to separate even at low strains, leading to significant piezoresistance. Herein, deformable conductors are fabricated by spray‐coating a nitrile substrate with a graphene–elastomer solution. The electrical resistance of the coatings shows a decrease after thousands of bending cycles and a slight increase after repeated folding‐unfolding events. The deformable conductors double their electrical resistance at 12% strain and are washable without changing their electrical properties. The conductivity–strain behavior is modeled by considering the nanofiller separation upon deformation. To boost the conductivity at higher strains, the production process is adapted by stretching the nitrile substrate before spraying, after which it is released. This adaption meant that the electrical resistance doubles at 25% strain. The electrical resistance is found sufficiently low to give a 1.9 dB µm−1 shielding in the 8–12 GHz electromagnetic band. The physical and electrical properties, including the electro magnetic screening, of the flexible conductors, are found to deteriorate upon cycling but can be recovered through reheating the coating

Highly stretchable and sensitive self-powered sensors based on the N-Type thermoelectric effect of polyurethane/Na_{x}(Ni-ett)_{n}/graphene oxide composites

The development of stretchable organic thermoelectric materials is prompted by fast evolving application fields like flexible electronic devices, soft robotics, health monitoring and internet-of-things. Stretchability in thermoelectric materials is usually obtained by using an insulating elastomer, either as a substrate or as a matrix in a blend or composite, which, unfortunately, leads to a compromise in thermoelectric performance. Herein, a potential solution is reported exploiting the addition of graphene oxide as a secondary (nano)filler in a polyurethane/poly nickel-ethenetetrathiolates film. Compared with traditional binary blends, our ternary composite shows an increased electrical conductivity (4 times), air-stability (∼20 times after 3 months), and stretchability (38% increase in strain at break). With a gauge factor (GF) of ∼58, this new composite film shows high sensitivity to tensile strain. Thanks to its Seebeck coefficient of ∼ −40 μV K^{−1}, the composite film can generate a thermopower of ∼0.25 pW when subjected to a small temperature difference (30 °C), which could be exploited by self-powered strain sensors. Therefore, the ternary polyurethane/poly nickel-ethenetetrathiolates/graphene oxide composite film can work as a stretchable strain sensor, providing a strategy to reconcile the compromise between thermoelectric performance and stretchability

Synthesis and Characterization of In-Situ-Prepared Nanocomposites Based on Poly(Propylene 2,5-Furan Dicarboxylate) and Aluminosilicate Clays

Poly(propylene 2,5-furan dicarboxylate) (PPF), or poly(trimethylene 2,5-furan dicarboxylate) (PTF), is a biobased alipharomatic polyester that is expected to replace its fossil-based terephthalate (PPT) and naphthate (PPN) homologues. PPF possesses exceptional gas barrier properties, but its slow crystallization rate might affect its success in specific applications in the future. Therefore, a series of PPF based nanocomposites with the nanoclays Cloisite®-Na (MMT), Cloisite®-20A (MMT 20A), and halloysite nanotubes (HNT) were synthesized via the in situ transterification and polycondensation method. The effect of the nanoclays on the structure, thermal, and crystallization properties of PPF was studied with several methods including infrared spectroscopy (IR), Nuclear Resonance Spectroscopy (1H-NMR), Wide Angle X-ray Diffraction (WAXD), Thermogravimetric Analysis (TGA), and Differential Scanning Calorimetry (DSC). The insertion of the nanofillers in the polymer matrix altered the crystallization rates, and TGA results showed good thermal stability, since no significant mass loss occurred up to 300 °C. Finally, the degradation mechanism was studied in depth with Pyrolysis-Gas Chromatography/Mass Spectroscopy, and it was found that β-scission is the dominant degradation mechanism

Thermal Decomposition Kinetics and Mechanism of In-Situ Prepared Bio-Based Poly(propylene 2,5-furan dicarboxylate)/Graphene Nanocomposites

Bio-based polyesters are a new class of materials that are expected to replace their fossil-based homologues in the near future. In this work, poly(propylene 2,5-furandicarboxylate) (PPF) nanocomposites with graphene nanoplatelets were prepared via the in-situ melt polycondensation method. The chemical structure of the resulting polymers was confirmed by 1H-NMR spectroscopy. Thermal stability, decomposition kinetics and the decomposition mechanism of the PPF nanocomposites were studied in detail. According to thermogravimetric analysis results, graphene nanoplatelets did nοt affect the thermal stability of PPF at levels of 0.5, 1.0 and 2.5 wt.%, but caused a slight increase in the activation energy values. Pyrolysis combined with gas chromatography and mass spectroscopy revealed that the decomposition mechanism of the polymer was not altered by the presence of graphene nanoplatelets but the extent of secondary homolytic degradation reactions was increased

High-performance fluoroelastomer-graphene nanocomposites for advanced sealing applications

High-performance sealing materials that can guard key components against high pressure gases and liquid chemicals while withstanding mechanical deformation are of utmost importance in a number of industries. In this present work, graphene nanoplatelets (GNPs) were introduced into a fluoroelastomer (FKM) matrix to improve its mechanical and barrier properties and test its suitability for sealing applications. Nanocomposites filled with different loadings of GNPs were prepared and compared with their counterparts loaded with carbon black (CB). GNPs were dispersed homogeneously with a high degree of in-plane alignment. The tensile and barrier properties of the FKM were improved significantly by the addition of GNPs. Micromechanical modelling based on the shear-lag/rule-of-mixtures theory was used to analyse the reinforcing efficiency of the GNPs. Upon the addition of the GNPs, the elastomer was able to swell anisotropically in liquids, a fact that can be used to tune the swelling properties for sealing applications. In terms of gas permeability, a modification of the well-established Nielsen's theory was introduced to analyse the CO2 permeability for the bulk composite samples. The significantly improved mechanical, thermal and barrier properties at relatively low filler loadings, reveal that the FKM/GNP nanocomposites produced are very promising for use in advanced sealing applications