In the last decade, due to the rapid development of telecommunications and the increased application of wireless communications, the human population has been increasingly exposed to electromagnetic radiation from various electronic devices incorporated into smart buildings. Because this electromagnetic pollution causes serious operational and health-related problems, electromagnetic interference (EMI) shielding has attracted great interest. Practically, EMI shielding is achieved by minimizing the signal transfer through a system via surface reflections and/or the absorption of the radiated power. Different metal-based EMI shielding materials have been developed and are widely available on the market. In recent years, intensive research has focused on the design and development of new polymer-based composite materials filled with various conductive graphene nanostructures, aimed at producing more efficient EMI shielding materials and protection [
1,
2]. Generally, polymer nanocomposites filled with graphene, multi-walled carbon nanotubes (MWCNTs), or their hybrids are attractive alternatives due to their unique combination of electrical, thermal, dielectric, magnetic, and mechanical properties. The main challenges are related to the application of specific graphene nanostructures with higher electrical conductivity, as well as the optimization of processing techniques to obtain a uniform dispersion within the polymer matrix. By combining two-dimensional (2D) graphene sheets with one-dimensional (1D) MWCNTs, the 1D tubes can physically bridge adjacent 2D graphene layers, constructing a more robust three-dimensional interconnected conductive network that effectively lowers the percolation threshold. Therefore, the main research goals focus on the design and development of thin, lightweight, highly flexible, next-generation smart materials capable of absorbing strong electromagnetic (EM) radiation over a wide frequency range [
3,
4].
Since its discovery in 2004, graphene has become one of the most attractive carbon-based nanostructures. Graphene is the foundational structural unit of all graphitic materials, giving it enormous application potential in various sectors, from the electrical industry, nanoelectronics, and environmental nanosensors to medicine and diagnostics [
1,
2]. Due to the sp
2-hybridized carbon atoms in the monolayer graphene lattice, it has a very low mass density compared to conventional fillers and possesses high electrical and thermal conductivity. Besides its very efficient conductivity, graphene exhibits superior mechanical behavior and is estimated to be significantly stronger than steel. Due to this superior electrical conductivity (higher than 10
7 S m
-1), excellent mechanical properties (exceptional mechanical strength and flexibility), and high specific surface area (resulting in a light and durable structure), graphene has been intensively tested as an ideal nanofiller in polymer nanocomposites for efficient electromagnetic shielding applications. Graphene can very effectively dissipate absorbed electromagnetic radiation, reducing overheating risks and ensuring device reliability [
4,
5]. However, some critical factors that affect the EMI shielding efficiency in graphene-based polymer nanocomposites include the filler loading, uniform graphene dispersion, and the resulting morphology of the graphene and modified graphene nanostructures inside the polymer matrices [
6,
7].
In order to improve the absorption performance of the EMI shielding effectiveness (SE) of graphene/polymer nanocomposites, some of the latest research trends are directed towards the modification of graphene by the incorporation of dielectric and/or magnetic nanoparticles. The incorporation of dielectric nanoparticles into graphene nanostructures has become one of the most efficient strategies to extend loss mechanisms beyond conduction alone. Dielectric nanoparticles, including titanium dioxide (TiO
2), barium titanate (BaTiO
3), nickel oxide (NiO), aluminum oxide (Al
2O
3), and silicon carbide (SiC), can introduce interfacial polarization, dipole relaxation, and space-charge accumulation [
8,
9]. As a result of the formation of heterojunctions between the graphene layers and dielectric fillers, Maxwell–Wagner–Sillars (MWS) polarization is induced [
10], thereby enhancing dielectric loss within the microwave frequency range. Furthermore, these dielectric fillers disrupt the continuity of the graphene conductive network, resulting in increased internal scattering and improved impedance matching—critical factors for maximizing absorption while minimizing specular reflection. Similar effects have also been achieved through the irradiation treatment of graphene nanostructures [
11,
12]. Specifically, electron-beam irradiation can induce controlled structural defects, cross-linking, and localized charge centers within the carbon nanostructures, which alter their complex permittivity and create additional sites for polarization loss. For instance, Yuchang
et al. worked on tailoring the EMI shielding properties of graphene nanosheets incorporated with BaTiO
3 ceramics [
13]. Their results showed that both the real and imaginary components of the complex permittivity increased with higher graphene nanosheet (GN) content. The results regarding EMI shielding effectiveness indicated that the absorption mechanism was the primary contributor to the overall EMI SE. The total EMI SE surpassed 40 dB in the X-band at a thickness of 1.5 mm, suggesting that GN/BaTiO
3 ceramics are excellent candidates for highly efficient EMI shielding materials throughout the X-band [
13]. Bhaskaran
et al. analyzed the EMI shielding effectiveness of epoxy nanocomposites with graphene nanoplatelets (GNPs) and Fe
3O
4 nanoparticles, referred to as Fe
3O
4/GNP hybrids, in the frequency range of 8–12.4 GHz. A series of epoxy nanocomposites with different ratios of Fe
3O
4/GNP, GNPs, and/or Fe
3O
4 nanoparticles was developed and assessed for their EMI SE. Overall, the incorporation of Fe
3O
4/GNP hybrids resulted in enhanced EMI shielding performance compared to samples containing only GNPs or Fe
3O
4 in equivalent amounts [
14]. Additionally, Q. Lu investigated the application of e-beam and neutron-irradiation effects on the EMI SE of nanocomposite materials [
15]. They studied MWCNT-based composites irradiated to fluence levels of 10
16 electrons/cm
2 with 500 keV electrons. An increase in EMI SE and conductivity was observed following electron irradiation in two of the tested epoxy-based systems.
However, a direct comparative assessment of how chemical metal decoration versus high-energy physical e-beam irradiation modifies the local interface and porous topology within a PMMA matrix for S-band attenuation remains largely unexplored. This paper reports a comparative study of the EMI SE of PMMA-based nanocomposite materials reinforced with two different treated graphene nanostructures: metal-modified graphene (G/Ag) and an e-beam-irradiated graphene/MWCNT hybrid, designated as AM1 and AH50, respectively.