Polyimide Aerogels Research Articles

Regulating porous microstructure of polyimide aerogels toward efficient shape memory performance

The development of lightweight shape memory materials with exceptional thermal insulation properties is highly important in aerospace applications. Herein, shape memory polyimide (PI) aerogels was fabricated by molecularly designed PI molecular chains through freeze gelation and subsequent thermal imidization. The freezing conditions were controlled to regulate the porous microstructures of the aerogels. The interactions between PI chains formed physically crosslinked netpoints, which could overcome the expansive force and capillary force, thereby creating a stable porous structure. Because shape memory was thermally activated, the shape memory mechanisms associated with the thermal conductivity of the aerogels were comprehensively explored. Upon decreasing the pore size, dense frameworks were formed, contributing to the improved thermo-mechanical and compressive properties. Moreover, the heat transfer efficiency in the aerogel skeleton was enhanced, resulting in a rapid shape recovery response. Benefiting from the physically crosslinked structures, including entangled chains and π-π interactions, the fabricated PI aerogels demonstrated exceptional shape fixation and recovery capabilities. These findings may provide guidelines for designing smart aerogels for aerospace applications.

Mechanically robust poly(urethane-imide) aerogels with excellent thermal insulation and sound absorption by ambient drying

Polyimide (PI) aerogels are the great candidates for sound absorption, thermal insulation and mechanical cushioning materials due to their low density, excellent mechanical properties and good thermal stability. However, the high shrinkage and hydrophilicity of PI aerogels, as well as the time-consuming and complexity of the process directly limit their wide application in many fields. Herein, a facile one-step method for the synthesis of porous monolithic poly(urethane-imide) (PUI) aerogels was successfully developed. Hydrothermal synthesis and ambient drying methods were adopted in the construction of monolithic chemically cross-linked PUI aerogels, which avoids the complex imidization process. PUI aerogels were homogeneously produced by a chemical cross-linking copolymerization reaction between polyurethane (PU) oligomers, Benzene-1,2,4,5-tetracarboxylic dianhydride (PMDA) and 1, 3, 5-tris (6-isocyanatohexyl)-1, 3, 5-triazine-2, 4, 6(1H, 3H, 5H)-trione without any catalysts. Interestingly, the introduction of linear flexible PU oligomers chain segments effectively prevented the shrinkage of the network backbone and enhanced the hydrophobicity of PUI aerogels. The obtained PUI aerogels have low density (0.196 g/cm3), low shrinkage (9.30%), high porosity (79.54%) and hydrophobicity (water contact angle of 129.2°). Under high pressure, PUI aerogel was compressed but not break and the compression Young's modulus as high as 3.638 MPa. Moreover, the thermal conductivity of PUI aerogels was only 59.92 mW/m/K at 150 °C. When the back cavity depth was 5 mm, the highest sound absorption coefficient of PUI aerogel was up to 0.7219. This work provides a new method for the development of lightweight, high-mechanical-strength polymer aerogels, and the prepared aerogels have a potential application in the field of multifunctional integrated sound absorption materials.

Surface Modification of Polyimide Aerogel by Thermoplastic Polyurethane for Enhanced Mechanical Strength and Thermal Insulation Performance.

Polyimide (PI) aerogel is a good thermal insulation material with the highest temperature resistance in practical application. But the mechanical strength of PI aerogels prepared by freeze-drying or thermoimide methods is weak. In this research, TPU was selected as an aging solution to solve the problem of the low mechanical strength of PI aerogel prepared by the freeze-drying method. Previous work has certified that the coupling of PI and thermoplastic polyurethane (TPU) can enhance the mechanical strength of PI aerogel to a certain extent due to the flexibility of TPU. But excessive TPU will change the PI structure in the cross-linking process and decrease the mechanical strength of the aerogel. Thus, a new kind of PI gel modification method was provided by using TPU as an aging solution, and the mechanical strength of PI aerogel is improved to 3.06 MPa. Furthermore, the shrinkage, specific surface area, waterproof angle, and thermal conductivity all show good performance, thus enabling PI aerogel to be used in many aspects. Specially, the method is simple and can be used to prepare some other high-strength aerogels.

Effect of polymer concentration and cross-linking density on the microstructure and properties of polyimide aerogels

Polyimide aerogels display excellent mechanical strength, high thermal stability, low thermal conductivity, and outstanding dielectric properties. Typically, the synthesis of polyimide aerogels involves the polycondensation of dianhydride and diamine into poly(amic acid) (PAA) oligomers, which are then cross-linked and chemically imidized into polyimide. The stoichiometry of dianhydride and diamine determines the number of repeat units and length of the PAA oligomers, which in turn determines the cross-linking density. Despite the critical role of polymer concentration and number of repeating units in determining the microstructure and properties of polyimide aerogels, few detailed studies exist on these two parameters. Here, we synthesized and characterized 16 polyimide aerogel formulations from the common monomers biphenyl-3,3′,4,4′-tetracarboxylic dianhydride (BPDA) and 4,4′-oxydianiline (ODA), with different repeat units (n = 5, 15, 30, 45) and total polymer concentrations (4, 7, 10, 13 wt%). An increased polymer concentration accelerated gelation and enhanced the mechanical performance of aerogels, but surprisingly, it also led to higher volumetric shrinkage during aging, solvent exchange, and supercritical drying (SCD). Specific surface areas (SSAs) reached a maximum at intermediate polymer concentrations. A shorter oligomer chain length, i.e., a higher cross-linking density, led to moderately higher SSAs (between 320 and 400 m2/g) and reduced shrinkage, resulting in lower densities for a given polymer concentration. The density dependence of the thermal conductivity exhibits a pronounced U-shaped curve with a minimum in thermal conductivity of 21–23 mW/(m·K) between 0.080 and 0.120 g/cm3, with somewhat lower values for more highly cross-linked aerogels. This systematic study of polyimide aerogels forms the basis for designing polyimide aerogels with tailored properties for targeted applications.Graphical

Ceramic Fiber-Reinforced Polyimide Aerogel Composites with Improved Shape Stability against Shrinkage.

Polyimide (PI) aerogels, renowned for their nano-porous structure and exceptional performance across a spectrum of applications, often encounter significant challenges during fabrication, primarily due to severe shrinkage. In this study, we innovatively incorporated ceramic fibers of varying diameters into the PI aerogel matrix to enhance the shape stability against shrinkage. The structure of the resulting ceramic fiber-reinforced PI (CF-PI) aerogel composites as well as their performance in thermal decomposition, thermal insulation, and compression resistance were characterized. The results revealed that the CF-PI aerogel composites dried by supercritical ethanol achieved greatly reduced shrinkage as low as 5.0 vol.% and low thermal conductivity ranging from 31.2 mW·m-1·K-1 to 35.3 mW·m-1·K-1, showcasing their excellent performance in shape stability and thermal insulation. These composites also inherited the superior residue-forming ability of ceramic fibers and the robust mechanical attributes of PI, thereby exhibiting enhanced thermal stability and compression resistance. Besides, the effects of different drying conditions on the structure and properties of CF-PI aerogels were also discussed. The coupling use of supercritical ethanol drying with the addition of ceramic fibers is preferred. This preferred condition gives birth to low-shrinkage CF-PI aerogel composites, which also stand out for their integrated advantages include high thermal stability, low thermal conductivity, and high mechanical strength. These advantages attribute to CF-PI aerogel composites substantial potential for a wide range of applications, particularly as high-performance thermal insulation materials for extreme conditions.

Metal-phenolic networks-engineered polyimide aerogels for high-efficiency gold extraction and separation from e-waste mixture

Engineering adsorption materials that offer easy handling, efficient, and selective recovery of precious metals, such as gold, from electronic waste (e-waste) are of significant interest, especially given the escalating volume of discarded electronic devices. However, the harsh digested solvents (e.g., aqua regia), ultralow gold concentrations (several ppm), and competitive interference from various metals present significant challenges. Herein, we engineer a porous polyimide (PI) aerogel with chemically reductive, mechanically resilient, and environmentally recyclable capabilities, using biomass-derived metal-phenolic networks (MPNs), for highly selective and efficient gold extraction and separation. The resulting aerogels show a high adsorption efficiency (∼97.4 %), selective extraction of gold ions from 12 metal ions in simulated leached solutions, and superior purity (∼100 %) in the reduced gold particles. The gold ions are reduced, nucleate, and grow into large agglomeration (∼12 μm) as observed in experiments and confirmed by density functional theory (DFT) calculations, facilitating their separation from the aerogels without the need for complex processes (e.g., membrane separation). On application to a central processing unit (CPU), our aerogels effectively extracted > 96 % of gold ions even at ultralow concentrations of 3.6 ppm in aqua regia, generating at least 66 times more profit compared to the cost (profit/cost = ∼52.9/∼0.8 $⋅g−1). These results demonstrated that MPNs-engineered aerogels are promising economical and practical adsorbents for gold recovery in e-waste.

Distributed activation energy treatment of polyimide aerogel and its blocking effect on thermal runaway propagation of ternary battery

The thermal runaway of lithium batteries has become an urgent problem that needs to be solved today. In this study, polyimide aerogel materials with high temperature resistance and low thermal conductivity were prepared by supercritical drying equipment. Firstly, the activation energy distribution of the two pseudo-components of polyimide aerogels was calculated by TGA data at different heating rates, and then the optimal kinetic parameters were obtained. Secondly, a series of experiments were designed to study the blocking effect of polyimide aerogel films with different thicknesses (0.5 mm, 1 mm, 1.5 mm, and 2 mm) on the uncontrolled transmission of batteries, which showed that 2 mm film could successfully block the uncontrolled transmission of battery heat at 711.9 °C. 0.5 mm, 1 mm and 1.5 mm polyimide aerogel films can delay the thermal runaway of the battery, and the delay time was 182 s, 224 s and 259 s respectively. At the same time, the indicator gas was detected and analyzed, indicating that the barrier material can effectively reduce the content of CO2 gas and heat release rate. This study provides new enlightenment for the development of polyimide aerogels, and new ideas for the thermal insulation design of batteries.

Synthesis of micro/nano multi-scale polyimide aerogels via confinement-controlled freeze-casting

The freeze-casting is widely utilized as a tool for regulating micro-scale pore structures in the fabrication of flexible polyimide (PI) aerogels for applications in adsorption, filtration, and fire-retardant. Herein, a confinement-controlled freeze-casting method is developed to fabricate PI aerogels with excellent thermal insulation properties by designing multi-scale structural adaptability. In a confinement-controlled system, the enhanced solid/solid and solid/liquid interface interactions in the solution dispersion system induce dendritic evolution of ice crystals. Under the directional freezing, grown dendritic ice crystals squeeze the loaded particles to form polyamic acid salt (PAAs) cryogels. Followed by template removal and thermal imidization, PI aerogels with a micro/nano-scale slit-like porous structure were obtained. The PI aerogels are characterized by ultra-low density (as low as 9.82 mg/cm3) and exceptional thermal insulation performance (25.0 mW/(m·K) at 25 °C).

Enhanced sound absorption property of polyimide aerogels by the incorporation of macropores

Polyimide (PI) aerogels hold immense potential in the fields of thermal insulation and sound absorption. However, their sound absorption capabilities have been hindered by the high air flow resistance. To mitigate the air flow resistance and enhance the sound absorption performance of PI aerogels, we employed a self-sacrificing templating strategy to introduce macropores into the PI aerogels, thus creating PI aerogels with microporous (MPI). Investigation into the insulating properties and sound absorption performance of MPI revealed a thermal conductivity of 35.82 mW m−1 K−1. Within the frequency range of 500–6300 Hz, MPI exhibited peak absorption coefficients ranging from 0.66 to 0.78, with peaks occurring between 1250 Hz and 2000 Hz. This represents a significant improvement over traditional PI aerogels, which have an absorption coefficient of 0.39 at 3150 Hz. And a notable shift of the peak absorption coefficient of MPI towards lower frequencies. The introduction of macropores significantly enhances the sound absorption performance of PI aerogels.

Tailoring the electron free path in an ultra-lightweight gas-solid composite insulation system for high dielectric strength

Reliable electric insulation is the premise for the application of high-voltage technologies, such as power transmission, emergent electrified transportations, and advanced propulsion systems. With the current insulation strategy, the credibility of insulation system depends on the sufficient insulation materials usage, suffering from bulky structure, expensive production costs and environmental pollution. Here, we propose a strategy that applies a lightweight multiple-barrier skeleton in gas insulation to tailor electron free path and restrain electron avalanche, thus realizing a high insulation strength with less material usage. This strategy is verified by the composite insulation of porous polyimide aerogel and various types of insulating gases. It achieves a comparable insulation strength to conventional polymers by less than 10% materials usage. With above insulation strategy, a 152.5% improvement in power density and a 54.6% weight reduction are acquired in the cable system for more or all electric aircraft. This strategy inspires the design of efficient insulation solution with both high breakdown strength and lightweight.

Low shrinkage polyimide aerogel cross-linked with amino-functionalized hollow glass microbeads for thermal and acoustic insulation

As a nanoporous material, polyimide (PI) aerogels have excellent thermal and acoustic properties. However, their high air flow resistance is detrimental to the development of their acoustic properties. To enhance the thermal and acoustic insulation properties of PI aerogels, we have selected hollow glass microbeads (HGM) with a low thermal conductivity coefficient to be combined with the PI aerogel, leading to the fabrication of PI/HGM aerogel composite materials. In this study, there are two preprocessing methods for HGM: untreated and aminized (HGM-NH2). These were then individually combined with PI aerogel to fabricate two distinct PI/HGM composite aerogels: a physically blended variant (PIHGM) and a chemically bonded one (PHN). The thermal insulation and acoustic properties of these two composite aerogels were compared. The results show that HGM-NH2 not only functions as a cross-linking agent but also plays a key role in forming the three-dimensional network structure, which effectively reduces the shrinkage rate and density of the composite aerogel. Moreover, the thermal conductivity of PHN reached a low of 27.92 mW m⁻1 K⁻1, which is a reduction compared to PIHGM's thermal conductivity of 29.83 mW m⁻1 K⁻1. Moreover, the PHN composite aerogel with 10% HGM addition exhibited an average sound insulation level that was 120% higher than that of PIHGM. The method of incorporating pore structures with different scales also offers valuable insights for enhancing the sound insulation performance of other materials.

Carbon Nanofibrous Aerogels Derived from Electrospun Polyimide for Multifunctional Piezoresistive Sensors.

The fabrication of carbon aerogels with ultralow density, high electrical conductivity, and ultraelasticity still remains substantial challenges. This study utilizes electrospun polyimide aerogel as the source to fabricate flexible carbon nanofibrous aerogel (PI-CNA) capable of multifunctional applications. The lightweight PI-CNA based piezoresistive sensor shows a wide linear range (0-217 kPa), rapid response/recovery time, and fatigue resistance (12,000 cycles). More importantly, the superior pressure sensing enables the PI-CNA for all-range healthcare sensing, including pulse monitoring, physiological activity detection, speech recognition, and gait recognition. Moreover, the EMI SE and the A coefficient of the PI-CNA reach 45 dB and 0.62, respectively, indicating the outstanding absorption dominated EMI shielding effects due to the multiple reflections and absorption. Furthermore, PI-CNA exhibits satisfying Joule heating performance up to 120 °C with rapid response time (10-30 s) under low supply voltages (1.5-5 V) and possesses sufficient heating reliability and repeatability in long-term repeated heating/cooling cycles. The fabricated PI-CNA shows significant potential applications in wearable technologies, energy conversion, electronic skin, and artificial intelligence.

Continuous and strong polyimide aerogel fibers enhanced by para-aramid nanofibers prepared via a “Reaction Spinning” for thermal insulation

Strong and flexible aerogel fibers and their textiles with low density are attractive candidates for high-efficiency thermal insulation. However, most of the previously reported aerogel monoliths and fibers suffered from weak mechanical properties. Continuous polyimide aerogel fibers enhanced by para-aramid nanofibers (PANFs) were prepared via a novel “reaction spinning” method combined with supercritical CO2 drying. Attributed to the 3D interconnected porous structure, the polyimide-based aerogel fibers exhibit high porosity (83.0 %∼85.5 %) and specific surface area (55 ∼ 105 m2/g). Meanwhile, the continuous and flexible polyimide-based aerogel fibers reinforced by 2 wt% PANFs possess good mechanical properties with an optimal tensile strength (5.3 MPa) and initial modulus (299 MPa). Additionally, the modified polyimide aerogel fibers and their textiles are endowed with good hydrophobicity and thermal insulation properties, expanding their potential thermal management applications under hygrothermal environments.

The Discharge Behavior and Mechanism of Polyimide Aerogel under Electron Irradiation.

The response and mechanism of polyimide aerogel under electron irradiations were investigated. The experimental results indicated that electron irradiation could not damage the skeleton polyimide in the aerogel due to its high stability, but could result in a discharge within. The morphology of the discharge shows some dendritic discharge patterns, and the material surrounding the discharge channels was carbonized. The numerical simulation results indicated that the incident electrons, and also large amount induced secondary electrons, would be deposited inhomogeneously within the nano-porous polyimide aerogel. This would result in forming an ultra-high electrical potential of up to about 8.5 × 1010 V/m (which is far higher than the breakdown strength (2 × 108 V/m) of bulk polyimide materials) in a local region. This may be the leading cause of the obvious discharge in the materials. Furthermore, it was found that the actual reason for the discharge is related to the residual gas within the nano-porous structure; namely, the more internal residual gas (as a shorter-time vacuum pumping in the irradiated chamber), the more serious the discharge phenomenon. Correspondingly, the phenomenon may largely consist of both residual-gas discharge and surface flashover due to ultra-high local potentials induced by unevenly deposited charges in the porous aerogel.

Preparation of anisotropic polyimide aerogels for thermal protection with outstanding flexible resilience using the freeze-drying method.

Polyimide aerogels (PIAs) not only possess excellent thermodynamic properties but also have a high porosity structure, making them an exceptional protective and thermal insulation material, and further broadening their application scope in aerospace and other cutting-edge fields. In this work, a series of anisotropic polyimide aerogels (3,3',4,4'-biphenyltetracarboxylic dianhydride (S-BPDA), p-phenylenediamine (PDA), 4,4'-diaminodiphenyl ether (ODA)) with excellent properties were prepared. These PIAs were obtained by unidirectional freeze-drying and thermal amination of two different precursor solutions mixed in proportion. These PIAs possess an irregularly oval tubular structure, exhibiting pronounced anisotropy. (PIA-2 exhibits outstanding flexible resilience in the radial direction. It can still regain its original form after half an hour of compression by a universal testing machine, yet it cannot do so in the axial direction. The thermal diffusivity of PIA-5 in the radial direction at room temperature is as low as 0.067 mm2 s-1, and even at 200 °C, the thermal diffusivity is as low as 0.057 mm2 s-1. Meanwhile, the thermal diffusivity in the axial direction at room temperature is 0.11 mm2 s-1, surpassing the value of 0.106 mm2 s-1 of aerogels prepared from monomeric raw materials and dried under supercritical conditions). PIAs exhibit outstanding thermal stability (the axial strength and modulus retention of PIA-8 at 200 °C are as high as 52.63% and 44.82%), and its weight loss temperature of 5% is as high as 603 °C and it has a glass softening temperature of 387 °C. PIAs also demonstrate exceptional flame retardancy in imitation flame retardant experiments and exhibit outstanding thermal insulation performance when heated on a 150 °C heating plate for 10 minutes (the radial surface temperature of PIA-5 was only 49.9 °C). These anisotropic PIAs materials exhibit outstanding flexible resilience, and thermal protection performance, holding significant importance for their widespread adoption as thermal insulation materials in aerospace, high-precision electronic components, and other domains.

Polyimide aerogels with a dual electrically conductive network for electromagnetic interference shielding, piezoresistive sensing, and thermal management

The constant iteration of wearable devices necessitates lightweight electromagnetic shielding materials with multiple functions. In this study, an elastic reduced graphene oxide/polyimide (rGO/PI) aerogel skeleton was prepared through freeze-drying and thermal annealing. Then the highly conductive two-dimensional (2D) transition metal carbide (MXene) was coated onto the rGO/PI skeleton using vacuum impregnation to fabricate MXene@rGO/PI composite aerogels. Due to the dual electrically conductive network formed by rGO and MXene, the MXene@rGO/PI composite aerogels exhibit exceptional electromagnetic interference shielding effectiveness (EMI SE) of 58.7 dB in the X-band at a density of 0.063 g cm−3. Additionally, these composite aerogels demonstrate sensitive piezoresistive sensing capabilities (the electrical resistance variation caused by compressive stress) for detecting human body motion and also possess excellent thermal management properties including efficient Joule heating (up to 108 °C at 10 V) and superior thermal insulation performance. This work presents a feasible strategy for developing polymer-based composites for multi-functional applications such as wearable electronics.

Thermal Isolation Performance of Polyimide Aerogel within a Die-Embedded Glass Interposer

Thermal Isolation Performance of Polyimide Aerogel within a Die-Embedded Glass Interposer

Biomineralization-Inspired Confined-Space Fabrication of Polyimide Aerogels.

The biomineralization process endows biominerals with unique hierarchically porous structures and physical-chemical properties by filling the restricted microreaction space with amorphous phases before the growth of inorganic crystals. In this paper, a confined-space fabrication method inspired by biomineralization for preparing hierarchically porous polyimide (PI) aerogels and PI-derived carbon aerogels is introduced. The confined structure is established through a self-assembly method of vacuum impregnation and ultrasound-assisted freeze-drying. The hierarchically porous structure is controlled by adjusting the structure characteristics of the confined space and secondary aerogels. Subsequently, a variety of performance demonstrations are conducted to demonstrate the mechanical properties and application prospects in the fields of thermal insulation and electromagnetic shielding of the prepared aerogel.

Direct ink writing of polyimide aerogels for battery thermal mitigation

Direct ink writing of polyimide aerogels enables custom-fit thermal insulators, increasing the ionic conductivity of a solid-state electrolyte battery tenfold.

Direct Synthesis of Polyimide Curly Nanofibrous Aerogels for High-Performance Thermal Insulation Under Extreme Temperature.

Maintaining human body temperature is one of the basic needs for living, which requires high-performance thermal insulation materials to prevent heat exchange with external environment. However, the most widely used fibrous thermal insulation materials always suffer from the heavy weight, weak mechanical property, and moderate capacity to suppress heat transfer, resulting in limited personal cold and thermal protection performance. Here, an ultralight, mechanically robust, and thermally insulating polyimide (PI) aerogel is directly synthesized via constructing 3D interlocked curly nanofibrous networks during electrospinning. Controlling the solution/water molecule interaction enables the rapid phase inversion of charged jets, while the multiple jets are ejected by regulating charge density of the fluids, thus synergistically allowing numerous curly nanofibers to interlock and cross-link with each other to form porous aerogel structure. The resulted PI aerogel integrates the ultralight property with density of 2.4mg cm-3, extreme temperature tolerance (mechanical robustness over -196 to 300 °C), and thermal insulation performance with ultralow thermal conductivity of 22.4mW m-1 K-1, providing an ideal candidate to keep human thermal comfort under extreme temperature. This work can provide a source of inspiration for the design and development of nanofibrous aerogels for various applications.