Multiphase Symbiotic Engineered Elastic Ceramic-Carbon Aerogels with Advanced Thermal Protection in Extreme Oxidative Environments.

Elastic aerogels can dissipate aerodynamic forces and thermal stresses by reversible slipping or deforming to avoid sudden failure caused by stress concentration, making them the most promising candidates for thermal protection in aerospace applications. However, existing elastic aerogels face difficulties achieving reliable protection above 1500 °C in aerobic environments due to their poor thermomechanical stability and significantly increased thermal conductivity at elevated temperatures. Here, a multiphase sequence and multiscale structural engineering strategy is proposed to synthesize mullite-carbon hybrid nanofibrous aerogels. The heterogeneous symbiotic effect between components simultaneously inhibits ceramic crystalline coarsening and carbon thermal etching, thus ensuring the thermal stability of the nanofiber building blocks. Efficient load transfer and high interfacial thermal resistance at crystalline-amorphous phase boundaries on the microscopic scale, coupled with mesoscale lamellar cellular and locally closed-pore structures, achieve rapid stress dissipation and thermal energy attenuation in aerogels. This robust thermal protection material system is compatible with ultralight density (30 mg cm-3), reversible compression strain of 60%, extraordinary thermomechanical stability (up to 1600 °C in oxidative environments), and ultralow thermal conductivity (50.58 mW m-1 K-1 at 300 °C), offering new options and possibilities to cope with the harsh operating environments faced by space exploration.

Multiscale Interpenetrated/Interconnected Network Design Confers All-Carbon Aerogels with Unprecedented Thermomechanical Properties for Thermal Insulation under Extreme Environments.

With ultralight weight, low thermal conductivity, and extraordinary high-temperature resistance, carbon aerogels hold tremendous potential against severe thermal threats encountered by hypersonic vehicles during the in-orbit operation and re-entry process. However, current 3D aerogels are plagued by irreconcilable contradictions between adiabatic and mechanical performance due to monotonicity of the building blocks or uncontrollable assembly behavior. Herein, a spatially confined assembly strategy of multiscale low-dimensional nanocarbons is reported to decouple the stress and heat transfer. The nanofiber framework, a basis for transferring the loading strain, is covered by a continuous thin-film-like layer formed by the aggregation of nanoparticles, which in combination serve as the fundamental structural units for generating an elastic behavior while yielding compartments in aerogels to suppress the gaseous fluid thermal diffusion within distinct partitions. The resulting all-carbon aerogels with a hierarchical cellular structure and quasi-closed cell walls achieve the best thermomechanical and insulation trade-off, exhibiting flyweight density (24 mg cm-3 ), temperature-constant compressibility (-196-1600 °C), and a low thermal conductivity of 0.04 829 W m-1 K-1 at 300 °C. This strategy provides a remarkable thermal protection material in hostile environments for future aerospace exploration.

Way to a Library of Ti-Series Oxide Nanofiber Sponges that are Highly Stretchable, Compressible, and Bendable.

Ti-series oxide ceramics in the form of aerogels, such as TiO2, SrTiO3, BaTiO3, and CaCu3Ti4O12, hold tremendous potential as functional materials owing to their excellent optical, dielectric, and catalytic properties. Unfortunately, these inorganic aerogels are usually brittle and prone to pulverization owing to weak inter-particulate interactions, resulting in restricted application performance and serious health risks. Herein, a novel strategy is reported to synthesize an elastic form of an aerogel-like, highly porous structure, in which activity-switchable Ti-series oxide sols transform from the metastable state to the active state during electrospinning, resulting in condensation and solidification at the whipping stage to obtain curled nanofibers. These curled nanofibers are further entangled when flying in the air to form a physically interlocked, elastic network mimicking the microstructure of high-elasticity hydrogels. This strategy provides a library of Ti-series oxide nanofiber sponges with unprecedented stretchability, compressibility, and bendability, possessing extensive opportunities for greener, safer, and broader applications as integrated or wearable functional devices. As a proof-of-concept demonstration, a new, elastic form of TiO2, composed of both "white" and "black" TiO2 nanofiber sponges, is constructed as spontaneous air-conditioning textiles in smart clothing, buildings, and vehicles, with unique bidirectional regulation of radiative cooling in summer and solar heating in winter.

Elastic and compressible Al2O3/ZrO2/La2O3 nanofibrous membranes for firefighting protective clothing.

Developing ceramic nanofibrous membranes for the thermal insulation layer of firefighting protective clothing is vital. However, previous ceramic nanofibrous membranes were brittle and easy to break during service in high-temperature environments. The lack of elastic and compressible properties has limited the high-end applications of ceramic nanofibrous membranes. In this work, elastic and compressible Al2O3/ZrO2/La2O3 nanofibrous membranes were fabricated via sol-gel electrospinning and calcination in air at different temperatures. The as-fabricated Al2O3/ZrO2/La2O3 nanofibrous membranes can maintain excellent elasticity and compressibility in the temperature ranging from -196 to 1400 °C. Moreover, they have low thermal conductivity and high working temperatures. These favorable characteristics make the Al2O3/ZrO2/La2O3 nanofibrous membranes a promising candidate for the thermal insulation layer of firefighting protective clothing.

Direct synthesis of highly stretchable ceramic nanofibrous aerogels via 3D reaction electrospinning.

Ceramic aerogels are attractive for many applications due to their ultralow density, high porosity, and multifunctionality but are limited by the typical trade-off relationship between mechanical properties and thermal stability when used in extreme environments. In this work, we design and synthesize ceramic nanofibrous aerogels with three-dimensional (3D) interwoven crimped-nanofibre structures that endow the aerogels with superior mechanical performances and high thermal stability. These ceramic aerogels are synthesized by a direct and facile route, 3D reaction electrospinning. They display robust structural stability with structure-derived mechanical ultra-stretchability up to 100% tensile strain and superior restoring capacity up to 40% tensile strain, 95% bending strain and 60% compressive strain, high thermal stability from -196 to 1400 °C, repeatable stretchability at working temperatures up to 1300 °C, and a low thermal conductivity of 0.0228 W m-1 K-1 in air. This work would enable the innovative design of high-performance ceramic aerogels for various applications.

All-Ceramic and Elastic Aerogels with Nanofibrous-Granular Binary Synergistic Structure for Thermal Superinsulation.

High-performance thermally insulating ceramic materials with robust mechanical properties, high-temperature resistance, and excellent thermal insulation characteristics are highly desirable for thermal management systems under extreme conditions. However, the large-scale application of traditional ceramic granular aerogels is still limited by their brittleness and stiff nature, while ceramic fibrous aerogels often display high thermal conductivity. To meet the above requirements, in this study, ceramic nanofibrous-granular composite aerogels with lamellar multiarch cellular structure and leaf-like fibrous-granular binary networks are designed and fabricated. The resulting composite aerogels possess ultralow weight, superelasticity with recoverable compression strain up to 80%, and large mechanical strength. Furthermore, excellent fatigue resistance with 1.2% plastic deformation after 1000 cyclic compressions, temperature-invariant dynamic mechanical stability from -100 to 500 °C, and an operational temperature range from -196 to 1100 °C are successfully achieved in the proposed composites. The nanosized silica granular aerogels are assembled into a leaf-like shape and wrapped around the fibrous cell walls, endowing low thermal conductivity (0.024 W m-1 K-1) as well as favorable high-temperature thermal superinsulation properties. Benefiting from the favorable compatibility, the present strategy for nanofiber-granular composite ceramic aerogels provides a dominant route to produce thermally insulated and mechanically robust composite cellular materials for use in harsh environments.

Ultrastrong, Superelastic, and Lamellar Multiarch Structured ZrO2-Al2O3 Nanofibrous Aerogels with High-Temperature Resistance over 1300 °C.

Advanced ceramic aerogel materials with a performance combining sufficient mechanical robustness and splendid high-temperature resistance are urgently needed as thermal insulators in harsh environments. However, the practical applications of ceramic aerogel materials are always limited by poor mechanical performance and degradation under thermal shock. Here, we report the facile creation of lamellar multiarch structured ceramic nanofibrous aerogels that are simultaneously ultrastrong, superelastic, and high temperature resistant by combining ZrO2-Al2O3 nanofibers with Al(H2PO4)3 matrices. The resulting ZrO2-Al2O3 nanofibrous aerogels exhibit the integrated properties of rapid recovery from a strain of 90%, high compression strength of more than 1100 kPa (at a strain of 90%), high fatigue resistance, and temperature-invariant superelasticity. Moreover, the all-ceramic component feature also provides the ceramic nanofibrous aerogels with high-temperature resistance up to 1300 °C and thermal insulation performance with low thermal conductivity (0.0322 W m-1 K-1). These superior performances make the ceramic aerogels ideal for high-temperature thermal insulation materials in extreme conditions.

Hierarchical Cellular Structured Ceramic Nanofibrous Aerogels with Temperature-Invariant Superelasticity for Thermal Insulation.

Silica aerogels are attractive for thermal insulation due to their low thermal conductivity and good heat resistance performance. However, the fabrication of silica aerogels with temperature-invariant superelasticity and ultralow thermal conductivity has remained extremely challenging. Herein, we designed and synthesized a hierarchical cellular structured silica nanofibrous aerogel by using electrospun SiO2 nanofibers (SNFs) and SiO2 nanoparticle aerogels (SNAs) as the matrix and SiO2 sol as the high-temperature nanoglue. This pathway leads to the intrinsically random deposited SNFs assembling into a fibrous cellular structure, and the SNAs are evenly distributed on the fibrous cell wall. The unique hierarchical cellular structure of the ceramic nanofibrous aerogels endows it with integrated performances of the ultralow density of ∼0.2 mg cm-3, negative Poisson's ratio, ultralow thermal conductivity (23.27 mW m-1 K-1), temperature-invariant superelasticity from -196 to 1100 °C, and editable shapes on a large scale. These favorable multifeatures present the aerogels ideal for thermal insulation in industrial, aerospace, and even extreme environmental conditions.

Highly flexible, mesoporous structured, and metallic Cu-doped C/SiO2 nanofibrous membranes for efficient catalytic oxidative elimination of antibiotic pollutants.

The development of inorganic membranous catalysts with both large mesopores and superb flexibility is extremely favorable for the enhancement of their catalytic oxidation activity for the degradation of antibiotic pollutants in wastewater via sulfate radical-based advanced oxidation processes; however, there still exists a huge challenge for inorganic materials to simultaneously realize these two properties. Herein, metallic copper-doped carbon/silica nanofibrous membranes (Cu@C/SiO2 NFMs) with large mesopores, superb flexibility, and robust mechanical strength were fabricated through a sol-gel electrospinning and subsequent in situ carbonization reduction method. The synthesized Cu nanoparticles were homogeneously distributed throughout the mesoporous C/SiO2 nanofiber matrix, which enabled the resultant Cu@C/SiO2 NFMs to be applied as heterogeneous catalysts, and their catalytic performance was systematically assessed through activating persulfate for the elimination of tetracycline hydrochloride (TCH) in water. The fabricated Cu@C/SiO2 NFMs provided outstanding catalytic performance towards TCH with a high removal efficiency of 95% in 40 min and a rapid removal speed of 0.054 min-1. Moreover, the membranes could be facilely recycled through being directly separated from water without any post-processing. Such a facile strategy for preparing mesoporous and flexible metal-doped inorganic nanofibrous membranes may offer novel insights for designing new types of heterogeneous catalysts for antibiotic-containing wastewater treatment or other potential applications.