Search Results (12)

This study introduces an efficient and scalable method for the top-down exfoliation of graphite into graphite nanoplatelets (GNPs) using polyketones (PKs) functionalized with Diels–Alder (DA) active groups. Leveraging the reversible covalent interactions facilitated by furan and thiophene moieties in PK, combined with melt-mixing and shear force, this process achieves significant exfoliation while preserving the structural integrity of the resulting material. Thermal and rheological analyses demonstrate enhanced interfacial adhesion and stability within polymer composites attributed to the DA-driven interactions between functionalized PK and graphite. Comparative evaluations demonstrate that furan-functionalized PK exhibits superior exfoliation efficiency, highlighting its potential for producing high-quality exfoliated graphite suitable for advanced nanocomposite applications that require enhanced thermal, mechanical, and electrical properties. This method seamlessly integrates sustainability with industrial scalability, offering significant advancements in developing GNP-based materials. Full article

Furanoate polyesters are an extremely promising new class of materials for packaging applications, particularly furanoate-based nanocomposites, which have gained a high interest level in research and development in both academia and industries. The monomers utilised for the synthesis of furanoate-based polyesters were derived from lignocellulosic biomass, which is essential for both eco-friendliness and sustainability. Also, these polyesters have a lower carbon footprint compared to fossil-based plastics, contributing to greenhouse gas reduction. The furanoate-based nanocomposites exhibit enhanced performance characteristics, such as high thermal stability, excellent mechanical strength, superior barrier resistance, and good bacteriostatic rate, making them suitable for a wide range of industrial applications, especially for food-packaging applications. This paper reviews the recent trends in the synthesis routes of monomers, such as the various catalytic activities involved in the oxidation of 5(hydroxymethyl)furfural (HMF) into 2,5-furandicarboxylic acid (FDCA) and its ester, dimethyl furan-2,5-dicarboxylate (DMFD). In addition, this review explores the fabrication of different furanoate-based nanocomposites prepared by in situ polymerization, by melt mixing or solvent evaporation methods, and by using different types of nanoparticles to enhance the overall material properties of the resulting nanocomposites. Emphasis was given to presenting the effect of these nanoparticles on the furanoate polyester’s properties. Full article

The nanocomposites with reversible cross-linking covalent bonds were prepared by reacting furfurylamine (FA)-modified diglycidyl ether of bisphenol A (DGEBA) and furfuryl-functionalized aniline trimer-modified graphene (TFAT-G) with bismaleimide (BMI) via the Diels-Alder (DA) reaction. The successful synthesis of the TFAT modifier is confirmed by nuclear magnetic resonance (NMR) hydrogen spectroscopy and IR spectroscopy tests. The structure and properties of TFAT-G epoxy nanocomposites are characterized by scanning electron microscopy (SEM), differential scanning calorimeter (DSC), tensile, and resistivity. The results show that TFAT-G was uniformly dispersed in the resin, and 1 wt% TFAT-G composites increased to 233% for tensile strength, 63% for elongation at break, 66% for modulus, and 7.8 °C for Tg. In addition, the addition of unmodified graphene degrades the mechanical properties of the composite. Overall, the graphene/self-healing resin nanocomposites have both good self-healing function and electrical conductivity by adding 1 wt% modified graphene; this allows for the maintenance of the original 83% strength and 89% electrical conductivity after one cycle of heating repair. Full article

Microwave-absorbing materials have attracted extensive attention due to the development of electronic countermeasures. In this study, novel nanocomposites with core–shell structures based on the core of Fe-Co nanocrystals and the shell of furan methylamine (FMA)-modified anthracite coal (Coal-F) were designed and fabricated. The Diels-Alder (D-A) reaction of Coal-F with FMA creates a large amount of aromatic lamellar structure. After the high-temperature treatment, the modified anthracite with a high degree of graphitization showed an excellent dielectric loss, and the addition of Fe and Co effectively enhanced the magnetic loss of the obtained nanocomposites. In addition, the obtained micro-morphologies proved the core–shell structure, which plays a significant role in strengthening the interface polarization. As a result, the combined effect of the multiple loss mechanism promoted a remarkable improvement in the absorption of incident electromagnetic waves. The carbonization temperatures were specifically studied through a setting control experiment, and 1200 °C was proved to be the optimum parameter to obtain the best dielectric loss and magnetic loss of the sample. The detecting results show that the 10 wt.% CFC-1200/paraffin wax sample with a thickness of 5 mm achieves a minimum reflection loss of −41.6 dB at a frequency of 6.25 GHz, indicating an excellent microwave absorption performance. Full article

In situ intercalative polymerization has been investigated as a strategic way to obtain poly(propylene 2,5-furandicarboxylate) (PPF) and poly(hexamethylene 2,5-furandicarboxylate) (PHF) nanocomposites with different graphene types and amounts. Graphene (G) has been dispersed in surfactant stabilized water suspensions. The loading range in composites was 0.25–0.75 wt %. For the highest composition, a different type of graphene (XT500) dispersed in 1,3 propanediol, containing a 6% of oxidized graphene and without surfactant has been also tested. The results showed that the amorphous PPF is able to crystallize during heating scan in DSC and graphene seems to affect such capability: G hinders the polymer chains in reaching an ordered state, showing even more depressed cold crystallization and melting. On the contrary, such hindering effect is absent with XT500, which rather induces the opposite. Concerning the thermal stability, no improvement has been induced by graphene, even if the onset degradation temperatures remain high for all the materials. A moderate enhancement in mechanical properties is observed in PPF composite with XT500, and especially in PHF composite, where a significative increase of 10–20% in storage modulus E’ is maintained in almost all the temperature range. Such an increase is also reflected in a slightly higher heat distortion temperature. These preliminary results can be useful in order to further address the field of application of furan-based polyesters; in particular, they could be promising as packaging materials. Full article

The present work investigates the microstructural, thermo-mechanical, and electrical properties of a promising, but still not thoroughly studied, biobased polymer, i.e., poly(decylene furanoate) (PDeF), and its performance when multi-walled carbon nanotubes (CNTs) are added. After sample preparation by solution mixing and film casting, the microstructural investigation evidences that the fracture surface becomes smoother and more homogeneous with a small fraction of CNTs, and that the production process is suitable to achieve good disentanglement and dispersion of CNTs within the matrix, although some aggregates are still observable. CNTs act as nucleating agents for PDeF crystals, as evidenced by differential scanning calorimetry, as the crystallinity degree increases from 43.2% of neat PDeF to 55.0% with a CNT content of 2 phr, while the crystallization temperature increases from 68.4 °C of PDeF to 91.7 °C of PDeF-CNT-2. A similar trend in crystallinity is confirmed by X-ray diffraction, after detailed Rietveld analysis with a three-phase model. CNTs also remarkably improve the mechanical performance of the bioderived polymer, as the elastic modulus increases up to 123% and the stress at break up to 131%. The strain at break also increases by +71% when a small amount of 0.25 phr of CNTs are added, which is probably the consequence of a more homogeneous microstructure. The long-term mechanical performance is also improved upon CNT addition, as the creep compliance decreases considerably, which was observed for both the elastic and the viscoelastic component. Finally, the films become electrically dissipative for a CNT content of 1 phr and conductive for a CNT amount of 2 phr. This study contributes to highlight the properties of bioderived furan-based polymer PDeF and evidences the potential of CNTs as a promising nanofiller for this matrix. Full article

Poly(hexylene 2,5 furan-dicarboxylate) (PHF) is a relatively new biobased polyester prepared from renewable resources, which is targeted for use in food packaging applications, owing to its great mechanical and gas barrier performance. Since both properties are strongly connected to crystallinity, the latter is enhanced here by the in situ introduction in PHF of graphene nanoplatelets and fumed silica nanoparticles, as well as mixtures of both, at low amounts. For this investigation, we employed Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), X-ray diffraction (XRD) and dielectric spectroscopy (BDS). The fillers were found to improve crystallization in both the rate (increasing T_c) and fraction (CF), which was rationalized via the concept of fillers acting as crystallization agents. This action was found stronger in the case of graphene as compared to silica. BDS allowed the detection of local and segmental dynamics, in particular in PHF for the first time. The glass transition dynamics in both BDS (α relaxation) and DSC (T_g) are mainly dominated by the relatively high CF, whereas in the PHF filled uniquely with silica strong spatial confinement effects due to crystals were revealed. Finally, all samples demonstrated the segmental-like dynamics above T_g, which screens the global chain dynamics (normal mode). Full article

In this paper, a self-healable nanocomposite based on the Diels-Alder reaction is developed. A graphene-based nanofiller is introduced to improve the self-healing efficiency, as well as the mechanical properties of the nanocomposite. Graphene oxide (GO) is modified with maleimide functional groups, and the maleimide-modified GO (mGO) enhanced the compatibility of the polymer matrix and nanofiller. The tensile strength of the nanocomposite containing 0.030 wt% mGO is improved by 172%, compared to that of a polymer film incorporating both furan-functionalized polymer and bismaleimide without any nanofiller. Moreover, maleimide groups of the surface on mGO participate in the Diels-Alder reaction, which improves the self-healing efficiency. The mechanical and self-healing properties are significantly improved by using a small amount of mGO. Full article

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. Full article

This study examines the preparation of electrically conductive polymer networks based on furan-functionalised polyketone (PK-Fu) doped with multi-walled carbon nanotubes (MWCNTs) and reversibly crosslinked with bis-maleimide (B-Ma) via Diels-Alder (DA) cycloaddition. Notably, the incorporation of 5 wt.% of MWCNTs results in an increased modulus of the material, and makes it thermally and electrically conductive. Analysis by X-ray photoelectron spectroscopy indicates that MWCNTs, due to their diene/dienophile character, covalently interact with the matrix via DA reaction, leading to effective interfacial adhesion between the components. Raman spectroscopy points to a more effective graphitic ordering of MWCNTs after reaction with PK-Fu and B-Ma. After crosslinking the obtained composite via the DA reaction, the softening point (tan(δ) in dynamic mechanical analysis measurements) increases up to 155 °C, as compared to the value of 130 °C for the PK-Fu crosslinked with B-Ma and that of 140 °C for the PK-Fu/B-Ma/MWCNT nanocomposite before resistive heating (responsible for crosslinking). After grinding the composite, compression moulding (150 °C/40 bar) activates the retro-DA process that disrupts the network, allowing it to be reshaped as a thermoplastic. A subsequent process of annealing via resistive heating demonstrates the possibility of reconnecting the decoupled DA linkages, thus providing the PK networks with the same thermal, mechanical, and electrical properties as the crosslinked pristine systems. Full article

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. Full article

Conductive rubber nanocomposites were prepared by dispersing conductive nanotubes (CNT) in thermoreversibly cross-linked ethylene propylene rubbers grafted with furan groups (EPM-g-furan) rubbers. Their features were studied with a strong focus on conductive and mechanical properties relevant for strain-sensor applications. The Diels-Alder chemistry used for thermoreversible cross-linking allows for the preparation of fully recyclable, homogeneous, and conductive nanocomposites. CNT modified with compatible furan groups provided nanocomposites with a relatively large tensile strength and small elongation at break. High and low sensitivity deformation experiments of nanocomposites with 5 wt % CNT (at the percolation threshold) displayed an initially linear sensitivity to deformation. Notably, only fresh samples displayed a linear response of their electrical resistivity to deformations as the resistance variation collapsed already after one cycle of elongation. Notwithstanding this mediocre performance as a strain sensor, the advantages of using thermoreversible chemistry in a conductive rubber nanocomposite were highlighted by demonstrating crack-healing by welding due to the joule effect on the surface and the bulk of the material. This will open up new technological opportunities for the design of novel strain-sensors based on recyclable rubbers. Full article