碳纳米角限域TiC和MoC纳米颗粒的耐腐蚀及吸波性能研究

doi:10.11949/0438-1157.20250907

摘要/Abstract

摘要：

近年来，吸波材料在实际应用环境应用中，如海洋环境、高温条件和潮湿大气等恶劣环境中，极易被腐蚀氧化而失效。为满足复杂应用环境需求，吸波材料必须具备卓越的耐腐蚀性和热稳定性。本研究通过高温碳化工艺成功合成了新型复合材料——碳纳米角限域TiC和MoC纳米颗粒（TiC/MoC@NCNHs）。该复合材料在微波吸收性能上表现优异，并展现出卓越的耐腐蚀性和热稳定性能。碳纳米角因其优异的物理和化学稳定性以及抗渗透性，可作原子级屏障，保护基材免受腐蚀和氧化。MoC的引入增强了TiC/MoC@NCNHs复合材料的磁损耗，改善了阻抗匹配，低密度的TiC提供了显著的导电损耗并减少了复合材料的质量。这种多功能材料可在高温高湿及海洋环境中实现持续性能。TiC/MoC@NCNHs复合材料实现了最低反射损耗-50.89 dB和5.87 GHz的有效吸收带。此外，该复合材料在3.5% NaCl溶液中浸泡30天后仍保持低腐蚀电流，展现出优异的抗腐蚀性能，且在高温处理后仍保持最佳反射损耗，证明其具有优异的热稳定性。

关键词: 微波吸收, 碳纳米角, 阻抗匹配, 反射损耗, 腐蚀保护

Abstract:

Environmental factors pose substantial challenges to the practical utilization of microwave absorbing materials, particularly in harsh conditions such as oceanic environments, elevated temperatures, and humid atmospheres. To meet these demands, materials must possess exceptional corrosion, oxidation, and high-temperature resistance. This study presents the successful synthesis of a novel composite, TiC and MoC Nanoparticles Confined in Carbon Nanohorns (TiC/MoC@NCNHs), via a high-temperature carbonization process. The resulting composite excels in microwave absorption and demonstrates outstanding resilience to corrosion and thermal oxidation. The carbon nanohorns, celebrated for their superior physical and chemical stability and impermeability, function as an atomic-scale shield that protects the embedded nanoparticles against corrosion and oxidation. The integration of MoC enhances the magnetic loss of the TiC/MoC@NCNHs composites, thereby improving impedance matching, while the low-density TiC provides significant conductive loss and reduces the mass of composite. This multifunctional material is adept for sustained performance in severe environments. The TiC/MoC@NCNHs composites have achieved a minimum reflection loss of -50.89 dB and an effective absorption bandwidth of up to 5.87 GHz. Moreover, the composites retained a low corrosion current after 30 days of immersion in a 3.5% NaCl solution, showing excellent corrosion resistance, and maintained optimal reflection loss after high temperature treatment, demonstrating excellent high temperature resistance.

Key words: microwave absorption, carbon nanohorns, impedance matching, reflection loss, corrosion protection

中图分类号:

TB333

许莉, 王栖, 朱启程, 王钊禹, 任金翠, 南艳丽. 碳纳米角限域TiC和MoC纳米颗粒的耐腐蚀及吸波性能研究[J]. 化工学报, DOI: 10.11949/0438-1157.20250907.

Li XU, Qi WANG, Qicheng ZHU, Zhaoyu WANG, Jincui REN, Yanli NAN. Corrosion Resistance and Microwave Absorption Properties of TiC and MoC Nanoparticles Confined in Carbon Nanohorns[J]. CIESC Journal, DOI: 10.11949/0438-1157.20250907.

图/表 8

图1 (a) TiC/MoC@NCNHs的透射电子显微镜（TEM）图像（插图为SAED图案），(b) TiC/MoC@NCNHs的扫描电子显微镜（SEM）图像，(b-f) TiC/MoC@NCNHs的高分辨率透射电子显微镜（HRTEM）图像

Fig 1 (a) TEM image of TiC/MoC@NCNHs (inset of the SAED pattern), (b) SEM image of TiC/MoC@NCNHs (b-f) HRTEM images of TiC/MoC@NCNHs

图2 (a) 1-TiC-1-MoC的XPS全谱； (a1-a3) C、Mo和Ti峰的高分辨率光谱；(b) TiC/MoC@NCNHs的XRD图谱；(c) TiC/MoC@NCNHs的拉曼光谱

Fig 2 (a) Wide XPS spectra of 1-TiC-1-MoC. (a1-a3) The high-resolution spectrum of C, Mo and Ti peaks. (b) Raman spectra of TiC/MoC@NCNHs. (c) XRD patterns of TiC/MoC@NCNHs.

图3 TiC/MoC@NCNHs的电磁参数： (a) 实部介电常数，(b) 虚部介电常数，(c) 介电损耗正切，(d) 实部磁导率，(e) 虚部磁导率，(f) 磁损耗正切

Fig. 3 Electromagnetic parameters of TiC/MoC@NCNHs: (a) real permittivity, (b) imaginary permittivity, (c) dielectric loss tangents, (d) real permeability, (e) imaginary permeability, and (f) magnetic loss tangents.

图4 TiC/MoC@NCNHs的Cole-Cole曲线

Fig 4 Cole-Cole semicircles of TiC/MoC@NCNHs.

图5 (a) TiC/MoC@NCNHs的涡流损耗C0，(b) TiC/MoC@NCNHs的衰减常数α

Fig 5 (a) Frequency dependences of C0 for TiC/MoC@NCNHs, (b) Attenuation constant α of TiC/MoC@NCNHs.

图6 (a1-a2) 1-TiC-1-MoC的RL值和阻抗匹配Z图， (b1-b2) 1-TiC-2-MoC的RL值和阻抗匹配Z图，(c1-c2) 2-TiC-1-MoC的RL值和阻抗匹配Z图

Fig 6 (a1-a2) The RL values and impedance matching Z of 1-TiC-1-MoC. (b1-b2) The RL values and impedance matching Z of 1-TiC-2-MoC. (c1-c2) The RL values and impedance matching Z of 2-TiC-1-MoC.

图7 (a) 热处理后TiC/MoC@NCNHs的XRD谱图，(b) 热处理后1-TiC-1-MoC的XPS谱图，(c) 1-TiC-1-MoC-450℃的RL值，(d) 1-TiC-2-MoC-450℃的RL值，(e) 2-TiC-1-MoC-450℃的RL值。

Fig 7 (a) XRD patterns of heat-treated TiC/MoC@NCNHs. (b) XPS patterns of heat-treated 1-TiC-1-MoC (c) The RL values of 1-TiC-1-MoC-450℃. (d) The RL values of 1-TiC-2-MoC-450℃. (e) The RL values of 2-TiC-1-MoC-450℃.

图8 TiC/MoC@NCNHs复合材料、裸露的Q235钢和纯EP在3.5% NaCl溶液中浸泡30天后的电化学特性表征：（a）Bode图，（b）动极化曲线，（c）TiC/MoC@NCNHs可能的耐腐蚀机制示意图。

Fig 8 Electrochemical characterization of the TiC/MoC@NCNHs composites, bare Q235 and pure EP after the immersion in a 3.5 wt% NaCl solution for 30 days (a) Bode plots, (b) Potentiodynamic polarization curves, (c)Schematic illustration of the possible corrosion protection mechanism for the TiC/MoC@NCNHs

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