低温快速制备具有雷达/红外双模传输特性的莫来石陶瓷

doi:10.15541/jim20250489

摘要/Abstract

摘要： 随着高速飞行器技术的快速发展,对极端环境下兼具雷达透波与红外传输功能的材料提出迫切需求。莫来石陶瓷因具有优异的高温力学性能、介电性能及一定的红外透明性,成为理想候选材料之一。然而,莫来石陶瓷的传统制备方法温度高、工艺复杂,限制了其实际应用。本研究开发了一种低成本、短周期的莫来石陶瓷低温制备方法,选用高活性廉价多孔原料,采用放电等离子烧结(SPS)技术,利用介孔结构坍塌释放高活性表面与SPS场效应的协同作用,在1200 ℃下实现莫来石陶瓷的一步快速烧结制备,显著降低烧结温度和缩短制备周期。深入研究了烧结工艺参数对陶瓷的微结构、力学性能、介电性能以及红外传输性能的影响。1200 ℃、70 MPa、升温速率100 ℃·min^-1条件下制备陶瓷密度可达3.06 gcm^-3,孔隙率低至1.6%;弯曲强度达152.9 MPa,弯曲模量达87.1 GPa。较高的机械压力促使莫来石晶粒由针状向短柱状转变,断裂模式由沿晶断裂过渡为穿晶断裂,从而获得优异的力学性能;在8~16 GHz波段的平均介电常数为6.77且呈现出良好的稳定性,损耗角正切值为4.7×10^-4,透波率高于70%,这得益于陶瓷烧结后的残余气孔显著降低了介质极化。同时,近红外波段透过率达45.11%,在雷达/红外双模透波材料领域展现出良好的应用前景。

关键词: 莫来石陶瓷, 放电等离子烧结, 低温制备, 介电性能, 红外透过率

Abstract: Rapid development of high-speed aircraft technology poses an urgent demand for materials capable of integrating radar wave transmission and infrared transmission under extreme environments. Mullite ceramics have emerged as a promising candidate materials due to their excellent high-temperature mechanical properties, dielectric properties, and inherent infrared transparency. However, the traditional preparation methods of mullite ceramics typically require high sintering temperature and involve complex processes, which limit their practical applications. In this work, one-step rapid sintering of mullite ceramics at 1200 ℃ was successfully achieved by utilizing highly active, low-cost porous raw materials and spark plasma sintering (SPS) technology, significantly reducing the sintering temperature and shortening the preparation cycle. This process relies on the synergistic effect between the high-active surfaces released by mesoporous structure collapse and the SPS field effect, thereby developing a low-cost, short-cycle, and low-temperature preparation process. The effects of sintering process parameters on the microstructure, mechanical properties, dielectric properties, and infrared transmission properties of the ceramics were investigated in depth. Under the conditions of 1200 ℃, 70 MPa and a heating rate of 100 ℃·min^-1, the prepared ceramics exhibit a density of up to 3.06 g·cm^-3 and a porosity as low as 1.6%; the flexural strength reaches 152.9 MPa and the flexural modulus is 87.1 GPa. The high mechanical pressure promotes the transformation of mullite grains from acicular to short columnar, and the fracture mode transitions from intergranular to transgranular, endowing the ceramics with excellent mechanical properties. In the 8-16 GHz band, the average dielectric constant is 6.77 with good stability, the dielectric loss tangent (tanδ) is 4.7×10^-4, and the wave transmittance exceeds 70%, which is attributed to the significant reduction in dielectric polarization caused by the residual pores in the sintered ceramics. Meanwhile, the transmittance in the near-infrared (NIR) band reaches 45.11%, demonstrating promising application prospects in the field of radar/infrared dual-mode wave-transparent materials.

Key words: mullite ceramics, spark plasma sintering, low-temperature preparation, dielectric properties, infrared transmittance

中图分类号:

TB32

崔楷敏, 李端, 曾雷, 彭江山, 王衍飞, 刘荣军. 低温快速制备具有雷达/红外双模传输特性的莫来石陶瓷[J]. 无机材料学报, DOI: 10.15541/jim20250489.

CUI Kaimin, LI Duan, ZENG Lei, PENG Jiangshan, WANG Yanfei, LIU Rongjun. Rapid Low-Temperature Fabrication of Mullite Ceramics with Dual-Mode Radar/Infrared Transmission Characteristics[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20250489.

参考文献

[1] KOČÍ J, HAMÁČEK J, MACHÁČEK J,et al. Effect of long-term high-temperature exposure in a controlled atmosphere on mullite-corundum ceramics for advanced applications in nuclear power technology. Ceramics International, 2024, 50(13): 24273.
[2] ROY S.Properties and advanced applications of porous ceramic composites.Open Ceramics, 2025, 21: 100714.
[3] LIN Y W, JING Z, CHEN H T,et al. Ablative properties of SiC_p doped C_f/Li₂O-Al₂O₃-SiO₂ composites. Journal of Inorganic Materials, 2025, 40(10): 1153.
[4] CHENG X T, LIU Y T, SI Y,et al. Direct synthesis of highly stretchable ceramic nanofibrous aerogels via 3D reaction electrospinning. Nature Communications, 2022, 13: 2637.
[5] WANG Y L, PENG Z W, TIAN R,et al. Microwave-transparent refractory materials for high-temperature metallurgical applications. Journal of Alloys and Compounds, 2025, 1033: 181063.
[6] ZHU Z X, WANG F, YAO H J.High-temperature insulation property of opacifier-doped Al₂O₃-SiO₂ aerogel/mullite fiber composites.Journal of Inorganic Materials, 2018, 33(9): 969.
[7] K S, BABU N, GOVINDARAJAN S,et al. Hot corrosion behaviour of mullite thermal barrier coatings for marine diesel engines. Ceramics International, 2024, 50(2): 2808.
[8] GAO J M, WANG B, DU Z Y,et al. Molten salt synthesis of mullite whiskers entirely derived from fly ash for electronic packaging toughening ceramic applications. Journal of Materials Research and Technology, 2022, 21: 3719.
[9] ZHANG J X, ZHANG M J, GU H Z,et al. Processing and properties of Al-Si microcapsules with a biomimetic-corrugated structure and corundum-mullite composite shell. Journal of Materiomics, 2025, 11(3): 100906.
[10] LI X, HU C, LIU Q,et al. Fluoride transparent ceramics for solid-state lasers: A review. Journal of Advanced Ceramics, 2024, 13(12): 1891.
[11] XU J, SHAO Y Q, FENG X Y,et al. Low sintering shrinkage porous ceramics: Principles, progress, and perspectives. Journal of Advanced Ceramics, 2025, 14(2): 9221015.
[12] SHAO J H, BAI C Y, LI X Y,et al. Open-cell mullite ceramic foams derived from porous geopolymer precursors with tailored porosity. Journal of Advanced Ceramics, 2023, 12(2): 279.
[13] GREGOROVIČOVÁ E, POSPÍŠIL J. Ceramic filters for high-temperature flue gas filtration and their regeneration: A review of the current state of knowledge.Process Safety and Environmental Protection, 2024, 190: 688.
[14] DUN Y H, LIU Y F, XU J,et al. Advancements in rare earth mullite oxides(AMn₂O₅)for catalytic oxidation: Structure, activity and design strategies. Applied Catalysis A: General, 2024, 685: 119872.
[15] GUO X Z, LI W Y, NAKANISHI K,et al. Preparation of mullite monoliths with well-defined macropores and mesostructured skeletons via the sol-gel process accompanied by phase separation. Journal of the European Ceramic Society, 2013, 33(10): 1967.
[16] SANAD M M S, RASHAD M M, ABDEL-AAL E A,et al. Synthesis and characterization of nanocrystalline mullite powders at low annealing temperature using a new technique. Journal of the European Ceramic Society, 2012, 32(16): 4249.
[17] XU H Q, LI D X, LUO R W,et al. Low-temperature synthesis of mullite and its structural evolution during mullitization. Ceramics International, 2025, 51(6): 7100.
[18] KAYA C, HE J Y, GU X,et al. Nanostructured ceramic powders by hydrothermal synthesis and their applications. Microporous and Mesoporous Materials, 2002, 54(1-2): 37.
[19] LIU R P, XIANG D P.Recycling photovoltaic silicon waste for fabricating porous mullite ceramics by low-temperature reaction sintering.Journal of the European Ceramic Society, 2021, 41(12): 5957.
[20] HUO W L, ZHANG X Y, CHEN Y G,et al. Novel mullite ceramic foams with high porosity and strength using only fly ash hollow spheres as raw material. Journal of the European Ceramic Society, 2018, 38(4): 2035.
[21] MA B Y, SU C, REN X M,et al. Preparation and properties of porous mullite ceramics with high-closed porosity and high strength from fly ash via reaction synthesis process. Journal of Alloys and Compounds, 2019, 803: 981.
[22] AKPINAR S, KUSOGLU I M, ERTUGRUL O,et al. In situ mullite foam fabrication using microwave energy. Journal of the European Ceramic Society, 2012, 32(4): 843.
[23] HAN L, DENG X G, LI F L,et al. Preparation of high strength porous mullite ceramics via combined foam-gelcasting and microwave heating. Ceramics International, 2018, 44(12): 14728.
[24] LÜ Q K, DONG X F, ZHU Z W,et al. Environment-oriented low-cost porous mullite ceramic membrane supports fabricated from coal gangue and bauxite. Journal of Hazardous Materials, 2014, 273: 136.
[25] VIJAYAN S, WILSON P, PRABHAKARAN K.Ultra low-density mullite foams by reaction sintering of thermo-foamed alumina-silica powder dispersions in molten sucrose.Journal of the European Ceramic Society, 2017, 37(4): 1657.
[26] FUKUSHIMA M, YOSHIZAWA Y.Fabrication and morphology control of highly porous mullite thermal insulators prepared by gelation freezing route.Journal of the European Ceramic Society, 2016, 36: 2947.
[27] HOU Z P, ZHANG B, ZHANG R,et al. Fabrication of highly porous mullite microspheres via oil-drop molding accompanied by freeze casting. Ceramics International, 2017, 43(12): 8809.
[28] LI J S, ZENG L, LIU R J,et al. Functional strontium tantalum oxynitride ceramics: efficient synthesis, densification and dielectric performance. Journal of Inorganic Materials, 2023, 38(8): 885.
[29] IRSHAD H M, HAKEEM A S, AHMED T,et al. Tribological and thermomechanical behaviour of alumina-based hybrid nanocomposites. Materials Chemistry and Physics, 2025, 341: 130828.
[30] YANG J W, LEI L W, ZHANG J Y.Preparation of alumina ceramicsvia a two-step sintering process. Materials, 2025, 18(8): 1789.
[31] MAJIDIAN H, NIKZAD L, FARVIZI M,et al. Reactive spark plasma sintering of alumina-mullite-zirconia composites. Ceramics International, 2025, 51(23): 38636.
[32] REN L, FU Z Y, WANG Y C,et al. Fabrication of transparent mullite ceramic by spark plasma sintering from powders synthesized via sol-gel process combined with pulse current heating. Materials & Design, 2015, 83: 753.
[33] LIU Y, ZHANG K Y, LI T Y,et al. Electric-field assisted joining technology for the ceramics materials: current status and development trend. Journal of Inorganic Materials, 2023, 38(2): 113.
[34] HUANG P, ZHOU B Y, ZHENG Q,et al. Nano wave plates structuring and index matching in transparent hydroxyapatite-YAG: Ce composite ceramics for high luminous efficiency white light-emitting diodes. Advanced Materials, 2020, 32(1): 1905951.
[35] FARBER E M, SERAPHIM N M, TAMAKUWALA K,et al. Porous materials: the next frontier in energy technologies. Science, 2025, 390(6772): 9391.
[36] LI X Q, CHEN F Y, ZHANG L L,et al. Preparation of low-dielectric porous silica ceramics by sintering mesoporous silica. Integrated Ferroelectrics, 2012, 135(1): 144.
[37] YU S Y, LI Z F, CUI J P,et al. Preparation of pressureless-sintered dense cordierite ceramics with high flexural strength by mesoporous powder. Ceramics International, 2025, 51(17): 24202.
[38] FANG H L, GU S J, FAN S J, et al. Rapidly fabricating Y₂O₃ transparent ceramics at low temperature by SPS with mesoporous powder. Journal of the American Ceramic Society, 20230401, 106(4): 2491.
[39] HENNING L M, MÜLLER J T, SMALES G J,et al. Hierarchically porous and mechanically stable monoliths from ordered mesoporous silica and their water filtration potential. Nanoscale Advances, 4(18): 3892.
[40] PÉREZ J M, RINCÓN J Ma, ROMERO M. Effect of moulding pressure on microstructure and technological properties of porcelain stoneware.Ceramics International, 2012, 38(1): 317.
[41] HSIUNG C H H, PYZIK A J, DE CARLO F,et al. Microstructure and mechanical properties of acicular mullite. Journal of the European Ceramic Society, 2013, 33(3): 503.
[42] XIA L, YANG Y N, ZHANG X Y,et al. Crystal structure and wave-transparent properties of lithium aluminum silicate glass-ceramics. Ceramics International, 2018, 44(12): 14896.
[43] SHANG X B, ZHAI D, LIU M H,et al. Dielectric properties and electromagnetic wave transmission performance of aluminium silicate fibreboard at 915 MHz and 2450 MHz. Ceramics International, 2021, 47(6): 7539.
[44] TU G S, XU P Y, CHEN B W,et al. Reaction-sintered highly transparent MgGa₂O₄ ceramics with enhanced dielectric properties. Journal of the European Ceramic Society, 2025, 45(3): 117024.
[45] AHMADI S, YEKTA B E, SARPOOLAKY H,et al. Preparation of monolithic transparent mullite-based glass-ceramics by the sol-gel method. Journal of Non-Crystalline Solids, 2022, 575: 121186.
[46] YE J H, ZHOU Z Z, HU C, et al. Yb:Sc₂O₃ transparent ceramics fabricated from Co-precipitated nano-powders: microstructure and optical property. Journal of Inorganic Materials, 2025, 40(2): 215.
[47] HŘÍBALOVÁ S, PABST W. Modeling light scattering by spherical pores for calculating the transmittance of transparent ceramics-all you need to know.Journal of the European Ceramic Society, 2021, 41(4): 2169.
[48] PABST W, HŘÍBALOVÁ S. Light scattering models for describing the transmittance of transparent and translucent alumina and zirconia ceramics.Journal of the European Ceramic Society, 2021, 41(3): 2058.
[49] 张桂敏, 王玉成, 傅正义, 等. 单相胶的化学组成对莫来石微观结构及红外透波性能的影响. 硅酸盐学报, 2009, 37(6): 987.
[50] SHEPILOV M, DYMSHITS O, ALEKSEEVA I,et al. Structure and anomalous light scattering of Er-doped transparent glass-ceramics containing ZnO nanocrystals. Journal of Non-Crystalline Solids, 2021, 571: 121067.