Zhao Qingyuan, Chen Guoliang, Wang Shuqi, Zou Yongchun, Xie Enyu, Peng Zijian, Yao Junteng, Ouyang Jiahu, Wang Yaming, Jia Dechang, Zhou Yu
State Key Laboratory of Precision Welding & Joining of Materials and Structures, Harbin Institute of Technology, Harbin, 150001, China.
Institute for Advanced Ceramics, Harbin Institute of Technology, Harbin, 150080, China.
Small. 2025 Sep 12:e08247. doi: 10.1002/smll.202508247.
Conventional entropy-driven strategies introduce lattice distortion to enhance phonon scattering, yet do not always lead to improved photon absorption for high emissivity thermal protection. Herein, an effective strategy of energy-level engineering driven multi rare earth ion doping in rare earth hafnate systems for broadband high emissivity, aiming to solve the transparency to thermal radiation of rare earth hafnate materials is proposed. The multiple dopants, including La, Sm, Eu, and Gd, are utilized to absorb the thermal radiation energy alternatively by their characteristic 4f-4f transition of electronic energy levels. According to theoretical optimization and experimental verification, (LaSmEuGd)HfO (4RH-Eu) exhibits the highest average emissivity of 0.86 at 400 °C across 2.5-14 µm and persist such the high level up to 1200 °C. Such high emissivity of 4RH-Eu is beneficial to its thermal radiation shielding performance improvement, leading to its transmittance below 0.12. The synergistic effect of those dopants contourites to a broadband high photon absorption, and accordingly high emissivity across the whole thermal radiation range. These findings lay the theoretical foundation for the next-generation radiation thermal protection materials.
传统的熵驱动策略会引入晶格畸变以增强声子散射,但对于高发射率热防护而言,并不总能提高光子吸收。在此,提出了一种在稀土铪酸盐体系中通过能级工程驱动多稀土离子掺杂实现宽带高发射率的有效策略,旨在解决稀土铪酸盐材料对热辐射的透明性问题。包括La、Sm、Eu和Gd在内的多种掺杂剂通过其电子能级的特征4f-4f跃迁交替吸收热辐射能量。根据理论优化和实验验证,(LaSmEuGd)HfO(4RH-Eu)在400℃下2.5-14μm范围内平均发射率最高可达0.86,并在高达1200℃时仍保持这一高水平。4RH-Eu的这种高发射率有利于其热辐射屏蔽性能的提高,使其透过率低于0.12。这些掺杂剂的协同作用促成了宽带高光子吸收,进而在整个热辐射范围内实现高发射率。这些发现为下一代辐射热防护材料奠定了理论基础。