Double-Phase-Networking Polyimide Hybrid Aerogel with Exceptional Dimensional Stability for Superior Thermal Protection System.

Polyimide aerogels have been extensively used in thermal protection domain because they possess a combination of intrinsic characteristics of aerogels and unique features of polyimide. However, polyimide aerogels still suffer significant thermally induced shrinkage at temperatures above 200 °C, restricting their application at high temperature. Here, a novel "double-phase-networking" strategy is proposed for fabricating a lightweight and mechanically robust polyimide hybrid aerogel by forming silica-zirconia-phase networking skeletons, which possess exceptional dimensional stability in high-temperature environments and superior thermal insulation. The rational mechanism responsible for the formation of double-phase-networking aerogel is further explained, generally attributing to chemical crosslinking reactions and supramolecular hydrogen bond interactions derived from the main chains of polyimide and silane/zirconia precursor/sol. The as-prepared aerogels exhibit excellent high-temperature (270 °C) dimensional stability (5.09% ± 0.16%), anti-thermal-shock properties, and low thermal conductivity. Moreover, the hydrophobic treatment provides aerogels high water resistance with water contact angle of 136.9°, further suggestive of low moisture content of 3.6% after exposure to 70 °C and 85% relative humidity for 64 h. The proposed solution for significantly enhancing high-temperature dimensional stability and thermal insulation provides a great supporting foundation for fabricating high-performance organic aerogels as thermal protection materials in aerospace.

Research progress on polybenzoxazine aerogels: Preparation, properties, composites and hybrids fabrication, applications.

The unremitting pursuit of high-performance and multifunctional materials has consistently propelled modern industries forward, stimulating research and motivating progress in related fields. In such materials, polybenzoxazine (PBz) aerogel, which combines the virtues of PBz and aerogel, has attracted salient attention recently, emerging as a novel research focus in the realm of advanced materials. In this review, the preparation scheme, microscopic morphology, and fundamental characteristics of PBz aerogels are comprehensively summarized and discussed in anticipation of providing a clear understanding of the correlation between preparation process, structure, and properties. The effective strategies for enhancing the performance of PBz aerogels including composite fabrication and hybridization are highlighted. Moreover, the applications of PBz-based aerogels in various domains such as adsorption (including wastewater treatment, CO2 capture, and microwave adsorption), thermal insulation, energy storage as well as sensors are covered in detail. Furthermore, several obstacles and potential directions for subsequent research are delineated with a view to surmounting the prevailing constraints and achieving a realization of the shift from experimental exploration to practical applications.

Cellulose Diacetate Aerogels with Low Drying Shrinkage, High-Efficient Thermal Insulation, and Superior Mechanical Strength.

The inherent characteristics of cellulose-derived aerogels, such as their natural abundance and environmental friendliness, make them highly interesting. However, its significant shrinkage before and after the supercritical drying procedure and low mechanical strength limit its potential application. Here, we propose a strategy to prepare cellulose diacetate aerogels (CDAAs) with low drying shrinkage, exceptional thermal insulation, and superior mechanical strength. The low drying shrinkage (radial drying shrinkage of 1.4%) of CDAAs is attributed to their relative strong networking skeletons, which are greatly formed by tert-butanol solvent exchange in exerting the interaction of reducing the surface tension force. In this case, CDAAs are eventually endowed with the low bulk density of 0.069 g cm-3 as well. Additionally, as-prepared CDAAs possess an abundant three-dimensional networking structure whose pore size is concentrated in the diameter range of ~50 nm, and the result above is beneficial for improving the thermal insulation performance (thermal conductivity of 0.021 W m-1 K-1 at ambient environmental and pressure conditions). On the other hand, the optimal compressive stresses of CDAAs at 3% and 5% strain are 0.22 and 0.27 MPa respectively, indicating a mechanically well robustness. The above evidence demonstrates indeed the exceptional thermal insulation and superior compressive properties of CDAAs. This work may provide a new solution for developing a kind of high-performance cellulose-derived aerogel in the future.

Chitosan/silica hybrid aerogels with synergistic capability for superior hydrophobicity and mechanical robustness.

Chitosan aerogels could be applied potentially in thermal insulation for energy-saving buildings, separation/adsorption, and catalysis. However, disadvantages of chitosan aerogels include their hydrophilicity and low insufficient mechanical strength. Here we propose a silica-phase hybriding route to create chitosan/silica hybrid aerogels with a synergistic capability for favourable hydrophobicity and superior mechanical strength, demonstrating an emergent finding (hydrophobicity optimised with the improved mechanical strength). The aerogels exhibit low drying shrinkage (as low as 13.41 %), lightweight (lowest to 0.149 g cm-1), high-efficient thermal insulation (thermal conductivity as low as to 0.024 W m-1 K-1 at room temperature and normal pressure) either under cryogenic (-196 °C) or high-temperature conditions, exceptional fire-retardancy (self-extinguishing in 1.8 s) and environmentally friendly characteristic (initial mineralisation after 10 d). High hydrophobic property (water contact angle up to 142°) of the aerogels were achieved depending upon 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane of vapor deposition, presenting a discovery concerning substantial improvement of mechanical properties (up to 0.188 MPa at 5 % strain, increased by 25 %). Furthermore, we demonstrate that a plausible mechanism for simultaneous hydrophobic and mechanical enhancement is depending upon the modulation of networking skeletons at the nanoscale.

Ambient Pressure Drying to Construct Cellulose Acetate/Benzoxazine Hybrid Aerogels with Flame Retardancy, Excellent Thermal Stability, and Superior Mechanical Strength Resistance to Cryogenic Temperature.

Cellulose aerogels are highly attractive candidates in various applications, such as thermal insulation, adsorption separation, biomedical field, and as carriers, due to their intrinsic merits of low density, high porosity, biodegradability, and renewability. However, the expensive cost of the supercritical drying process and poor mechanical properties limit their practical applications. Herein, a new method was presented to fabricate cellulose acetate/benzoxazine hybrid aerogels (CBAs) with low cost, low drying shrinkage, excellent mechanical properties under cryogenic condition (-196 °C), outstanding thermal insulation, flame retardancy, and good thermal stability by ambient pressure drying. In more detail, the weighted drying shrinkage rate of CBAs-T2 can be controlled to 6.8% (the average value along the radial and axial directions), mainly due to the enhanced skeleton, by introducing polybenzoxazine networking chains. The resultant CBAs-T2 exhibit outstanding mechanical properties at room temperature because of the presence of the polybenzoxazine hybrid in the cellulose networking system. CBAs-T2 still have good mechanical properties even after subjecting them to liquid nitrogen treatment. In addition, the optimal value of thermal conductivity (0.033 W m-1 K-1) is gained easily because of the uniform cross-linking networking structure and small pore size. A superior flame retardance of CBAs-T2 is endowed to achieve self-extinguishment after ignition, which is attributed to the presence of the aromatic ring in the backbone structure. Moreover, the good thermal stability of CBAs-T2 is attributed to the fact that polybenzoxazine components could resist the decomposition of cellulose acetate and inhibit heat release during the combustion process. Our study would provide a novel method for obtaining biomass aerogels including the cellulose-based materials system with low drying shrinkage and superior mechanical properties despite bearing a cryogenic environment by the low-cost ambient pressure drying approach.

Hydrophobic Cellulose Acetate Aerogels for Thermal Insulation.

As naturally derived material, cellulose aerogels have excellent thermal insulation properties due to their unique high porosity and three-dimensional mesoporous structure. However, its hydrophilic properties limit its application in the field of building insulation. Here, we propose a method to prepare high hydrophobicity by adopting the sol-gel method and chemical vapor reaction strategy using cellulose acetate type II as raw material and 2,4-toluene diisocyanate as the cross-linking agent. Thermal properties of cellulose acetate aerogels (CAAs) were measured, where pyridine was the catalyst, acetone was the solvent, and perfluorodecyltriethoxysilane (PFDS), hexamethyldisilazane (HMDS), and methyltriethoxysilane (MTES) were used as hydrophobic agents (by process hydrophobic test). Compared with MTES-modified cellulose acetate aerogels (M-CAAs) and HMDS (H-CAAs)-modified cellulose acetate aerogels, PFDS-modified (P-CAAs) cellulose acetate aerogels are the most hydrophobic. By implementing hydrophobic modification of PFDS both inside and outside the structure of cellulose acetate aerogels, the water contact angle can reach up to 136°, strongly demonstrating the potential of PFDS as a hydrophobic agent. The results show that the thermal conductivity and compressive strength of cellulose acetate aerogel with the best hydrophobic properties are 0.035 W m-1 K-1 at normal pressure and 0.39 MPa at 3% strain, respectively. This work shows that the highly hydrophobic cellulose acetate aerogel has potential as a waterproof material in the field of building thermal-insulation materials.

Chitosan Based Aerogels with Low Shrinkage by Chemical Cross-Linking and Supramolecular Interaction.

Chitosan (CTS) aerogel is a new type of functional material that could be possibly applied in the thermal insulation field, especially in energy-saving buildings. However, the inhibition method for the very big shrinkage of CTS aerogels from the final gel to the aerogel is challenging, causing great difficulty in achieving a near-net shape of CTS aerogels. Here, this study explored a facile strategy for restraining CTS-based aerogels' inherent shrinkage depending on the chemical crosslinking and the interpenetrated supramolecular interaction by introducing nanofibrillar cellulose (NFC) and polyvinyl alcohol (PVA) chains. The effects of different aspect ratios of NFC on the CTS-based aerogels were systematically analyzed. The results showed that the optimal aspect ratio for NFC introduction was 37.5 from the comprehensive property perspective. CTS/PVA/NFC hybrid aerogels with the aspect ratio of 37.5 for NFC gained a superior thermal conductivity of 0.0224 W/m K at ambient atmosphere (the cold surface temperature was only 33.46 °C, despite contacting the hot surface of 80.46 °C), a low density of 0.09 g/cm3, and a relatively high compressive stress of 0.51 MPa at 10% strain.

Constructing Cellulose Diacetate Aerogels with Pearl-Necklace-like Skeleton Networking Structure.

Cellulose and its derivative aerogels have attracted much attention due to their renewable and biodegradable properties. However, the significant shrinkage in the supercritical drying process causes the relatively high thermal conductivity and low mechanical property of cellulose and its derivatives aerogels. Considering the pearl-necklace-like skeleton network of silica aerogels, which can improve thermal insulation property and mechanical property. Herein, we propose a new strategy for fabricating cellulose diacetate aerogels (CDAAs) with pearl-necklace-like skeletons by using tert-butanol (TBA) as exchange solvent after experiencing the freezing-drying course. CDAAs obtained have the low density of 0.09 g cm-3, the nanopore size in the range of 10-40 nm, the low thermal conductivity of 0.024 W m-1 K-1 at ambient conditions, and the excellent mechanical properties (0.18 MPa at 3% strain, 0.38 MPa at 5% strain). Ultimately, CDAAs with moderate mechanical property paralleled to cellulose-derived aerogels obtained from supercritical drying process are produced, only simultaneously owning the radial shrinkage of 6.2%. The facile method for fabricating CDAAs could provide a new reference for constructing cellulose/cellulose-derived aerogels and other biomass aerogels.

Construction and Nanostructure of Chitosan/Nanocellulose Hybrid Aerogels.

Biomass aerogels have received extensive attention due to their unique natural characteristics. However, biomass-based chitosan aerogels are often confronted with the traditional issue concerning a weak skeleton structure, namely, the corresponding huge shrinkage for chitosan aerogels in the stage from the final gel to the aerogel. Herein, we put forward a new approach to enhance chitosan aerogels by introducing natural biomaterial cellulose nanocrystal (CNC). CNC is applied to connect/cross-link chitosan chains to form its networking construction through supramolecular interaction/physical entanglement, eventually realizing the enhancement of the chitosan aerogel network structure. Chitosan aerogels modified with CNC exhibit a high specific surface area of 578.43 cm2 g-1, and the pore size distribution is in the range of 20-60 nm, which is smaller than the mean free path of gas molecules (69 nm), triggering a "no convection" effect. Hence, the gaseous heat transfer of chitosan aerogel is effectively suppressed. Chitosan aerogels with the addition of CNC show an excellent thermal insulation property (0.0272 W m-1 K-1 at ambient condition) and an enhanced compressive strength (0.13 MPa at a strain of 3%). This improvement method of chitosan aerogel in enhancing the skeleton structure aspect provides a new kind of idea for strengthening the nanoscale morphology structure of biomass aerogels.

Compressible, Flame-Resistant and Thermally Insulating Fiber-Reinforced Polybenzoxazine Aerogel Composites.

The preparation of novel polymer aerogel materials with enhanced flame-retardancy, superior thermal insulation and mechanical strength is of great practical significance in energy-savings and fire-prevention for buildings. Herein, we reported the fiber-reinforced polybenzoxazine (PBO) aerogel composites with flame retardance and thermal insulation, which were prepared under room temperature and atmospheric pressure, and using 4,4'-diaminodiphenlymethane (MDA) benzoxazine monomer as the raw material and oxalic acid (OA) as the catalyst. Several outstanding attributes were achieved in the aerogel composites, such as relatively low thermal conductivity (0.069 W/m·K at 105 Pa, 0.031 W/m·K at 5 Pa), high limiting oxygen index (LOI) up to 32.5, and enhanced mechanical properties. It can be compressed to more than 80% of the deformation without obvious cracks, and shows high compressive modulus and specific modulus (20.69 MPa and 5.05 × 104 N·m/Kg, respectively). All the excellent comprehensive properties mean that fiber-reinforced PBO aerogel composites have broad application prospects in the fields of flame retardancy and thermal insulation.

Low temperature catalytic oxidative aging of LDPE films in response to heat excitation.

The waste treatment of polymer materials is often conducted using the photocatalytic technique; however, complete decomposition is frequently inhibited owing to several shortcomings such as low quantum yield and the requirement of ultraviolet irradiation. Herein, we report a strategy to implement moderate management of polymeric films via thermocatalytic oxidative route, which is responsive to heat stimulus. Diverse LDPE-matrix films together with as-prepared thermal catalysts (TCs) or initiators were synthesized to further investigate heat-dependent-catalytic degradation effects. After artificial ageing, structural textures of the as-synthesized films could be chemically deteriorated, followed by a huge increase in surface roughness values, and appreciable loss was also found in the average molecular weights and mechanical parameters. We found an emergent phenomenon in which crystallization closely resembled two-dimensional (2D) growth, which displayed rod-like or disc-type crystal shapes. New chemical groups generated on film surfaces were monitored, and led to a higher limiting oxygen index because of strong catalytic oxidation, thus demonstrating the success of catalytic oxidative ageing by heat actuation. The underlying mechanism responsible for thermocatalytic oxidative pattern is also discussed. Accordingly, these findings may have important implications for better understanding the development of polymeric-matrix waste disposal.

New insights on degradation of methylene blue using thermocatalytic reactions catalyzed by low-temperature excitation.

Although photocatalysis has been actively surveyed on removing organic pollutants in ultraviolet (UV) environment, because of lacking UV in solar exposure, photodegradation is difficult to be considerably degraded in conventional exposure condition. In this work, an innovative approach was proposed to compensate for it, which was developed in model wastewater using thermal sensitizer at room temperature. At the optimal component condition, the removal rate of adsorption and thermocatalytic degradation processes can reach the highest level of 82.07% solely response to temperature in the dark. Moreover, the kinetics of degradation rate was modeled considering that it was found similarly to Langmuir-Hinshelwood behavior, and a tentative mechanism was objectively established, describing reasonably well in line with the experimental results. On the other hand, it was found that high amount of methylene blue (MB) adsorbed onto thermal sensitizer was of unambiguous importance to subsequent thermocatalytic performance. Briefly, all above suggest that the feasibility to the thermodegradation route has been successfully verified under room temperature excitation. Herein the insight into degradation pattern of dye over thermal excitation may further enlarge applications for wastewater treatment.