Startseite Naturwissenschaften Multi-core/shell SiO2@Al2O3 nanostructures deposited on Ti3AlC2 to enhance high-temperature stability and microwave absorption properties
Artikel Open Access

Multi-core/shell SiO2@Al2O3 nanostructures deposited on Ti3AlC2 to enhance high-temperature stability and microwave absorption properties

  • Yang Guo EMAIL logo , Kehua Tan , Xiaoying Guo EMAIL logo , Huirong Li und Xian Jian
Veröffentlicht/Copyright: 24. Mai 2023
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Abstract

Poor high-temperature stability (HTS) and weak microwave absorption performance (MAP) are a major restriction for wave-absorbing materials in elevated temperature ambient. Consequently, the Stöber process and the sol–gel method are first devised and used to create multi-core/shell SiO2@Al2O3 nanostructures (MCSNs) on Ti3AlC2 (TAC). The MCSNs with a thickness of 135–215 nm raise the starting oxidation temperature of the matrix by 400°C. Furthermore, the weight gain drops from 17.44 to 2.32% within 1 h at 800°C. The effective absorption bandwidth with a reflection loss (RL) ≤ −10 dB of the MCSNs-coated TAC is 3.25 GHz (8.68–11.27 and 11.63–12.29 GHz) at a thickness of 2.0 mm, which is 4.7 times that of the matrix. The minimum RL is reduced by a factor of 2.77 from −10.68 to −29.55 dB. The enhanced MAP is due to the introduced multiple reflection events and scattering mechanism as well as the enhanced electronic polarization, interface polarization, and polarization relaxation. The growth of the MCSNs provides a reference for the design and preparation of bifunctional materials with good HTS and MAP.

1 Introduction

The extreme electromagnetic environment (including high temperature, high damp heat, and salt fog) have brought high-temperature (>300°C), oxidation-resistant microwave absorbing materials (MAMs) into focus [1,2,3,4]. These materials can be used in civil, military, and aerospace equipment (such as for the nozzle, heat shield, and nose cone) [5,6,7,8]. Therefore, materials with outstanding high-temperature stability (HTS) and microwave absorption performance (MAP) are widely studied [9,10]. In order to meet these requirements, various MAMs have been developed, mainly including magnetic materials (such as magnetic metals [11,12] and ferrites [13]), carbon-based materials (such as carbon nanotubes [14,15], carbon fibers [16], and graphene [5]), and ceramic-based materials (such as SiCnp/Cf [17], PyC–SiCf/SiC [18], and Cf/SiCnw [19]). The general use of magnetic materials in high-temperature situations is severely constrained by the low Curie temperature [20]. Furthermore, once the temperature reaches 300°C, carbon-based materials begin to oxidize [21]. Naturally, SiC-based materials with good HTS and chemical stability become one of the best choice for high-temperature MAMs [22]. However, the low carrier concentration and single polarization mechanism prevent SiC from achieving excellent MAP.

Until now, the introduction of dielectric materials to tune the complex permittivity and polarization mechanism of SiC-based materials has been a commonly used strategy to improve their MAP [18,23]. Han et al. prepared SiC nanowires reinforced SiCf/SiC composites via chemical vapor infiltration [24]. The conductivity and complex permittivity of the composites showed a significant uplift dependence on temperature. Furthermore, the minimum reflection loss (RLmin) was −47.5 dB at a thickness of 2.5 mm at 11.4 GHz and 600°C, and the effective absorption bandwidth (EAB; RL ≤ −10 dB) was 2.8 GHz. Huo et al. prepared heterogeneous SiC/ZrC/SiZrOC hybrid nanofibers containing different highly conductive ZrC phases via electrospinning and high-temperature pyrolysis [25]. When the content of ZrC was up to 10 wt%, the conductivity of the SiC/ZrC/SiZrOC hybrid nanofibers increased from 0.34 to 2.57 S/cm. For SiC/ZrC/SiZrOC hybrid nanofibers containing 7 wt% ZrC, the initial oxidation temperature was around 600°C. When the thickness of the absorber was 3 mm, the EAB was 3 GHz (8.2–11.2 GHz), and the RLmin was −17.5 dB at 10.3 GHz. These results indicate that the inclusion of dielectric materials can considerably improve the MAP of SiC. However, the excellent chemical properties of SiC are degraded, especially its HTS. Therefore, finding a MAM with good HTS and complex polarization mechanism is necessary.

Good electrical characteristics and high-temperature oxidation resistance are displayed by the ternary-layered compound Ti3AlC2 (TAC) [26,27]. TAC is a promising replacement for SiC due to these benefits. The notion that TAC has a good HTS is supported by the modest mass gain at 800°C [28]. The abundant interface and the Ti–C bond endow TAC with a high interface polarization and electronic polarization. Li et al. successfully doped TAC with Fe (xFe-TAC) through high-temperature solid-state sintering [29]. Doping has the ability to improve defect dipole polarization and considerably diversify the phase interface of TAC. They found that when the absorber thickness was 1.5 mm, the RLmin was −33.3 dB, and the EAB was 3.9 GHz. In addition, the core–shell design based on a heterogeneous interface can adjust the complex permittivity and interface polarization mechanism, thus optimizing impedance matching [30]. It is envisaged that TAC with a core–shell structure can achieve not only an excellent MAP but also a good HTS. SiO2 can be exploited in this aspect since it has high thermo-stability, antioxidant properties, and high microwave transmittance characteristics [31]. It hardly inhibits the coupling between matrixes. On the other hand, the antioxidant Al2O3 also holds the potential to maintain the diffusion barrier integrity by supplying adequate environmental protection [32].

Herein the Stöber process (SP) and the sol–gel method (SGM) based on heterogeneous interface engineering were used to construct multi-core/shell SiO2@Al2O3 nanostructures (MCSNs) in situ on TAC. The results show that the MCNMs with a thickness of 135–215 nm have a significant effect on the HTS and MAP of TAC. In instance, they can nearly double the initial oxidation temperature of TAC (from 400 to 800°C) and reduce the mass gain of TAC by a factor of 6.52 (from 17.44 to 2.32%). Furthermore, the EAB can be broadened by a factor of 4.7 (from 0.69 to 3.25 GHz) with a thickness of 2.0 mm, and the RLmin can be increased by a factor of 2.77 (from −10.68 to −29.55 dB). The results presented in this work can serve as a guide for designing MAMs with good MAP and HTS.

2 Experimental method

2.1 Materials

The high-temperature solid-state sintering method was employed to create the TAC that was used in the current study. Figure S1 displays the comprehensive process and composition analysis. The reagents used mainly include tetraethyl orthosilicate (TEOS; Si(OC2H5)4), aluminum nitrate (Al(NO3)3·9H2O), ammonia (NH3·H2O), absolute ethanol (EtOH), and deionized water (H2O). The above reagents were analytically pure and were purchased from Sinopharm Group Chemical Agent Co. Ltd.

2.2 Sample synthesis

First, a solution was made by combining 14 ml of deionized water, 56 ml of EtOH, and 2 ml of ammonia. After 5 g TAC was added to the aforementioned solution and mechanically mixed (300 rpm) for 10 min, 14.4 ml of TEOS was added and reacted for 6 h at 30°C. The reaction products were then cleaned, dried for 24 h at 80°C in a vacuum drying oven, and the resulting sample is known as TAC@SiO2.

Next 14 ml of deionized water and 56 ml of EtOH were mixed together in a solution. 5 g TAC@SiO2 and 5 g Al(NO3)3·9H2O were added sequentially, and the solution was mechanically stirred for 10 min at 300 rpm. Then, ammonia water was added dropwise, so that the PH was corrected to 11. The reaction took place for 6 h at 30°C. Furthermore, the product obtained by suction filtration of the solution was repeatedly washed and dried in a vacuum drying oven for 24 h at 80°C. Finally, the dried product was placed in a tube furnace for annealing; the obtained product is named TAC@SiO2@Al2O3. The annealing temperature was 800°C (heated at the rate of 10°C/min). The annealing time was 2 h, the protective gas was N2, and the gas flow was 80 ml/min.

2.3 Characterization

The surface morphology and element distribution of the samples were observed using a Thermo Quattro S (USA) field-emission scanning electron microscope (FESEM) equipped with an EDAX ELECT PLUS spectrometer. The working voltage was 10 kV. A FEI Tecnai G2 F20 (USA) transmission electron microscope (TEM) equipped with an energy spectrometer (Oxford 80 T) was used for the microstructure analysis and energy-dispersive spectroscopy (EDS). The acceleration voltage was 200 kV. The phase composition of the samples was analyzed using an Ultima IV (Japan) X-ray diffractometer (XRD) with a Cu Kα radiation source. The scanning rate was 5°/min. X-ray photoelectron spectroscopy (XPS) measurements were carried out using a Thermo Fisher Nexsa (USA) spectrometer with a standard Al Kα X-ray source (1486.7 eV). The Raman spectra were acquired using a Thermo DXR2xi (USA), and the laser wavelength was 532 nm. Thermogravimetric (TG), differential thermogravimetric (DTG), and differential scanning calorimetric (DSC) analyses were performed using an STA 449 F3 (Germany) in the temperature range of 30–1,300°C (the heating rate was 10°C/min). The electromagnetic parameters were measured using a N5230A network vector analyzer (USA) in the frequency range of 0.5–18 GHz at room temperature. The samples used for these measurements consisted of a circular workpiece with an outer diameter of 7.0 mm and an inner diameter of 3.0 mm. The samples were composed of the different TAC-based absorbents and paraffin with a mass ratio of 4:1. The dielectric dispersion, power flow, electric field strength, and power loss density of the absorbers were computed from the measured electromagnetic parameters using the CST Studio Suite 2019 program. The simulation model consisted of a square plate with a thickness of 2.0 mm. Incident electromagnetic waves (EWs) were set to transmit in the opposite direction along the z-axis. All directions were open within the boundary conditions.

3 Results and discussion

The preparation process of TAC@SiO2@Al2O3 is schematically depicted in Figure 1. First, the TAC was coated with SiO2 using the classical SP. In this process, the silanol groups’ bonding and dangling bonds at the TAC surface change the polarity state of the substrate, causing the TAC@SiO2 particles to couple together [33,34]. Second, the surface of the coupled TAC@SiO2 particles was coated with materials containing Al. Furthermore, after annealing at 800°C for 2 h in N2, a flaky Al2O3 coating was formed around the linked TAC@SiO2 particles; this sample is named TAC@SiO2@Al2O3. This is the first report on the preparation of TAC coated with MCSNs using such a simple strategy.

Figure 1 
               Schematic diagram of the synthesis process of TAC@SiO2@Al2O3.
Figure 1

Schematic diagram of the synthesis process of TAC@SiO2@Al2O3.

Figure 2 displays the microscopic morphology and composition analyses of the TAC-based absorbents. This graphic demonstrates how significantly different the morphology and structure of TAC@SiO2 are from those of TAC. It can be inferred that a coupling reaction occurred between the TAC@SiO2 particles [35]. Additionally, the TAC@SiO2 surface is covered with rough products during the SGM and subsequent annealing process (AP), as depicted in Figure 2(c). The linked TAC@SiO2@Al2O3 particles’ TEM images are displayed in Figure 2(d) and (e). Amorphous SiO2 has a thickness of around 135 nm. The thickness of the Al2O3 shell is in the range of 10–80 nm. According to Figure 2(f), the (107) and (103) crystal planes of TAC correspond to the crystal plane spacings of 1.8 and 1.3, respectively. The crystal plane spacing of 2.4 Å corresponds to the (140) crystal plane of Al2O3, which reconfirms the presence of Al2O3, as shown in Figure 2(g).

Figure 2 
               SEM images showing the surface appearance of (a) TAC, (b) TAC@SiO2, and (c) TAC@SiO2@Al2O3. (d) and (e) TEM images and (f) and (g) corresponding high resolution TEM images of TAC@SiO2@Al2O3. (h) TEM image of the as-fabricated TAC@SiO2@Al2O3 and corresponding elemental mapping of (i) Ti, (j) Al, (k) C, (l) Si, and (m) O.
Figure 2

SEM images showing the surface appearance of (a) TAC, (b) TAC@SiO2, and (c) TAC@SiO2@Al2O3. (d) and (e) TEM images and (f) and (g) corresponding high resolution TEM images of TAC@SiO2@Al2O3. (h) TEM image of the as-fabricated TAC@SiO2@Al2O3 and corresponding elemental mapping of (i) Ti, (j) Al, (k) C, (l) Si, and (m) O.

The Ti, Al, C, Si, and Al element mappings for the paired TAC@SiO2@Al2O3 particles are shown in Figure 2(i)–(m). The Al, Si, C, and O elements are uniformly distributed in the coupled TAC@SiO2@Al2O3 particles, indicating that SiO2 and Al2O3 interact to generate a homogeneous heterostructure. The defects in heterostructures can be used as polarization centers to generate a dipole polarization [36].

Figure 3(a) shows the XRD patterns of TAC, TAC@SiO2, and TAC@SiO2@Al2O3. It can be seen that the XRD pattern of TAC is made up of 11 diffraction peaks located at 9.5, 19.2, 33.7, 36.8, 39.0, 41.8, 48.5, 56.6, 61.0, 70.6, and 74.1°, corresponding to PDF#52-0875. After the SP, the TAC surface is coated with SiO2; however, SiO2 cannot be detected, which is mainly attributed to its amorphous state. Furthermore, after TAC@SiO2 is subjected to the SGM and the AP, the major diffraction peaks of TAC are retained, and the Al2O3 diffraction peaks appear at 12.8 and 34.5°, correlating to PDF#03-0066. This shows that Al2O3 was successfully deposited on to the TAC surface.

Figure 3 
               (a) XRD patterns of TAC, TAC@SiO2, and TAC@SiO2@Al2O3. (b) Raman spectra of TAC, TAC@SiO2, and TAC@SiO2@Al2O3. (c) High-resolution Ti 2p spectrum, (d) high-resolution Al 2p spectrum, and (e) high-resolution C 1s spectrum of TAC. (f) High-resolution Si 2p spectrum and (g) high-resolution O 1s spectrum of TAC@SiO2. (h) High-resolution Al 2p spectrum and (i) high-resolution O 1s spectrum of TAC@SiO2@Al2O3.
Figure 3

(a) XRD patterns of TAC, TAC@SiO2, and TAC@SiO2@Al2O3. (b) Raman spectra of TAC, TAC@SiO2, and TAC@SiO2@Al2O3. (c) High-resolution Ti 2p spectrum, (d) high-resolution Al 2p spectrum, and (e) high-resolution C 1s spectrum of TAC. (f) High-resolution Si 2p spectrum and (g) high-resolution O 1s spectrum of TAC@SiO2. (h) High-resolution Al 2p spectrum and (i) high-resolution O 1s spectrum of TAC@SiO2@Al2O3.

The Raman shifts of TAC, TAC@SiO2, and TAC@SiO2@Al2O3 were collected in order to more precisely investigate the structure and composition of the TAC-based absorbers, as shown in Figure 3(b). The three Raman bands located at 250, 400, and 600 cm−1 represent the vibration modes of the non-stoichiometric Ti–C bond in TAC. The two broad peaks located between 1,300 and 1,600 cm−1 are the D and G modes of the C atom [37]. Interestingly, the Raman peaks of TAC in TAC@SiO2@Al2O3 appear blue shift and move to a position with higher Raman shift, which will be caused by the high bond energy of the Si–O and Al–O bonds [38]. For TAC@SiO2, there are roughly five Raman shifts in the Raman peak corresponding to the vibration mode of the non-stoichiometric Ti–C bond. For TAC@SiO2@Al2O3, the Raman peak representing the non-stoichiometric Ti–C bond experiences about 25 Raman shifts. In addition, the intensity ration of D and G (I D/I G) peak of TAC@SiO2@Al2O3 is 1.02, which is comparable to the I D/I G value of TAC@SiO2. This shows that the MCSNs have not significantly altered the inherent state of the C atom in TAC. The findings further indicate that the MCSNs have no significant influence on the composition and structure of TAC.

Furthermore, the chemical composition and element valence state of the TAC-based absorbents were revealed via XPS, as shown in Figure 3(h)–(j). Figure 3(c) shows the high-resolution Ti 2p spectrum of TAC, which can be fitted with six peaks. The Ti 2p1/2 peak at 454.0 eV and the Ti 2p3/2 peak at 460.1 eV correspond to the Ti–C bond in TAC, confirming the existence of TAC [26,39]. The Ti 2p1/2 peak at 455.0 eV and the Ti 2p3/2 peak at 461.5 eV correspond to the Ti–O bond in non-stoichiometric TiO2 [40]. The Ti 2p1/2 peak at 458.6 eV and the Ti 2p3/2 peak at 464.4 eV correspond to the Ti–O bond in TiO2 [41]. As shown in Figure 3(d), two peaks with binding energies of 71.8 and 74.3 eV are observed in the high-resolution Al 2p spectrum of TAC, corresponding to the Ti–Al bond in TAC and the Al–O bond in Al2O3, respectively [42,43]. The high-resolution C1s spectrum is fitted with four peaks (as shown in Figure 3(e)) located at 281.2, 284.8, 286.4, and 288.9 eV, corresponding to the C–Ti, C–C, C–O, and O–C═O bonds, respectively [44]. These results show that the investigated samples are mainly composed of TAC and contain only small amounts of TiO2 and Al2O3. Figure 3(f) and (g) show the high-resolution Si 2p and O 1s spectra of TAC@SiO2. Figure 3(f) shows that the high-resolution Si 2p spectrum can be decomposed into three peaks with binding energies of 99.7, 102.4, and 103.5 eV, corresponding to SiO x (0 < x < 2), SiO x (0 < x < 2), and SiO2, respectively [45,46,47]. The high-resolution O 1s spectrum of TAC@SiO2 can be divided into two peaks located at 530.2 and 532.2 eV, as shown in Figure 3(g), corresponding to the Si–O and C–O bonds, respectively [48]. The high-resolution Si 2p and O 1s spectra of TAC@SiO2 confirm the existence of SiO2. The position difference in the O 1s peaks of TAC and TAC@SiO2 is mainly caused by the C–O bond in air [49]. In the high-resolution Al 2p spectrum of TAC@SiO2@Al2O3, an intense peak is observed at 75.0 eV, corresponding to Al2O3 [50,51], as shown in Figure 3(h), while the peak at 72.3 eV corresponds to AlO x [52]. The appearance of Al2O3 is derived from the annealing of Al(OH)3 in N2·Al(OH)3 is from the hydrolysis of Al3(NO3)3·9H2O in NH3·H2O. The specific reaction equation is shown in equations (1) and (2).

(1) Al 3 ( N O 3 ) 3 · 9 H 2 O + 3 N H 3 · H 2 O + 27 H 2 O 3 Al ( OH ) 3 + 9 N H 4 N O 3 ,

(2) 2 Al ( OH ) 3 Al 2 O 3 + 3 H 2 O .

In the high-resolution O 1s spectrum of the coupled TAC@SiO2@Al2O3 particles (Figure 3(i)), the peaks at 529.9 and 531.9 eV correspond to the Al–O and C–O bonds, respectively [53,54,55]. The above analysis results fully confirm the successful preparation of TAC@SiO2@Al2O3. More importantly, the structural synergy of the three substances is the key to improve the HTS and MAP of the TAC-based absorbents.

The TG analysis can reveal the thermal stability and oxidation stability of samples at different temperatures and atmospheres. Therefore, we examined the HTS of the TAC-based absorbents from room temperature to 1,300°C, as shown in Figure 4. It is evident that all samples exhibit almost the same characteristic curves, as shown in Figure 4(a). It can be observed that the initial oxidation temperature of TAC is approximately 400°C. The initial oxidation temperature of TAC@SiO2 is around 500°C. Furthermore, the initial oxidation temperature of TAC@SiO2@Al2O3 is up to 800°C. As demonstrated, the MSCNs raise the TAC’s initial oxidation temperature by 400°C. Thus, it is clear that the MSCNs greatly enhance the HTS of TAC. It is possible mainly because of the MSCNs’ ability to significantly decrease the number of transport channels connecting oxygen and TAC. SiO2@Al2O3 can constitute a dense network structure [56]. This network structure can effectively reduce the number of transport channels between oxygen and the ceramic matrix and restrict oxygen diffusion to the interior, improving TAC’s high-temperature oxidation resistance. Figure 4(b) shows the DTG curves of TAC, TAC@SiO2, and TAC@SiO2@Al2O3. It can be noted that the weight gain rate of TAC is 0.03%/°C. On the other hand, the weight gain rate of TAC@SiO2@Al2O3 coated with the MSCNs is only 0.008%/°C. Furthermore, the exothermic peaks of TAC, TAC@SiO2, and TAC@SiO2@Al2O3 are located at 944.59, 1,178, and 1,220°C, respectively, as shown in Figure 4(c). All these point to the fact that MSCN can greatly increase TAC’s high-temperature oxidation resistance. The TAC-based absorbents were submitted to isothermal TG tests at 800°C in air over the course of 1 h to verify that the HTS of TAC is improved, as shown in Figure 4(d). It is obvious that TAC’s mass increase can reach 14.70%, whereas TAC@SiO2@Al2O3’s mass increase is just 2.72%.

Figure 4 
               HTS analysis of the TAC-based absorbents at high temperature. (a) TG, (b) DTG, and (c) DSC analysis of TAC, TAC@SiO2, and TAC@SiO2@Al2O3. (d) TG curves of TAC, TAC@SiO2, and TAC@SiO2@Al2O3; these curves were obtained at 800°C in air over the period of 1 h.
Figure 4

HTS analysis of the TAC-based absorbents at high temperature. (a) TG, (b) DTG, and (c) DSC analysis of TAC, TAC@SiO2, and TAC@SiO2@Al2O3. (d) TG curves of TAC, TAC@SiO2, and TAC@SiO2@Al2O3; these curves were obtained at 800°C in air over the period of 1 h.

To establish the MAP of MAMs, electromagnetic characteristics are crucial. As a result, we examined the real part (ɛ′) and imaginary part (ɛ″) of the TAC-based absorbers as well as the dielectric loss tangent (tan δ ε) of the complex permittivity, as shown in Figure S3. ɛ′ represents the capacity of a material to store electric energy, while ɛ″ and tan δ ε indicate the capacity of a material to dissipate the incident EWs. As is well known, TAC, SiO2, and Al2O3 are all non-magnetic materials, and the complex permeability is thus not considered here. The ɛ′ of TAC, TAC@SiO2, and TAC@SiO2@Al2O3 decreases with the increase in frequency, as shown in Figure S3(a) and (b). This is because the dipoles in the TAC-based absorbers rearrange when an electric field is applied. The dielectric polarization caused by the rearranged dipoles is reduced as the frequency rises, preventing them from following the electric field and causing a decrease in the dielectric response. In addition, the ɛ′ of TAC is 15.9–18.0 in the range of 0.5–18 GHz, and the ɛ′ of TAC coated with the MCSNs is 15.1–17.9. The ɛ″ of TAC is 0.007–0.33 at 0.5–18 GHz, and the ɛ″ of TAC@SiO2@Al2O3 is 0.04–0.51. It can be seen that the ɛ″ of TAC@SiO2@Al2O3 is significantly lower than that of TAC at 7–14 GHz. The TAC@SiO2@Al2O3 has a greater ɛ″ than TAC at 0.5–15 GHz. Additionally, the tan δ ε values of the TAC-based absorbers were determined. It was discovered that the tan δ ε of TAC@SiO2@Al2O3 is higher than that of TAC in the range of 0.5–13 GHz. It is clear that TAC@SiO2@Al2O3 has a greater ability than TAC to disperse incident EWs. In addition, the MAP of TAC@SiO2@Al2O3 around 11 GHz is almost unaffected by sample thickness. Two main reasons cause this: when the thickness of the absorber layer increases to a certain level, the absorption capacity of the material will reach its limit, i.e., saturation state [57]. Second, due to the particular shape and size of the TAC, there may be a resonance phenomenon at a specific frequency point [58]. That is, when the frequency of the microwave is equal to the resonance frequency of the material, the absorption performance will reach its peak.

In order to more intuitively analyze the impact of the MCSNs on the properties of the TAC, the RL values of the TAC-based absorbers were calculated using equations (3) and (4). The 3D RL maps of the TAC-based absorbers with a thickness of 0.5–5 mm in the frequency range of 0.5–18 GHz are shown in Figure 5(a)–(c) [59,60].

(3) Z in = Z 0 μ r ε r tanh j 2 π f c d μ r · ε r ,

(4) RL = 20 lg Z in Z 0 Z in + Z 0 ,

where Z in and Z 0 stand for the input impedance and internal impedance, respectively. Additionally, μ r stands for the complex permeability, ε r represents the complex dielectric constant, f is the microwave frequency, d marks the thickness of the absorber, and c specifies the speed of light.

Figure 5 
               Frequency and thickness dependence of the simulated three-dimensional (3D) RL maps of (a) TAC, (b) TAC@SiO2, and (c) TAC@SiO2@Al2O3. (d) RL curves of the TAC-based absorbers with a thickness of 2.5 mm in the range of 0.5–18 GHz.
Figure 5

Frequency and thickness dependence of the simulated three-dimensional (3D) RL maps of (a) TAC, (b) TAC@SiO2, and (c) TAC@SiO2@Al2O3. (d) RL curves of the TAC-based absorbers with a thickness of 2.5 mm in the range of 0.5–18 GHz.

According to the comparisons of the RL curves of the TAC-based absorbers with a thickness of 2.0 mm at 0.5–18 GHz, it is found that the EAB of TAC is 0.69 GHz (9.75–10.44 GHz), and the RLmin is −10.68 dB (10.09 GHz). The EAB of TAC@SiO2 is 1.50 GHz (9.03–9.42 GHz and 9.99–11.12 GHz), and the RLmin is −20.70 dB (10.39 GHz). The EAB of TAC@SiO2@Al2O3 is 3.25 GHz (8.68–11.27 and 11.63–12.29 GHz), and the RLmin is −29.55 dB (10.52 GHz). Compared with pure TAC, the EAB of TAC coated with MCSNs is 4.7 times higher and the RLmin is 2.77 times higher, demonstrating outstanding microwave absorption capabilities. This can be explained by the following two aspects: First, the multi-peak resonances induced by the heterogeneous interfaces broaden the EAB of the TAC. TAC@SiO2@Al2O3 is mainly composed of TAC, amorphous SiO2, and Al2O3. The four resonance peaks located at 6.64, 9.82, 12.64, and 14.56 GHz, as shown in Figure S3(b), are induced by the three-phase interactions, surface geometric enhancement effect, and local space charge accumulation [61,62,63]. Compared with the three resonance peaks of TAC located at 7.48, 11.38, and 13.76 GHz, both the number and intensity of the resonance peaks of TAC@SiO2@Al2O3 are higher. It is noteworthy that the resonance peak of TAC coated with the MCSNs moves to a lower frequency. This can be explained by the quarter-wavelength resonance equation f m = [ ( 2 k 1 ) c ] / ( 4 t m n ) [11], where f m is the resonant frequency, t m stands for the resonant thickness, k is a positive integer, and n = Re ( ε r μ r ) denotes the refractive index of the composite material. Second, the combination of the TAC and the MCSNs induces the establishment of multiple loss mechanisms. SiO2 and Al2O3 are wave transmitting materials with two predominant functionalities: First, being window materials, a small amount of RL is converted into heat energy when the EWs are refracted and penetrate into the absorber. Second, given a certain amount of incident EWs, wave transmitting materials can promote more of these EWs to penetrate into the absorber. In this process, the electronic polarization, interface polarization, and polarization relaxation generated by the conductive TAC core attenuate the incident EWs. According to the Debye relaxation theory, the main loss mechanisms of dielectric materials are polarization relaxation and conduction loss [64]. Generally, polarization relaxation and conduction loss can be studied using the Cole–Cole plots, as shown in Figure S4. ε′ and ε″ can be expressed using the following equation [65,66]:

(5) ε ( ε s + ε ) 2 2 + ( ε ) 2 = ε s ε 2 2 ,

where ε s denotes the static permittivity, and ε presents the high-frequency limited permittivity.

In the Cole–Cole plot, a semicircle represents a relaxation process. The polarization relaxation loss increases with the semicircle radius. In the Cole–Cole plot, the slope of a straight line represents the strength of conductive loss. The greater the slope of the line, the stronger the conduction loss [18]. As seen in Figure S4, TAC@SiO2@Al2O3 exhibits a stronger polarization loss and conduction loss than TAC. In addition, the numerous heterogeneous interfaces (such as those between TAC, amorphous SiO2, and Al2O3) can heighten the interface polarization. Compared with a single TAC@SiO2@Al2O3 particle, the coupling of different TAC@SiO2@Al2O3 particles gives rise to more heterogeneous interfaces, further enhancing the interfacial polarization. The existence of defect sites (such as Schottky defects and Frenkel defects) in the flaky Al2O3 structure and the SiO2/Al2O3 heterostructure can induce the generation of a dipole polarization and an atomic polarization centered on each defect, thereby boosting the polarization relaxation [67,68,69]. The attenuation constants of TAC, TAC@SiO2, and TAC@SiO2@Al2O3 for incident EWs in the range of 0.5–18 GHz are shown in Figure S5. It is clear that TAC@SiO2@Al2O3 has a much greater attenuation capacity than TAC for incident EWs.

In order to visually depict the positive effects of the MSCNs, the power flow (V·A/m2), electric field (V/m), and power loss density (W/m3) of the TAC-based absorbers were simulated using the CST software, as shown in Figure 6. To guarantee the validity of the result, the simulated S11 coefficient and calculated RL curves of the TAC-based absorbers were compared, as shown in Figure S6. The consistency of the S11 and RL results proves the correctness of the simulation model. The circular spots in Figure 6(a) show that the power flow of TAC@SiO2 is noticeably higher than that of TAC based on their size and color. The power flow of TAC@SiO2@Al2O3 is greater in the upper portion of the absorber than that of TAC@SiO2. The power going into TAC@SiO2@Al2O3 at the lower portion of the absorber is less than that flowing into TAC@SiO2. The high conductivity of coupled TAC@SiO2@Al2O3, which results in a potent reflection for the incident EWs, is responsible for this phenomenon. Figure 6(b) shows the electric field (V/m) of the TAC-based absorbers. In the TAC-based absorbers, the electric field intensity decreases from top to bottom. The reduction in the electric field strength (where the electric field represents the microwaves) indicates that the loss ability for EWs of the MAMs becomes gradually stronger [70]. TAC@SiO2@Al2O3 has a lower electric field intensity in the upper portion of the absorber than TAC and TAC@SiO2. Thus, TAC@SiO2@Al2O3 provides the best EW attenuation capability.

Figure 6 
               (a) Power flow, (b) electric field, and (c) power loss density distribution diagrams of TAC, TAC@SiO2, and TAC@SiO2@Al2O3 with a thickness of 2.0 mm at 10.48 GHz.
Figure 6

(a) Power flow, (b) electric field, and (c) power loss density distribution diagrams of TAC, TAC@SiO2, and TAC@SiO2@Al2O3 with a thickness of 2.0 mm at 10.48 GHz.

4 Conclusion

In this study, a simple combination of the SP and SGM based on heterogeneous interface engineering is first proposed to prepare MCSNs on TAC. The thickness of the MCSNs was roughly 145–215 nm. The HTS and MAP of TAC coated with the MSCNs are significantly enhanced. The starting oxidation temperature of TAC@SiO2@Al2O3 is 800°C, which is about 400°C higher than that of TAC. After holding at 800°C for 1 h, the mass gain of TAC is only 2.32%, which is 14.70% less than that of TAC. The EAB of TAC@SiO2@Al2O3 is 3.25 GHz (8.68–11.27 and 11.63–12.29 GHz) at a thickness of 2.0 mm, which is 4.7 times more than that of TAC. The RLmin is reduced by a factor of 2.77, from −10.68 dB at 10.09 GHz to −29.55 dB at 10.52 GHz. This is because there are fewer transport pathways between oxygen and TAC as a result of MSCNs. Additionally, they increase the number of multiple reflection events, strengthen the scattering mechanism, and enhance the electronic polarization, interface polarization, and polarization relaxation. Such a simple strategy to improve the HTS and MAP of the matrix is useful in the design of MAMs with excellent MAP and HTS.

  1. Funding information: The present study was financially supported by the National Natural Science Foundation of China (No. 52202368), the Natural Science Foundation of Sichuan (Nos. 2022NSFSC0347 and 2023NSFSC0586), the Open Projects of Vanadium and Titanium Resource Comprehensive Utilization Key Laboratory of Sichuan Province (Nos. 2021FTSZ05 and 2021FTSZ11), the Open project of Sichuan Vanadium Titanium Materials Engineering Technology Research Center (Nos. 2022FTGC01 and 2022FTGC02), and the guiding science and technology projects of Panzhihua (No. 2021ZD-G-4).

  2. Author contributions: All authors have accepted responsibility for the entire content of this manuscript and approved its submission.

  3. Conflict of interest: The authors state no conflict of interest.

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Received: 2023-01-28
Revised: 2023-03-15
Accepted: 2023-04-05
Published Online: 2023-05-24

© 2023 the author(s), published by De Gruyter

This work is licensed under the Creative Commons Attribution 4.0 International License.

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  34. Low-cost and large-scale preparation of ultrafine TiO2@C hybrids for high-performance degradation of methyl orange and formaldehyde under visible light
  35. Utilization of waste glass with natural pozzolan in the production of self-glazed glass-ceramic materials
  36. Mechanical performance of date palm fiber-reinforced concrete modified with nano-activated carbon
  37. Melting point of dried gold nanoparticles prepared with ultrasonic spray pyrolysis and lyophilisation
  38. Graphene nanofibers: A modern approach towards tailored gypsum composites
  39. Role of localized magnetic field in vortex generation in tri-hybrid nanofluid flow: A numerical approach
  40. Intelligent computing for the double-diffusive peristaltic rheology of magneto couple stress nanomaterials
  41. Bioconvection transport of upper convected Maxwell nanoliquid with gyrotactic microorganism, nonlinear thermal radiation, and chemical reaction
  42. 3D printing of porous Ti6Al4V bone tissue engineering scaffold and surface anodization preparation of nanotubes to enhance its biological property
  43. Bioinspired ferromagnetic CoFe2O4 nanoparticles: Potential pharmaceutical and medical applications
  44. Significance of gyrotactic microorganisms on the MHD tangent hyperbolic nanofluid flow across an elastic slender surface: Numerical analysis
  45. Performance of polycarboxylate superplasticisers in seawater-blended cement: Effect from chemical structure and nano modification
  46. Entropy minimization of GO–Ag/KO cross-hybrid nanofluid over a convectively heated surface
  47. Oxygen plasma assisted room temperature bonding for manufacturing SU-8 polymer micro/nanoscale nozzle
  48. Performance and mechanism of CO2 reduction by DBD-coupled mesoporous SiO2
  49. Polyarylene ether nitrile dielectric films modified by HNTs@PDA hybrids for high-temperature resistant organic electronics field
  50. Exploration of generalized two-phase free convection magnetohydrodynamic flow of dusty tetra-hybrid Casson nanofluid between parallel microplates
  51. Hygrothermal bending analysis of sandwich nanoplates with FG porous core and piezomagnetic faces via nonlocal strain gradient theory
  52. Design and optimization of a TiO2/RGO-supported epoxy multilayer microwave absorber by the modified local best particle swarm optimization algorithm
  53. Mechanical properties and frost resistance of recycled brick aggregate concrete modified by nano-SiO2
  54. Self-template synthesis of hollow flower-like NiCo2O4 nanoparticles as an efficient bifunctional catalyst for oxygen reduction and oxygen evolution in alkaline media
  55. High-performance wearable flexible strain sensors based on an AgNWs/rGO/TPU electrospun nanofiber film for monitoring human activities
  56. High-performance lithium–selenium batteries enabled by nitrogen-doped porous carbon from peanut meal
  57. Investigating effects of Lorentz forces and convective heating on ternary hybrid nanofluid flow over a curved surface using homotopy analysis method
  58. Exploring the potential of biogenic magnesium oxide nanoparticles for cytotoxicity: In vitro and in silico studies on HCT116 and HT29 cells and DPPH radical scavenging
  59. Enhanced visible-light-driven photocatalytic degradation of azo dyes by heteroatom-doped nickel tungstate nanoparticles
  60. A facile method to synthesize nZVI-doped polypyrrole-based carbon nanotube for Ag(i) removal
  61. Improved osseointegration of dental titanium implants by TiO2 nanotube arrays with self-assembled recombinant IGF-1 in type 2 diabetes mellitus rat model
  62. Functionalized SWCNTs@Ag–TiO2 nanocomposites induce ROS-mediated apoptosis and autophagy in liver cancer cells
  63. Triboelectric nanogenerator based on a water droplet spring with a concave spherical surface for harvesting wave energy and detecting pressure
  64. A mathematical approach for modeling the blood flow containing nanoparticles by employing the Buongiorno’s model
  65. Molecular dynamics study on dynamic interlayer friction of graphene and its strain effect
  66. Induction of apoptosis and autophagy via regulation of AKT and JNK mitogen-activated protein kinase pathways in breast cancer cell lines exposed to gold nanoparticles loaded with TNF-α and combined with doxorubicin
  67. Effect of PVA fibers on durability of nano-SiO2-reinforced cement-based composites subjected to wet-thermal and chloride salt-coupled environment
  68. Effect of polyvinyl alcohol fibers on mechanical properties of nano-SiO2-reinforced geopolymer composites under a complex environment
  69. In vitro studies of titanium dioxide nanoparticles modified with glutathione as a potential drug delivery system
  70. Comparative investigations of Ag/H2O nanofluid and Ag-CuO/H2O hybrid nanofluid with Darcy-Forchheimer flow over a curved surface
  71. Study on deformation characteristics of multi-pass continuous drawing of micro copper wire based on crystal plasticity finite element method
  72. Properties of ultra-high-performance self-compacting fiber-reinforced concrete modified with nanomaterials
  73. Prediction of lap shear strength of GNP and TiO2/epoxy nanocomposite adhesives
  74. A novel exploration of how localized magnetic field affects vortex generation of trihybrid nanofluids
  75. Fabrication and physicochemical characterization of copper oxide–pyrrhotite nanocomposites for the cytotoxic effects on HepG2 cells and the mechanism
  76. Thermal radiative flow of cross nanofluid due to a stretched cylinder containing microorganisms
  77. In vitro study of the biphasic calcium phosphate/chitosan hybrid biomaterial scaffold fabricated via solvent casting and evaporation technique for bone regeneration
  78. Insights into the thermal characteristics and dynamics of stagnant blood conveying titanium oxide, alumina, and silver nanoparticles subject to Lorentz force and internal heating over a curved surface
  79. Effects of nano-SiO2 additives on carbon fiber-reinforced fly ash–slag geopolymer composites performance: Workability, mechanical properties, and microstructure
  80. Energy bandgap and thermal characteristics of non-Darcian MHD rotating hybridity nanofluid thin film flow: Nanotechnology application
  81. Green synthesis and characterization of ginger-extract-based oxali-palladium nanoparticles for colorectal cancer: Downregulation of REG4 and apoptosis induction
  82. Abnormal evolution of resistivity and microstructure of annealed Ag nanoparticles/Ag–Mo films
  83. Preparation of water-based dextran-coated Fe3O4 magnetic fluid for magnetic hyperthermia
  84. Statistical investigations and morphological aspects of cross-rheological material suspended in transportation of alumina, silica, titanium, and ethylene glycol via the Galerkin algorithm
  85. Effect of CNT film interleaves on the flexural properties and strength after impact of CFRP composites
  86. Self-assembled nanoscale entities: Preparative process optimization, payload release, and enhanced bioavailability of thymoquinone natural product
  87. Structure–mechanical property relationships of 3D-printed porous polydimethylsiloxane films
  88. Nonlinear thermal radiation and the slip effect on a 3D bioconvection flow of the Casson nanofluid in a rotating frame via a homotopy analysis mechanism
  89. Residual mechanical properties of concrete incorporated with nano supplementary cementitious materials exposed to elevated temperature
  90. Time-independent three-dimensional flow of a water-based hybrid nanofluid past a Riga plate with slips and convective conditions: A homotopic solution
  91. Lightweight and high-strength polyarylene ether nitrile-based composites for efficient electromagnetic interference shielding
  92. Review Articles
  93. Recycling waste sources into nanocomposites of graphene materials: Overview from an energy-focused perspective
  94. Hybrid nanofiller reinforcement in thermoset and biothermoset applications: A review
  95. Current state-of-the-art review of nanotechnology-based therapeutics for viral pandemics: Special attention to COVID-19
  96. Solid lipid nanoparticles for targeted natural and synthetic drugs delivery in high-incidence cancers, and other diseases: Roles of preparation methods, lipid composition, transitional stability, and release profiles in nanocarriers’ development
  97. Critical review on experimental and theoretical studies of elastic properties of wurtzite-structured ZnO nanowires
  98. Polyurea micro-/nano-capsule applications in construction industry: A review
  99. A comprehensive review and clinical guide to molecular and serological diagnostic tests and future development: In vitro diagnostic testing for COVID-19
  100. Recent advances in electrocatalytic oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid: Mechanism, catalyst, coupling system
  101. Research progress and prospect of silica-based polymer nanofluids in enhanced oil recovery
  102. Review of the pharmacokinetics of nanodrugs
  103. Engineered nanoflowers, nanotrees, nanostars, nanodendrites, and nanoleaves for biomedical applications
  104. Research progress of biopolymers combined with stem cells in the repair of intrauterine adhesions
  105. Progress in FEM modeling on mechanical and electromechanical properties of carbon nanotube cement-based composites
  106. Antifouling induced by surface wettability of poly(dimethyl siloxane) and its nanocomposites
  107. TiO2 aerogel composite high-efficiency photocatalysts for environmental treatment and hydrogen energy production
  108. Structural properties of alumina surfaces and their roles in the synthesis of environmentally persistent free radicals (EPFRs)
  109. Nanoparticles for the potential treatment of Alzheimer’s disease: A physiopathological approach
  110. Current status of synthesis and consolidation strategies for thermo-resistant nanoalloys and their general applications
  111. Recent research progress on the stimuli-responsive smart membrane: A review
  112. Dispersion of carbon nanotubes in aqueous cementitious materials: A review
  113. Applications of DNA tetrahedron nanostructure in cancer diagnosis and anticancer drugs delivery
  114. Magnetic nanoparticles in 3D-printed scaffolds for biomedical applications
  115. An overview of the synthesis of silicon carbide–boron carbide composite powders
  116. Organolead halide perovskites: Synthetic routes, structural features, and their potential in the development of photovoltaic
  117. Recent advancements in nanotechnology application on wood and bamboo materials: A review
  118. Application of aptamer-functionalized nanomaterials in molecular imaging of tumors
  119. Recent progress on corrosion mechanisms of graphene-reinforced metal matrix composites
  120. Research progress on preparation, modification, and application of phenolic aerogel
  121. Application of nanomaterials in early diagnosis of cancer
  122. Plant mediated-green synthesis of zinc oxide nanoparticles: An insight into biomedical applications
  123. Recent developments in terahertz quantum cascade lasers for practical applications
  124. Recent progress in dielectric/metal/dielectric electrodes for foldable light-emitting devices
  125. Nanocoatings for ballistic applications: A review
  126. A mini-review on MoS2 membrane for water desalination: Recent development and challenges
  127. Recent updates in nanotechnological advances for wound healing: A narrative review
  128. Recent advances in DNA nanomaterials for cancer diagnosis and treatment
  129. Electrochemical micro- and nanobiosensors for in vivo reactive oxygen/nitrogen species measurement in the brain
  130. Advances in organic–inorganic nanocomposites for cancer imaging and therapy
  131. Advancements in aluminum matrix composites reinforced with carbides and graphene: A comprehensive review
  132. Modification effects of nanosilica on asphalt binders: A review
  133. Decellularized extracellular matrix as a promising biomaterial for musculoskeletal tissue regeneration
  134. Review of the sol–gel method in preparing nano TiO2 for advanced oxidation process
  135. Micro/nano manufacturing aircraft surface with anti-icing and deicing performances: An overview
  136. Cell type-targeting nanoparticles in treating central nervous system diseases: Challenges and hopes
  137. An overview of hydrogen production from Al-based materials
  138. A review of application, modification, and prospect of melamine foam
  139. A review of the performance of fibre-reinforced composite laminates with carbon nanotubes
  140. Research on AFM tip-related nanofabrication of two-dimensional materials
  141. Advances in phase change building materials: An overview
  142. Development of graphene and graphene quantum dots toward biomedical engineering applications: A review
  143. Nanoremediation approaches for the mitigation of heavy metal contamination in vegetables: An overview
  144. Photodynamic therapy empowered by nanotechnology for oral and dental science: Progress and perspectives
  145. Biosynthesis of metal nanoparticles: Bioreduction and biomineralization
  146. Current diagnostic and therapeutic approaches for severe acute respiratory syndrome coronavirus-2 (SARS-COV-2) and the role of nanomaterial-based theragnosis in combating the pandemic
  147. Application of two-dimensional black phosphorus material in wound healing
  148. Special Issue on Advanced Nanomaterials and Composites for Energy Conversion and Storage - Part I
  149. Helical fluorinated carbon nanotubes/iron(iii) fluoride hybrid with multilevel transportation channels and rich active sites for lithium/fluorinated carbon primary battery
  150. The progress of cathode materials in aqueous zinc-ion batteries
  151. Special Issue on Advanced Nanomaterials for Carbon Capture, Environment and Utilization for Energy Sustainability - Part I
  152. Effect of polypropylene fiber and nano-silica on the compressive strength and frost resistance of recycled brick aggregate concrete
  153. Mechanochemical design of nanomaterials for catalytic applications with a benign-by-design focus
Heruntergeladen am 21.1.2026 von https://www.degruyterbrill.com/document/doi/10.1515/ntrev-2022-0545/html?lang=de
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