The aggregation of carbon nanofillers within polymer matrices is a crucial phenomenon for the formation of conducting channels in electrically conductive composites. Herein, a systematic comparison of the effect of 1D and 2D carbon nanofillers, exploiting their dimension‐dependent aggregation in matrices, is performed. The role of flexible matrix in fractal formation is also highlighted by demonstrating that the presence of polar moieties in a polymer matrix affects the agglomeration geometries of functional carbon nanomaterials. Carboxylic acid derivatives of nanotubes and hydroxylated graphene are incorporated into both “functionally rich” polyurethane and apolar polydimethylsiloxane matrices to explore filler–filler and matrix–filler interactions. The in situ ultra‐small‐angle X‐ray scattering analysis performed with simultaneous conductivity measurements, and stretching of flexible film has established a distinct role for loading fraction of functional nanofillers in deciding the stability of conduction networks. The effect of topological differences in composites is observed to be most striking in the case of sheets, where it is shown that the 2D flakes can bend and unfold upon stress, exclusively affecting the percolation and conductive mechanism in composites. These findings help to select the suitable materials to design the next generation of flexible and wearable electronic devices, offering versatility and adaptability in applications.

Incorporation of carbon allotropes of different dimensions within elastomeric matrices has been established as an effective strategy to fabricate functional conductive polymer nanocomposites (PNCs). In this work, higher-dimensional 3D hybrid carbon nanofillers, comprising synergistically integrated multiwalled carbon nanotubes immobilized onto few-layer graphene, were incorporated into the thermoplastic polyurethane (TPU) matrix to demonstrate their effectiveness as strain sensors. The conductive films were fabricated through a simple solution casting technique, in which the mechanical, electrical, and strain-sensing characteristics were studied in view of filler distribution, structural confinement, and interfacial interactions. Analyses using wide-angle X-ray scattering, Raman spectroscopy, and tensile testing revealed a higher degree of filler reinforcement within the TPU moieties, indicating pronounced interfacial interactions. Further, the tensile modulus increased significantly with filler loading above its percolation threshold (363% for 20 wt % loading). The structural features of dispersed filler aggregates were explored through an iterative model fitting of the ultra-small-angle X-ray scattering (USAXS) data, along with scanning electron microscopy (SEM). As a strain sensor, the films displayed a superior working-strain Gauge Factor (GF = 123, up to 8%), with exceptional stability under both unidirectional and cyclic strain. The findings provide a fundamental understanding while validating the potential of hybrid carbonaceous fillers for the fabrication of PNCs with futuristic applications.

Vitrimeric nanocomposites (VNCs) are futuristic materials exhibiting multifunctional properties with sustainable capabilities. However, achieving filler-derived functionalities harmoniously with their dynamic characteristics is highly momentous in VNCs. Herein, the vitrimeric thiol-epoxy matrix incorporating tyre-waste-derived carbon nanosheets (CNS) is shown as a versatile nanocomposite integrating flexibility, high strength, and tunable electrical conductivity, together with self-healing and shape-memory characteristics. The transesterification-aided bond exchange reactions enabled vitrimeric features, while the CNS endorsed electrical transport, mechanical, thermal, and dimensional stabilities. Primary investigations, together with ultra-small angle X-ray scattering, explored the structural integrity of dispersed CNS. The hierarchically dispersed nanofillers provided efficient conductive pathways, offering a systematically varying electrical conductivity with filler concentration. They exhibited excellent dimensional stability even after multiple healing cycles, along with an exceptional stretchability up to 276%. Compared with the pristine matrix, a threefold increase in storage modulus has been observed at the maximum filler loading (15 wt%). They exhibited a commendable balance between the rigidity offered by CNS and excellent matrix flexibility, showing their versatility. As a result of accelerated thermoresponsive bond-exchange reactions, a complete shape recovery with an impressive healing efficiency of 99.6% is observed. This study not only provides a detailed elucidation of a multifunctional system but also offers practical insights for developing highly efficient epoxy-based vitrimers suitable for a wide range of applications.