FTIR Analysis
Noticeable changes in the intensity and position of the peaks, reflecting the chemical changes due to NaOH treatment of Moringa fiber as shown in Fig. 2. Broad Peak around 3400 cm⁻¹ may corresponds to O-H stretching vibrations[15]. NaOH treated fiber shows a shift or change in intensity, indicating alteration in hydroxyl groups.
Peaks around 2900 cm⁻¹ may associated with C-H stretching vibrations[15]. Changes in these peaks after treatment suggest modifications in the aliphatic content of the fibers. Peak around 1600 cm⁻¹ to 1500 cm⁻¹ may related to aromatic C = C stretching[15]. Alterations in this region can indicate changes in the aromatic content or structure of lignin. Peaks in the 1300 − 1000 cm⁻¹ range represent C-O stretching and C-H bending[16, 17]. Changes in this region for NaOH treated fiber indicate modifications in cellulose and hemicellulose structures. Changes in the peak intensity around 1021 cm⁻¹ after NaOH treatment suggest alterations in the fiber's polysaccharide content[18]. NaOH treatment typically results in the removal of hemicellulose and partial removal of lignin, leading to an increase in the relative content of cellulose. This is reflected in the FTIR spectrum as changes in the C-O stretching region. NaOH treatment typically removes hemicellulose, lignin, and other extractives, leading to an increase in cellulose content and alteration in functional groups, as evidenced by the changes in peak positions and intensities[19]. The removal of hemicellulose and lignin increases the porosity and surface area of the fibers. Additionally, the increase in the relative cellulose content, lead to more ordered crystalline structure. This increased surface area and reduction in lignin content leads to enhance dielectric properties for better interaction with microwave radiation, leading to improved absorption capabilities[20].
Structural & Morphological Analysis
The SEM images of the MOF/EPOX composite demonstrate a well-mixed and uniformly distributed epoxy resin across the fiber surfaces. The smooth dispersion of epoxy on the fiber surfaces, with no visible voids at the interfaces, indicates strong adhesion between the fiber and matrix, which is crucial for effective load transfer. Figure 3(a) and Fig. 3(b) show the random orientation of fibers within the composite, which may contribute to non-uniform mechanical properties. The epoxy matrix appears in continuous phase with minimal voids or air gaps. The presence of these voids in the matrix can influence the electric field behavior and polarization effects within the composite. These voids can lead to multiple scattering of microwaves, increasing the path length of incident waves and promoting more absorption. Additionally, the presence of air in these voids can enhance impedance matching, leading to better absorption[21]. However, the presence of voids can also compromise the mechanical strength of the composite, making controlled distribution of voids crucial during fabrication. In some areas of the composite, epoxy-fiber fractures with rough surfaces are observed[21, 22]. These fractures increase the irregular surface area and create air gaps, contributing to dielectric loss mechanisms due to the interaction of incident microwaves with the discontinuities, resulting in more random scattering and absorption.
Figure 3(c) shows the SEM image of an rGO-reinforced MOF/EPOX composite. The well-dispersed rGO at the fiber-matrix interface facilitates improved interfacial bonding, leading to effective load transfer. The uniform distribution of rGO across the fiber surfaces is critical for enhancing the mechanical properties of the composite material. The well-dispersed and firmly adhered rGO particles to the fiber surface could be a result of sonication processes during impregnation. The incorporation of rGO into the composite forms more effective network of conductive pathways and creates additional interfacial regions, enhancing the dielectric properties and contributing to improved conductive loss. The SEM images reveal significant morphological changes in the composite post-impregnation with rGO, which can facilitate greater attenuation of microwaves passing through the composite.
Optical Microscope
The optical microscopy analysis of untreated Moringa fiber in Fig. 4(a) reveals an irregular and non-uniform surface texture, likely attributed to the presence of surface contaminants such as dirt, waxes, oils, residues from the plant's cellular structure, and other foreign particles. Bright patches observed on the fiber surface may result from prolonged exposure to sunlight and environmental factors during the plant's growth. Following alkali treatment, significant changes in the optical appearance of Moringa fiber are evident in Fig. 4(b).
The surface features appear cleaner, with enhanced visibility and longitudinal alignment of microfibrils. This improvement is attributed to the removal of non-cellulosic materials. However, dark spots observed on the treated fiber surface may indicate chemical modification or degradation of lignin, natural pigments, or impurities due to non-uniform treatment. Alkali treatment increases the porosity of the fiber surface, promoting scattering and multiple reflections of incident waves, thereby enhancing absorption efficiency. Figure 4(c) displays rGO-coated post treated natural fiber, revealing a non-uniform distribution and modified texture of the fiber surface. Small irregular spots and flake-like patches may result from overlapping or agglomeration of rGO nanoparticles. In Fig. 4(d), optical images of MOF/EPOX composite show no evidence of fibers due to a thick and opaque layer of epoxy. Additionally, the cracks, voids, and bubbles on the composite surface are possibly due to faulty curing processes. Figure 4(e) depicts rGO/MOF/EPOX composite with well-distributed rGO and randomly aligned fibers. Dark spots on the surface indicate dense rGO agglomeration, while dot-like spots may signify the presence of rGO nanoparticles. Furthermore, the images illustrate the adhesion of fibers with epoxy, indicating effective load transfer leading to enhancement in mechanical features. Additionally, due to this adhesion, the interface between fibers and epoxy allows for multiple reflections and random scattering of incident microwaves, facilitating efficient absorption of energy within the composite.
Water Absorption Test
From the data presented in Fig. 5(a) it is evident that alkali treatment of fibers results in a notable reduction in water absorption efficiency. This reduction can be attributed to the removal of hydrophilic components such as hemicellulose and lignin, as well as a decrease in voids and pores that tend to trap water. Furthermore, analysis of Fig. 5(b) reveals a significant decrease in the water absorption efficiency of the MOF/EPOX composite following the induction of reduced graphene oxide (rGO). This reduction can be attributed to the inherently hydrophobic nature of rGO nanoparticles[23]. The hydrophobicity of rGO arises from its sp2-hybridized carbon atoms, which create a non-polar surface that repels polar water molecules. Additionally, the reduction of oxygen-containing functional groups, lowers surface energy of rGO, thereby minimizing its interactions with higher surface energy entities such as water. Hence, the effective dispersion of rGO enhances hydrophobic nature of overall composite. It is important to note that water, having a significantly higher dielectric constant compared to Moringa fiber and Epoxy, can substantially increase the overall permittivity of the composite. This increase in permittivity may correspond to greater dielectric loss due to the high degree of polarization and relaxation processes.
Furthermore, water-filled voids within the composite may act as scattering centers, increasing the interaction time of
microwaves and facilitating absorption through multiple scattering events. However, it is crucial to consider the potential drawbacks of water absorption in composites. Water absorption can lead to swelling, ultimately resulting in mechanical degradation of the epoxy matrix by weakening of the fiber-matrix interface. This degradation can compromise the overall structural durability of the composite. Additionally, prolonged exposure to water may lead to the oxidation of filler particles, potentially impacting the microwave absorption efficiency of the composite. In summary, the analysis of water absorption behavior is essential for the fabrication of optimized designs of fiber-epoxy-based composites for microwave absorption performance, particularly in applications involving humid and wet environments.
Thermal Analysis
Thermal conductivity is a material property that quantifies a material's ability to conduct heat, determining how easily heat can pass through a material. In composite materials, thermal conductivity is influenced by the conductivities of the constituent materials, their volume fractions, and the nature of the interfaces. Heat in these materials is primarily carried by lattice vibrations known as phonons. In the Fig. 7 it can be observed that the thermal conductivity of MOF/EPOX and rGO/MOF/EPOX composite increases with increasing temperature, which can be explained by the Debye model of specific heat and thermal conductivity. At low temperatures, the phonon contribution to thermal conductivity increases as more phonon modes are excited. As temperature increases, phonon-phonon scattering becomes significant, affecting thermal conductivity. Furthermore, as shown in the Fig. 7, the thermal conductivity of the rGO/MOF/EPOX composite is significantly higher compared to the MOF/EPOX composite. This enhancement in thermal conductivity can be attributed to the high thermal conductivity of rGO, due to its two-dimensional structure and strong sp2 carbon-carbon bonds. Also the alignment of fibers within the composite has the potential to influence thermal conductivity.
The presence of rGO in the composite provides highly efficient pathways for heat transfer and better phonon coupling by bridging the gaps between fibers and the matrix[23]. In composite materials, multiple interfaces can hinder heat transfer. However, the well-dispersed rGO nanopowder in the composite helps to reduce this interfacial thermal resistance, promoting effective heat transfer. As temperature rises, anharmonic effects become more pronounced, leading to increased phonon scattering. The higher population of phonons results in more frequent phonon-phonon scattering events, which hinder the flow of thermal energy, thereby reducing the mean free path of phonons and decreasing the thermal conductivity. Thermal conductivity play a crucial role in the performance and stability of microwave absorbing materials. By optimizing thermal conductivity, these materials can be fabricated to efficiently attenuate microwave energy while maintaining thermal stability and compatibility.
Microwave absorption properties
The gradual decrease in the dielectric constant for MOF/EPOX and rGO/ MOF/EPOX composite can be attributed to the material's microstructure and the interactions between the composite components[24]. When Moringa oleifera fibers added to the epoxy matrix the interfacial areas between the fibers and the matrix increases which causes polarization effects leading to decrease of overall dielectric constant as shown in Fig. 8. At lower frequencies, different polarization mechanisms such as electronic, ionic, dipolar, and interfacial polarization contribute to the dielectric constant. As frequency increases, these polarization mechanisms cannot keep up with the rapidly changing electric field. Consequently, the contribution of these polarizations diminishes, leading to a decrease in the dielectric constant. At higher frequencies, the time available for dipole orientation is reduced, causing a lag in response[25]. This relaxation effect results in a lower dielectric constant at higher frequencies. The addition of rGO increases dielectric constant (ε’) at lower frequencies from 3.28 to 3.35 and at higher frequencies increase from 2.94 to 3.02 compared to MOF/EPOX composite. This may be attributed to rGO due to its high surface area and multiple conductive pathways, facilitating the accumulation and retention of electrical charges within the composite structure[25]. At higher frequencies, interfacial polarization effects become less significant because the dipoles at the interfaces cannot reorient quickly enough, leading to a reduction in the overall dielectric constant. In the X-band frequency range, the dielectric constant decreases because the material's response to the electric field is no longer in phase, resulting in reduced polarization efficiency and a lower dielectric constant.
The dielectric loss (ε”) of MOF/EPOX and rGO/ MOF/EPOX composite increases gradually with increase of frequency as shown in Fig. 9. This may be attributed due to enhanced surface roughness by the alkali treatment and introduces polar functional groups, leading to increased interfacial polarization and dielectric loss. Further, the incorporation of rGO enhances the conductivity of the composite, resulting in increased energy dissipation and dielectric loss[26]. Moreover, the synergistic effect between alkali-treated fibers and rGO promotes enhanced interfacial interactions, which contribute to the gradual rise in dielectric loss with increasing frequency in the X-band range.
The increase in tangent loss with frequency in MOF/EPOX and rGO/ MOF/EPOX composites can be attributed to the microstructure and material properties of the composites as shown in Fig. 10. At lower frequencies, the movement of molecules or particles within the composite material is relatively slow. This allows for better alignment and organization of the composite components, resulting in lower friction and energy dissipation at the interfaces between the epoxy matrixes, rGO coatings. However, as the frequency increases, the movement becomes more rapid, leading to increased friction and energy dissipation at these interfaces. Again, at higher frequencies, the polarization of molecules and dipoles may not be able to keep up with the rapidly changing electric field, leading to increased energy loss due to dielectric relaxation. As per Maxwell’s electromagnetic wave equation in an ionized medium[27]
where ε* is complex permittivity and μ* is magnetic permeability of the medium of propagation, the propagation of electromagnetic waves in materials depends on their dielectric properties
In heterogeneous materials like composites, variations in dielectric properties can lead to non-uniform electric field distributions, especially at interfaces between phases with different permittivity. This can cause local concentration of electric field lines, resulting in enhanced energy dissipation and increased tangent loss at higher frequencies. Further, dispersion mechanisms such as interfacial polarization, dipolar relaxation, and conductive losses can contribute to frequency-dependent tangent loss due to addition of rGO in composites, the conductivity of the rGO layers may lead to increased losses at higher frequencies due to eddy current losses and other conductivity-related mechanisms.The variation of reflection loss for MOF/EPOX and rGO/ MOF/EPOX composites with frequency shown in Fig. 11 can be explained based on Maxwell's wave propagation in dielectric media. Maxwell's equations in response to electric and magnetic fields interaction with matter, including dielectric materials like composites. The dielectric permittivity (ε*) of a material determines how much the material can polarize in response to an applied electric field. In composites, variations in permittivity arise from the different constituents (epoxy, Moringa oleifera fibers, and rGO coatings) and their spatial distribution. At lower frequencies, the wavelength of the incident electromagnetic wave is longer, and the polarization of the composite material can effectively follow the changing electric field. This results in lower reflection loss − 10.80dB for MOF/EPOX and − 13.86dB for rGO/ MOF/EPOX composite because the incident wave can penetrate deeper into the material before being reflected back.
However, at higher frequencies, where the wavelength becomes comparable to or smaller than the dimensions of the composite constituents, the mismatch in permittivity at interfaces causes more significant reflection loss at frequency 11.812GHz are found to be -11.46dB and − 17.71dB for MOF/EPOX and rGO/ MOF/EPOX respectively due to high mismatch of impedance as observed in the present investigation. Again at lower frequencies, the penetration depth of the incident wave is larger, allowing for more opportunities for absorption and dissipation of energy within the material[28]. However, at higher frequencies, where the penetration depth decreases, multiple scattering events at interfaces become more significant, leading to increased reflection loss. Further, the formation of large no. of resonance cavities as observed in SEM images of the composite material lead to frequency-dependent reflection behavior. As the material has high reflection loss in MOF/EPOX and rGO/ MOF/EPOX composites it corresponds to microwave absorption efficiency increase from 92.06–98.42% which is due to impregnation of rGO in MOF/EPOX composite.