The copolymerization between TEOS (tetraethoxysilane) and silane derivatives was promoted by the application of high power ultrasound to the precursor liquid mixtures in the same way as in the classical sol-gel method. The specific organic precursor was selected from the silanol-terminated polymer family with different molecular functionality and the inorganic precursor was from the silicon alkoxide family. Ultrasound, through the acoustic cavitation process, influences the formation of a very fine distribution of silica particles and avoids cyclidation of the polymer, thus favoring copolymerization with the inorganic particles and leading to the formation of a highly porous and rubber-like solid aerogel. Creep compliance curves, corresponding to the time-dependent depth response to a step load, are imprint site dependent, with pore, soft and stiff sites discerned. In all cases, an instantaneous elastic deformation is apparent. For longer test times, depending on the imprint sites, elastic deformation and newtonian flow produce the rise and fall of the creep curve. Linear parts of the curve on a log-log scale indicate potential growth with small exponents for the creep compliance level. Isochrones stress-strain diagrams show a superlinear trend and an increase with time, which reveals the nonlinear viscoelasticity of these hybrid aerogels. The elasto-plastic response to creep can be tuned by the molecular functionality of the different silane derivatives studied.

We present the synthesis of resorcinol-formaldehyde aerogels and carbon aerogels of different nanoporosities, emphasizing on the recent developments in fabrication pathways of lower cost. Recent results showed a simple way to the production of highly nanoporous carbon xerogels. While using an approach combined colloidal silica nanocasting and carbon dioxide supercritical drying, hydrophilicity-controlled carbon aerogels with high mesoporosity were synthesized. Then, we demonstrate the functions of these aerogels for template synthesis of hierarchically nanostructured zeolites having micropores and mesopores.

Resorcinol formaldehyde (R/F) aerogels have been used in a variety of laser targets for Inertial Confinement Fusion (ICF) experiments in the form of thin films, cast shapes such as cylinders and cubes, and hollow and solid microspheres. Besides ICF experiments, R/F aerogel can be used for capacitors, batteries, thermal insulation, absorption/filtration media, and chromatographic packing applications. Traditionally, R/F aerogel is synthesized using a 2-step (base/acid catalysis) polycondensation reaction. We have developed a novel process to synthesize the R/F aerogel using free radical UV initiator at room temperature in 10 minutes using a UV light source. This paper will review this process, which was developed to synthesize R/F aerogels using UV-free radical initiators. Scanning electron microscopy results will also be discussed to show that the aerogel pore structure is similar to traditional R/F aerogels. Fabrication of solid and hollow microspheres for ICF experiments using this R/F aerogel synthesis technique and the technique’s limitations will also be discussed.

Refrigeration, air conditioning, and other cooling requirements in buildings, industry, and transportation sectors account for about 10 quads of U.S. primary energy consumption. Therefore, advanced technologies for space cooling in buildings and vehicles – as well as for refrigeration in residential, commercial, and industrial applications – that are more energy efficient, avoid net direct greenhouse gas emissions, reduce lifecycle costs, and can impact large markets are needed. Although current technologies are reaching their efficiency limits, thermoelectric (TE) materials can be used for cooling applications and have potential for significant improvements. Compared to traditional bulk phase TE materials, literature results suggest that nanometer-scale materials allow additional opportunities to improve the efficiency of TE materials. Aerogels are one type of nano-material that offers opportunities to increase the efficiency of TE materials by controlling particle size, particle composition and by reducing the thermal conductivity. Bismuth telluride (Bi2Te3) is the most studied TE material and our objective was to produce bismuth telluride aerogels with controlled microstructures and thermal conductivities to increase the TE figure of merit. Aspen Aerogels developed a novel synthesis method to prepare Bi2Te3 aerogels using the principles of colloidal chemistry and sol-gel chemistry. The reaction conditions were investigated and optimized so that gels could be obtained at low reaction temperatures. The gels were aged and dried using supercritical CO2. The aerogels were characterized by BET, XRD, and SEM. The best aerogels were hot pressed and Seebeck coefficients were determined. The synthetic approach developed and the properties of the aerogels will be presented and compared with Bi2Te3 aerogels and materials prepared by other methods.

There are a lot of synthetic polymers which can be used for controlled drug delivery, however they are not easily accepted by the organism. Also incorporation of drugs into carriers runs under difficult conditions. Therefore scientists have been inclined to use natural-origin polymers, such as proteins and polysaccharides. Some of these promising natural polysaccharidic candidates are alginic acid sodium salt, guar gum and chitosan due to their outstanding merits. They are similar to extracellular matrix having high chemical versatility, good biological performance and cell or enzyme-controlled degradability. Many polysaccharidic hydrogels for drug delivery have already been prepared, but one of their weakness is their short life in dry air conditions; thus, special coating materials are being developed for enhancing their life time.

Alginates were used in the present research for synthesis of organic biodegradable gels by sol-gel process, which were further easily converted to aerogels by supercritical drying. They are safe for use, nontoxic, and derived from renewable sources. Aerogels made of alginate are dry and stable materials, which makes them interesting as a substitute to hydrogels. Alginates undergo reversible gelation in aqueous solution through interaction with divalent cations such as Ca2+, which create ionic inter-chain bridges. Two fundamental methods of ionic cross-linking were used to prepare alginate hydrogels: the diffusion method, where spheres are created and the internal setting method resulting in monoliths. After producing the hydrogel, alcogels were formed by solvent exchange using 100% ethanol. Ethanol was later replaced by supercritical CO2 with supercritical drying (100 bar, 35°C). Aerogels made from natural polysaccharides combine both biocharacteristics and aerogel characteristics such as high porosity and specific surface area, which makes them really attractive in drug delivery applications. The aerogels obtained in present research were therefore studied as drug carriers. The effects of the alginate composition and synthesis method on model drug nicotinic acid release were investigated. The results indicated that by using the internal setting cross-linking method for obtaining aerogels nicotinic acid was released in a more controlled manner. That is why further investigation was done on alginate spherical beads for prolonging their drug release. A multi-step sol-gel process was applied to generate complex aerogels with multi-membranes. First ionically cross-linked spherical cores were obtained by dropwise addition of sodium alginate solution into a CaCl2 solution. These cores were further immersed into alginate solution, filtered through a sieve and dropped into a salt solution again. By repeating the above process, different multi-membrane hydrogels were produced and further converted to aerogels. By adding more membranes around core burst drug release was successfully inhibited.

Aluminosilicate aerogels offer potential for extremely low thermal conductivities at temperatures greater than 900°C, beyond where silica aerogels reach their upper temperature limits. Aerogels have been synthesized at various Al:Si ratios, including mullite compositions, using Boehmite (AlOOH) as the Al source, and tetraethoxy orthosilicate as the Si precursor. The Boehmite-derived aerogels are found to form by a self-assembly process of AlOOH crystallites, with Si-O groups on the surface of an alumina skeleton. Morphology, surface area and pore size varies with the crystallite size of the starting Boehmite powder, as well as with synthesis parameters.

Ternary systems, including Al-Si-Ti aerogels incorporating a soluble Ti precursor, are possible with careful control of pH. The addition of Ti influences sol viscosity, gelation time pore structure and pore size distribution, as well as phase formation on heat treatment.

High performance polyimides have been widely investigated as materials with excellent thermal, mechanical, and electronic properties due to their highly rigid structures. Aspen has developed an approach to prepare polyimide aerogels which have applications as low dielectric constant materials, separation membranes, catalyst supports and insulation materials. In this paper, we will discuss the preparation of polyimide-silica hybrid aerogel materials with good mechanical strengths and low thermal conductivities. The polyimide-silica hybrid aerogels were made by a two-step process and the materials were characterized to determine thermal conductivity and compressive strength. Results show that compressive moduli of the polyimide-silica hybrid aerogels increase dramatically with density (power law relationship). Thermal conductivity of the aerogels is dependent on the aging conditions and density, with the lowest value achieved so far being ~12 mW/m-K at ambient conditions. The relationship between aerogel density and surface area, thermal stability, porosity and morphology of the nanostructure of the polyimide-silica hybrid aerogels are also described in this paper.

We describe organic aerogels derived from multifunctional isocyanates through reaction with water (polyureas), acid andydrides (polyimides) and carboxylic acids (polyamides). All processes are invariably single-step, one-pot and take place at room or slightly elevated temperatures. The resulting materials are robust, their density may vary over a very wide range and their nanomorphology can be either particulate or fibrous, but in all cases they all consist of similarly sized primary particles.

We have demonstrated that gas phase explosive combustion can lead to nanoparticle aerosols with sufficiently large volume fraction to cause a volume spanning gel to form on the order of ten’s of seconds. The term “aerosol gel” was coined to name these materials. So far we have made aerosol gels of carbon and silica. These aerosol gels are similar to well-known, liquid-phase, sol-gel synthesized aerogels.

This article examines, from the energy viewpoint, a new lightweight, slim, high energy efficient, light-transmitting envelope system, providing for seamless, free-form designs for use in architectural projects. The research was based on envelope components already existing on the market, especially components implemented with granular silica aerogel insulation, as this is the most effective translucent thermal insulation there is today. The tests run on these materials revealed that there is not one that has all the features required of the new envelope model, although some do have properties that could be exploited to generate this envelope, namely, the vacuum chamber of vacuum insulated panels (VIP), the monolithic aerogel used as insulation in some prototypes, and reinforced polyester barriers. By combining these three design components — the high-performance thermal insulation of the vacuum chamber combined with monolithic silica aerogel insulation, the free-form design potential provided by materials like reinforced polyester and epoxy resins—, we have been able to define and test a new, variable geometry, energy-saving envelope system.

Recent years, although silica aerogels are expected to be the promising material for energy savings, the lack of mechanical strength prevents from commercial applications such as to low-density thermal insulators. To improve mechanical properties, methyltrimethoxysilane (MTMS) and dimethyldimethoxysilane (DMDMS) are used in this study as the co-precursor of aerogels because the network becomes flexible due to the relatively low cross-linking density and to the unreacted methyl groups. Because of the strong hydrophobicity of MTMS/DMDMS-derived condensates, phase separation occurs in aqueous sol and must be suppressed to obtain uniform and monolithic gel. We employed surfactant n-hexadecyltrimethylammonium chloride (CTAC) in starting compositions to control phase separation during a 2-step acid/base sol-gel reaction. By changing the starting composition, various microstructures of pores are obtained. In the uniaxial compression test, the aerogel showed high flexibility and spring-back to the original shape after removing the stress.

Aerogels are regarded as ideal candidates for the design of functional nanocomposites containing supported metal or metal oxide nanoparticles. The large specific surface area together with the open pore structure enables aerogels to effectively host finely dispersed nanoparticles up to the desired loading, to provide nanoparticle accessibility and/or to prevent nanoparticle agglomeration, as required to supply their specific functionalities.

The preparation of highly porous nanocomposite aerogels containing magnetic metal, alloy or metal oxide nanoparticles dispersed into amorphous silica, with high purity and homogeneity, was successfully achieved by a novel sol-gel procedure involving urea-assisted co-gelation of the precursor phases. This method allows fast gelation, giving rise to aerogels with 97% porosity, and it is very versatile allowing to vary composition, loading and average size of the nanoparticles.

The characterization of the morphological and structural features of the nanocomposite aerogels is carried out using different techniques, such as X-ray diffraction, Transmission Electron Microscopy and X-ray Absorption Spectroscopy. The characterization of the magnetic properties is carried out by SQUID magnetometry.

A transition of porous structures in monolithic poly(methylsilsesquioxane) (PMSQ, CH3SiO1.5) gels from uniform mesopores to hierarchical pore structures consisting of macro- and mesopores, has been investigated using a sol-gel system containing surfactant Pluronic F127. A broad variation of porous morphology is controlled by changing the concentration of F127. Sufficient concentrations of F127 inhibit the occurrence of macroscopic phase separation of hydrophobic PMSQ condensates and lead to well-defined mesoporous transparent aerogels with high specific pore volume. Mesopores are developed through microscopic phase separation of PMSQ colloid-surfactant complexes in the solvent. Macroscopic phase separation regulates well-defined macropores in the micrometer range on decreasing concentrations of F127, in which microscopic phase separation concurrently takes place in the PMSQ-rich gelling phase after the onset of macroscopic phase separation. Monolithic PMSQ gels with hierarchical macro- and mesopore structures are consequently obtained.

Long duration storage of large quantities of cryogenic fluids for propulsion, power, and life-support is an essential requirement for missions into space. Efficient and reliable insulation materials are key to the success of these missions. The required insulation material must outperform the current standard multi-layer insulation (MLI) for thermal insulation and provide additional features such as durability, micrometeoroid orbital debris protection, and flexibility, all in one single-layer material. Ultra-low density and highly hydrophobic fiber reinforced aerogel material integrated with MLI has the potential to offer a great insulation package which will overcome several issues that the current standard MLI alone suffers from such as: 1) damage during installation, 2) high cost, and 3) degradation over time. The hybrid aerogel/MLI solution affords a more reliable alternative because it is robust, and will outperform the MLI in cases of vacuum loss. Low density and highly resilient methylsilicate aerogel will contribute less solid conductivity to the overall heat transfer within the aerogel/MLI system. Sol-gel optimization of low density and low dust methylsilicate aerogels will be presented. Thermal performance of two prototypes of hybrid aerogel/MLI composites and a baseline MLI system (1 inch thick, 90 layers) fabricated by Aerospace Fabrication and Materials (AFM) and tested at cryogenic temperatures under different vacuum level conditions (at Cryogenic Laboratory, NASA KSC) will also be presented.

Traditionally, the synthesis of resorcinol formaldehyde (R/F) aerogels consists of a 2-step (base/acid catalysis) polycondensation reaction. Since the acid catalyst in the reaction controls the gelation time, the replacement of the acid catalyst with a non-ionic photo-acid generator decreased the gelation time from hours, down to a few minutes at room temperature using a UV light source. The reaction rate was not only fast, but the liquid precursor was stable for several hours prior to UV exposure. After drying, the resulting aerogel porosity was characterized by scanning electron microscopy (SEM) and confirmed the internal structure of the aerogel was similar to the original R/F pore structures. This paper will discuss the modifications made to the traditional R/F formulation, as well as the benefits of a fast gelation time for aerogel casting applications such as thin films, cylinders, and solid and hollow microspheres.

Nanoporous MgAl2O4 particulates with high porosities were successfully prepared from sol-gel reactions, solvent exchange with castor oil and subsequent combustion and calcination at 700 °C. The products were crystalline and semitransparent. Changes in the metal precursor concentrations allowed control of pore volumes from 0.7 to 1.1 cm3/g and average pore sizes from 14 to 19 nm. The specific surface areas are about 200 m2/g regardless of the precursor concentrations. After heating at 1000 °C for 10 hours, the products kept about 70% of their original pore volume and about 60% of the original surface area. Heating at 1100 °C caused a drastic reduction of pore volume and surface area to 40 and 36%, respectively, as the average particle size increased to 23 nm.

Experiments and analysis have been conducted to characterize flow separators used in applications where heated fluid passes between layers of solid material such as in the manufacturing of gelatinous materials. The Biot number of the configuration is the key parameter, and must be taken into account when optimizing performance. It is shown that most prior work was for low Biot number systems, and the particular configurations under consideration operate at high Biot number. Existing designs developed for lower Biot number (such as membrane filter spacers) are shown to perform poorly for this application. An experimental apparatus was designed and fabricated to quantitatively assess pressure drop through the system using different separation strategies. These results were compared with a simplified two-term model based on the physics of viscous drag in these devices. Channels without separators behave like classical Poiseuille flow. Channels with separators can be modeled with a two-term equation: a baseline Poiseuille term and a form drag term. A variety of separator designs are compared and their overall performance is discussed. We also illustrate the high sensitivity to gap height in all configurations.

Mesoporous organosilicate materials combine tunable binding characteristics, high surface area, and low materials density with an ordered pore network. Surface modifications provide the potential for incorporation of a variety of functional groups. We have taken advantage of these characteristics for the development of a range of materials to be utilized in various applications. In one approach, porphyrins are incorporated into the materials to provide unique catalytic properties. In these materials, the organosilicate scaffold stabilizes the porphyrin catalyst and facilitates interaction of the catalyst and target. Catalysis can be stimulated through exposure to light or application of an electrical current. The selectivity of the materials can be influenced through choice of organic bridging groups in the organosilicate structure and through selection of the porphyrin component. In addition, a type of molecular imprinting can be applied to provide sites on the pore walls that enhance adsorption selectivity for the target. These materials are directed at the development of self-decontaminating surfaces and coatings. Similar materials characteristics have been utilized in the development of solidphase extraction materials for use in the pre-concentration of nitroenergetic targets from ground and surface water samples. These materials are being incorporated into systems for in situ water quality monitoring. Mesoporous organosilicates can also be applied to the encapsulation of proteins and nucleic acids, stabilizing them for wider application of technologies utilizing these reagents. Modifications to the pore surfaces, in this case, are used to incorporate stabilizing agents such as sugars and proteins which should extend shelf-life and reduce storage restrictions.