Direct 3D Electrospinning of Phase-Locked Amorphous/Crystalline Ceramic Fiber Aerogels with Enhanced Mechanical Properties and Thermal Stability

Abstract

Ceramic fiber aerogels have emerged as promising candidates for thermal insulation in extreme environments, yet their mechanical toughness and high-temperature stability remain critical bottlenecks. To address this challenge, we propose a multiscale structural engineering strategy integrated with scalable direct three-dimensional (3D) electrospinning technology to fabricate silicon–aluminum ceramic fiber aerogels (SACFAs) with a phase-locked amorphous/crystalline architecture. The entangled network constructed by crimped ribbon-shaped fibers reinforces the fiber junctions and provides ample deformation space. Concurrently, aluminum doping introduces Si–O–Al bonds and forms a phase-locked structure wherein nano-alumina/mullite crystallites are uniformly embedded within the amorphous silica matrix. This unique architecture intrinsically reinforces the fibers through grain boundary pinning, thereby synergistically enhancing both mechanical properties and thermal stability. The SACFAs exhibit a superior combination of tensile performance (a high tensile strength of 0.4772 MPa with a fracture strain of 47.58%), compressive resilience (complete recovery after 80% compressive strain, corresponding to a maximum compressive stress of 120.92 kPa), and near-zero Poisson’s ratio. The material maintains stable mechanical properties from −196 °C to 1200 °C, with a low thermal conductivity of 0.03254 W·m⁻¹·K⁻¹, a low density of 22.70 mg·cm⁻³, and a high porosity of 98.72%. Additionally, the direct 3D electrospinning method delivers a single-nozzle production rate of 1800 cm³·h⁻¹, highlighting its scalability for industrial production. This work provides a promising strategy for developing lightweight, flexible thermal insulation materials for aerospace and advanced energy applications.

Graphical Abstract

Keywords

Ceramic fiber aerogels / 3D electrospinning / Mechanical properties / Thermal stability / Thermal insulation

References

[1] Hou J, Chen R, Tan C, Zeng Y, Liu T, Fu Q, Zhang J. A biomimetic bifunctional composite enabling integrated thermal protection and insulation for ultra-high-temperature TPS. Adv Funct Mater, 2026, 36 ArticleID: e26634

[2] Guan Y, Gu C, Qiu G, Wu J, Lian X, Wang X, Fei B, Wang W, Zhang D, Guo W. A triple-network aerogel composite with thermally induced phoenix-like transformation: from elastic ablation resistance to efficient EMI shielding. Adv Funct Mater, 2026, 36 ArticleID: e28431

[3] Liu Z, Tang J, Zhang L, Liu F, Ye Y. High-entropy ceramic aerogels for thermal insulation: preparation, material systems, and compositional design strategies. Chem Eng J, 2025, 525 ArticleID: 169745

[4] Sun R, Liu Y, Liu F. A new vision in thermal insulation: a comprehensive review of silica aerogel coatings with sustainable potential. Renew Sustain Energy Rev, 2026, 233 ArticleID: 116865

[5] Zhang X, Han Y, Feng J, Jiang C, Zhang J, Liu W. Lightweight and flame-retardant nanocellulose porous materials with robust mechanical properties fabricated via microwave-assisted DES pretreatment. Carbohydr Polym, 2026, 382 ArticleID: 125291

[6] Fu S, Liu D, Deng Y, Li M, Zhao H, Guo J, Zhou J, Zhang P, Wang C, Yu H, Dang S, Zhang J, Hao M, Li H, Xu X. Medium-entropy ceramic aerogels for robust thermal sealing. J Mater Chem A, 2023, 11: 742

[7] Jiang X, Du T, Fan H, Liu J, Su Y, He P, Chen H, Hu L, Zhang Y, Zhang Q. Superelastic high-entropy oxide ceramic aerogels for thermal superinsulation and sealing at extreme conditions. Adv Sci, 2025, 3e16840

[8] Wu C, Jiang J, Dong C, Zhao L, Liu J, Liu C, Deng H, Hui KN, Pang H, Yan Y, Liu M. Remarkably enhance the stealth/resistance/mechanical properties of silica-zirconia ceramic aerogel by phase transitions and interface evolution. Adv Funct Mater, 2025, 35 ArticleID: 2505742

[9] Wang F, Dou L, Dai J, Li Y, Huang L, Si Y, Yu J, Ding B. In situ synthesis of biomimetic silica nanofibrous aerogels with temperature-invariant superelasticity over one million compressions. Angew Chem Int Ed Engl, 2020, 59: 8285

[10] Li P, Zhang X, Li Y, Zhao C, Yu J, Si Y. Electrospun Nanofiber-Based Ceramic Aerogels: Synergistic Strategies for Design and Functionalization. Nano-Micro Lett, 2025, 18: 23

[11] An L, Wang J, Petit D, Armstrong JN, Hanson K, Hamilton J, Souza M, Zhao D, Li C, Liu Y, Huang Y, Hu Y, Li Z, Shao Z, Desjarlais AO, Ren S. An all-ceramic, anisotropic, and flexible aerogel insulation material. Nano Lett, 2020, 20: 3828

[12] Huang T, Zhu Y, Zhu J, Yu H, Zhang Q, Zhu M. Self-reinforcement of light, temperature-resistant silica nanofibrous aerogels with tunable mechanical properties. Adv Fiber Mater, 2020, 2: 338

[13] Si Y, Yu J, Tang X, Ge J, Ding B. Ultralight nanofibre-assembled cellular aerogels with superelasticity and multifunctionality. Nat Commun, 2014, 5: 5802

[14] Si Y, Wang X, Dou L, Yu J, Ding B. Ultralight and fire-resistant ceramic nanofibrous aerogels with temperature-invariant superelasticity. Sci Adv, 2018, 4 ArticleID: eaas8925

[15] Dou L, Zhang X, Shan H, Cheng X, Si Y, Yu J, Ding B. Interweaved cellular structured ceramic nanofibrous aerogels with superior bendability and compressibility. Adv Funct Mater, 2020, 30 ArticleID: 2005928

[16] Wang S, Zhu C, Wang F, Yu J, Zhang S, Ding B. Ultralight and superelastic curly micro/nanofibrous aerogels by direct electrospinning enable high-performance warmth retention. Small, 2023, 19 ArticleID: 2302835

[17] Xu Z, Liu Y, Xin Q, Dai J, Yu J, Cheng L, Liu Y-T, Ding B. Ceramic meta-aerogel with thermal superinsulation up to 1700 °C constructed by self-crosslinked nanofibrous network via reaction electrospinning. Adv Mater, 2024, 36 ArticleID: 2401299

[18] Yu P-H, Gao Y, Zhang G-D, Zhang C, Guo C-H, Ramakrishna S, Long Y-Z, Zhang J. 3D self-supportive structures of micro/nanofiber assemblies constructed in situ in air turbulent flow fields for thermal protection at extreme conditions. Chem Eng J, 2025, 511 ArticleID: 161536

[19] Wang H, Zhang X, Wang N, Li Y, Feng X, Huang Y, Zhao C, Liu Z, Fang M, Ou G, Gao H, Li X, Wu H. Ultralight, scalable, and high-temperature–resilient ceramic nanofiber sponges. Sci Adv, 2017, 3 ArticleID: e1603170

[20] Cheng X, Liu Y-T, Si Y, Yu J, Ding B. Direct synthesis of highly stretchable ceramic nanofibrous aerogels via 3D reaction electrospinning. Nat Commun, 2022, 13: 2637

[21] Yang P, Liu C, Zhu J, Li N, Zhang S, Wang Z. Multiscale symbiotic carbonaceous silica nanofiber aerogels composed of a ZrO₂ pinning structure with high-temperature thermal insulation and high strength. J Mater Chem A, 2025, 13: 33729

[22] Zhang X, Liu Y, Guo X, Zhang X, Jin G, Li C, Cao D. Manipulating polymerization degree and charge density to achieve self-templated electrospinning superelastic silica curly nanofibrous aerogels for thermal insulation. Ceram Int, 2025, 51: 38571

[23] Schuh CA, Lund AC. Atomistic basis for the plastic yield criterion of metallic glass. Nat Mater, 2003, 2: 449

[24] Fu S, Liu D, Deng Y, Guo J, Zhao H, Zhou J, Zhang P, Yu H, Dang S, Zhang J, Li H, Xu X. Carbonaceous ceramic nanofibrous aerogels for high-temperature thermal superinsulation. Nano Res, 2023, 16: 5047

[25] Dou L, Zhang X, Cheng X, Ma Z, Wang X, Si Y, Yu J, Ding B. Hierarchical Cellular Structured Ceramic Nanofibrous Aerogels with Temperature-Invariant Superelasticity for Thermal Insulation. ACS Appl Mater Interfaces, 2019, 11: 29056

[26] Guo J, Fu S, Deng Y, Xu X, Laima S, Liu D, Zhang P, Zhou J, Zhao H, Yu H, Dang S, Zhang J, Zhao Y, Li H, Duan X. Hypocrystalline ceramic aerogels for thermal insulation at extreme conditions. Nature, 2022, 606: 909

[27] Yarin AL, Koombhongse S, Reneker DH. Bending instability in electrospinning of nanofibers. J Appl Phys, 2001, 89: 3018

[28] Moon S, Jones MS, Seo E, et al.. 3D jet writing of mechanically actuated tandem scaffolds. Sci Adv, 2021, 7 ArticleID: eabf5289

[29] Dong S, Maciejewska B, Millar R, Grobert N. 3D Electrospinning of Al₂O₃/ZrO₂ fibrous aerogels for multipurpose thermal insulation. Adv Compos Hybrid Mater, 2023, 6: 186

[30] Feng Y, Guo Y, Li X, Zhang L, Yan J. Continuous Rapid Fabrication of Ceramic Fiber Sponge Aerogels with High Thermomechanical Properties via a Green and Low-Cost Electrospinning Technique. ACS Nano, 2024, 18: 19054

[31] Wu F, Liu Y, Si Y, Yu J, Ding B. Multiphase ceramic nanofibers with super-elasticity from − 196–1600 °C. Nano Today, 2022, 44 ArticleID: 101455

[32] Gao Y, Yu P-H, Zhang J, Zhang G-D, Guo C-H, Zhou Y-Q, Long Y-Z, Wu H. Compressible piezoelectric ceramic nanofiber aerogels with multifunction. Adv Fiber Mater, 2025, 7: 937

[33] Li L, Fang B, Ren D, Fu L, Zhou Y, Yang C, Zhang F, Feng X, Wang L, He X, Qi P, Liu Y, Jia C, Zhao S, Xu F, Wei X, Wu H. Thermal-Switchable, Trifunctional Ceramic-Hydrogel Nanocomposites Enable Full-Lifecycle Security in Practical Battery Systems. ACS Nano, 2022, 16: 10729

[34] Koombhongse S, Liu W, Reneker DH. Flat polymer ribbons and other shapes by electrospinning. J Polym Sci B Polym Phys, 2001, 39: 2598

[35] Miao J, Song X, Xu J, Xu J, Duan Z, Song Y, Gao L, Han Y, Ran X. Ultralight, elastic, thermally insulating, and high-temperature resistant Al₂O₃–SiO₂–B₂O₃ nanofibrous aerogels prepared via the direct foaming method. ACS Appl Mater Interfaces, 2025, 17: 12402

[36] Thomason JL. The influence of fibre properties of the performance of glass-fibre-reinforced polyamide 6,6. Compos Sci Technol, 1999, 59: 2315

[37] Lichtenstein L, Büchner C, Yang B, Shaikhutdinov S, Heyde M, Sierka M, Włodarczyk R, Sauer J, Freund H-J. The atomic structure of a metal-supported vitreous thin silica film. Angew Chem Int Ed Engl, 2012, 51: 404

[38] Shan H, Wang X, Shi F, Yan J, Yu J, Ding B. Hierarchical porous structured SiO₂/SnO₂ nanofibrous membrane with superb flexibility for molecular filtration. ACS Appl Mater Interfaces, 2017, 9: 18966

[39] Tsai M-T, Chang S-W, Chen Y-J, Chen H-L, Lan P-H, Chen D-c, Ko F-H, Lo Y-C, Wang H-C, Wan D. Scalable, flame-resistant, superhydrophobic ceramic metafibers for sustainable all-day radiative cooling. Nano Today, 2023, 48 ArticleID: 101745

[40] Dou L, Cheng X, Zhang X, Si Y, Yu J, Ding B. Temperature-invariant superelastic, fatigue resistant, and binary-network structured silica nanofibrous aerogels for thermal superinsulation. J Mater Chem A, 2020, 8: 7775

[41] Zhang Z, Liu C, Li N, Guo W, Li Y, Yang P, Zhang S, Wang Z. Highly oriented SiC@SiO₂ ceramic fiber aerogels with good anisotropy of the thermal conductivity and high-temperature resistance. Adv Sci, 2025, 12 ArticleID: 2416740

[42] Zhou G, Qu X, Tong L, Wei B, Sun Y, Mou Z, Zhang Q, Ramakrishna S, Meng Q. Preparation and performance of Zr-Si based ultra thermal-insulating ceramic aerogels inspired by alpaca wool under extreme temperatures. Chem Eng J, 2025, 511 ArticleID: 162033

[43] Pfeifer S, Demirci P, Duran R, Stolpmann H, Renfftlen A, Nemrava S, Niewa R, Clauß B, Buchmeiser MR. Synthesis of zirconia toughened alumina (ZTA) fibers for high performance materials. J Eur Ceram Soc, 2016, 36: 725

[44] Xue R, Zhuge Y, Liu G, Liu F. Flexible fabrication of a novel SiO₂/AF/ZIF-L composite embedded with MOF structure and its thermal insulation properties. Ceram Int, 2023, 49: 36619

[45] Padture NP, Gell M, Jordan EH. Thermal barrier coatings for gas-turbine engine applications. Science, 2002, 296: 280

[46] Wan CL, Pan W, Xu Q, Qin YX, Wang JD, Qu ZX, Fang MH. Effect of point defects on the thermal transport properties of (La_xGd_1−x)₂Zr₂O₇: experiment and theoretical model. Phys Rev B, 2006, 74 ArticleID: 144109

[47] Su L, Jia S, Ren J, Lu X, Guo S-W, Guo P, Cai Z, Lu D, Niu M, Zhuang L, Peng K, Wang H. Strong yet flexible ceramic aerogel. Nat Commun, 2023, 14: 7057

[48] Chen G, Xie E, Sun Y, Tian J, Fu J, Cao J, Wang S, Qiu J, Zou Y, Zhao J, Wang Y, Ouyang J, Chen W, Shuai Y, Zhou Y. High-strength micron-thick layered ceramics with ultralow radiation transmittance for thermal shielding above 1273 K. Adv Funct Mater, 2026, 36 ArticleID: e12733

[49] Liu H, Zhao X. Thermal conductivity analysis of high porosity structures with open and closed pores. Int J Heat Mass Transfer, 2022, 183 ArticleID: 122089

[50] Zhang Y, Zhang X, Li Y, Xia Z, Yu H, Yang J, Wang X. High-strength, 3D interconnected alumina ceramic foams with high porosity comparable to aerogels. Ceram Int, 2023, 49: 39070

[51] Ferraro C, Garcia-Tuñon E, Rocha VG, Barg S, Fariñas MD, Alvarez-Arenas TEG, Sernicola G, Giuliani F, Saiz E. Light and strong SiC networks. Adv Funct Mater, 2016, 26: 1636

Funding

Natural Science Foundation of Beijing Municipal(No. 2252043)

the National Natural Science Foundation of China(No. 52170019)

Fundamental Research Funds for Central Universities of the Central South University(No. 06500100)

the Fundamental Research Funds for the Central Universities(ZY2602)

RIGHTS & PERMISSIONS

Donghua University, Shanghai, China

Just Accepted

This article has successfully passed peer review and final editorial review, and will soon enter typesetting, proofreading and other publishing processes. The currently displayed version is the accepted final manuscript. The officially published version will be updated with format, DOI and citation information upon launch. We recommend that you pay attention to subsequent journal notifications and preferentially cite the officially published version. Thank you for your support and cooperation.