Matthias M. Koebel

Aerogel-based thermal superinsulation: an overview

This review is focused on describing the intimate link which exists between aerogels and thermal superinsulation. For long, this applied field has been considered as the most promising potential market for these nanomaterials. Today, there are several indicators suggesting that this old vision is likely to become reality in the near future. Based on recent developments in the field, we are confident that aerogels still offer the greatest potential for non-evacuated superinsulation systems and consequently must be considered as an amazing opportunity for sustainable development. The practical realization of such products however is time-consuming and a significant amount of R&D activities are still necessary to yield improved aerogel-based insulation products for mass markets.

Transparent, Conducting ATO Thin Films by Epoxide-Initiated Sol–Gel Chemistry: A Highly Versatile Route to Mixed-Metal Oxide Films

A robust synthesis approach to transparent conducting oxide (TCO) materials using epoxide assisted sol-gel chemistry is reported. The new route utilizes simple tin and antimony chloride precursors in aqueous solution, thus eliminating the need for organometallic precursors. Propylene oxide acts as a proton scavenger and drives metal hydroxide formation and subsequent polycondensation reactions. Thin films of antimony-doped tin oxide (ATO) were prepared by dip-coating of mixed metal oxide sols. After annealing at 600 °C in air, structural, electrical and optical properties of undoped and Sb-doped tin oxide films were characterized. Single layer films with 5 mol % Sb doping exhibited an optical transparency which was virtually identical to that of the plain glass substrate and an electrical resistivity of 2.8 × 10(-2) Ω cm. SEM and AFM analysis confirmed the presence of surface defects and cracks which increased with increasing Sb dopant concentration. Multiple depositions of identical ATO films showed a roughly 1 order of magnitude decrease in the film resistivity after the third layer, with typical values below 5 × 10(-3) Ω cm. This suggests that a second and third deposition fill up residual cracks and defects in the first layer and thus brings out the full performance of the ATO material. The epoxide-assisted sol chemistry is a promising technique for the preparation of mixed oxide thin film materials. Its superiority over conventional alkoxide and metal salt-based methods is explained in the context of a general description of the reaction mechanism.

Aerogels for Superinsulation: A Synoptic View

The present chapter is focused on describing the intimate link which exists between aerogels and thermal superinsulation. For long, this applied field has been considered as the most promising potential market for these nanostructured materials. Most likely this old vision will become reality in the near future.Following a short presentation of the global need for superinsulation together with a closer look at the specific situation in the building sector, we propose within this synopsis a brief analysis of (1) the world’s insulation markets, (2) superinsulating aerogel materials and their alternatives, (3) commercial aerogel insulation products available today, and (4) our estimation of their most likely applications worldwide in the future. We conclude this chapter with some first considerations on health, toxicity, and environmental aspects.Based on recent developments in the field, it can be stated that aerogels still offer the greatest potential for nonevacuated superinsulation systems and consequently must be considered as an amazing opportunity for sustainable development. This chapter of the handbook bridges the gap between those dealing with thermal insulation properties of aerogel materials in general (Chap. 21) and the various commercial products described in Part XV.

Shape Changes of Pt Nanoparticles Induced by Deposition on Mesoporous Silica

Polyvinylpyrollidone (PVP)-capped platinum nanoparticles (NPs) are found to change shape from spherical to flat when deposited on mesoporous silica substrates (SBA-15). Transmission electron microscopy (TEM), small-angle X-ray scattering (SAXS), and extended X-ray absorption fine structure (EXAFS) analyses are used in these studies. The SAXS results indicate that, after deposition, the 2 nm NPs have an average gyration radius 22% larger than in solution, while the EXAFS measurements indicate a decrease in first neighbor co-ordination number from 9.3 to 7.4. The deformation of these small capped NPs is attributed to interactions with the surface of the SBA-15 support, as evidenced by X-ray absorption near-edge structure (XANES).

Fast and Minimal‐Solvent Production of Superinsulating Silica Aerogel Granulate

With their low thermal conductivity (λ), silica aerogels can reduce carbon emissions from heating and cooling demands, but their widespread adoption is limited by the high production cost. A one-pot synthesis for silica aerogel granulate is presented that drastically reduces solvent use, production time, and global warming potential. The inclusion of the hydrophobization agent prior to gelation with a post-gelation activation step, enables a complete production cycle of less than four hours at the lab scale for a solvent use close to the theoretical minimum, and limits the global warming potential. Importantly, the one-pot aerogel granulate retains the exceptional properties associated with silica aerogel, mostly λ=14.4±1.0 mW m-1 ⋅K-1 for the pilot scale materials, about half that of standing air (26 mW m-1 ⋅K-1 ). The resource-, time-, and cost-effective production will allow silica aerogels to break out of its niche into the mainstream building and industrial insulation markets.

Methyltrimethoxysilane (MTMS)-based silica–iron oxide superhydrophobic nanocomposites

We report a facile synthesis of superhydrophobic silica-iron oxide nanocomposites via a co-precursor sol-gel process. The choice of the silica precursor (Methyltrimethoxysilane, MTMS) in combination with iron nitrate altered the pore structure dramatically. The influence of iron oxide doping on the structural properties of pristine MTMS aerogel is discussed.

Dimensional and Structural Control of Silica Aerogel Membranes for Miniaturized Motionless Gas Pumps

With growing public interest in portable electronics such as micro fuel cells, micro gas total analysis systems, and portable medical devices, the need for miniaturized air pumps with minimal electrical power consumption is on the rise. Thus, the development and downsizing of next-generation thermal transpiration gas pumps has been investigated intensively during the last decades. Such a system relies on a mesoporous membrane that generates a thermomolecular pressure gradient under the action of an applied temperature bias. However, the development of highly miniaturized active membrane materials with tailored porosity and optimized pumping performance remains a major challenge. Here we report a systematic study on the manufacturing of aerogel membranes using an optimized, minimal-shrinkage sol-gel process, leading to low thermal conductivity and high air conductance. This combination of properties results in superior performance for miniaturized thermomolecular air pump applications. The engineering of such aerogel membranes, which implies pore structure control and chemical surface modification, requires both chemical processing know-how and a detailed understanding of the influence of the material properties on the spatial flow rate density. Optimal pumping performance was found for devices with integrated membranes with a density of 0.062 g cm(-3) and an average pore size of 142.0 nm. Benchmarking of such low-density hydrophobic active aerogel membranes gave an air flow rate density of 3.85 sccm·cm(-2) at an operating temperature of 400 °C. Such a silica aerogel membrane based system has shown more than 50% higher pumping performance when compared to conventional transpiration pump membrane materials as well as the ability to withstand higher operating temperatures (up to 440 °C). This study highlights new perspectives for the development of miniaturized thermal transpiration air pumps while offering insights into the fundamentals of molecular pumping in three-dimensional open-mesoporous materials.

Sodium Silicate Based Aerogels via Ambient Pressure Drying

The first step in the preparation of silica aerogels is a sol–gel process producing a gel. This is followed by drying of the gel by either supercritical drying (SCD) or ambient pressure drying (APD). Traditionally, silica aerogels are prepared by the more energy-intensive and -expensive SCD method using alkoxide precursors such as tetraethoxysilane (TEOS) or tetramethoxysilane (TMOS). This choice partly restricts the commercialization of aerogels. Recent developments have shown great potential of the APD as an alternative method employing sodium silicate (Na2SiO3) as a purely inorganic precursor. The properties of such aerogels are very similar to those obtained by more conventional methods. This chapter focuses on the preparation of sodium silicate based aerogels via APD and the effect of various parameters on their physicochemical properties. The process chemistry is further contrasted with factors relevant for large-scale production.

Monolithic nitrogen-doped carbon as a water sorbent for high-performance adsorption cooling

In the present study, we report on the development of carbon adsorbents for water adsorption heat pumps. Resorcinol-melamine-formaldehyde (RMF) resins were synthesized and molded into monolithic shapes before pyrolysis and chemical activation with KOH. The influence of the carbonization and activation treatments on the physicochemical properties and the water sorption behavior of the final adsorbent materials were investigated. Activated carbons with a one-to-one (C to KOH) impregnation mass ratio, an activation temperature of 800 °C and an activation time of one hour exhibited the highest water cycling ability. For isobaric adsorption at 23 mbar, the peak specific cooling power of the best monolithic activated carbon produced in this way was 192 W kg−1 for a temperature step from 90 °C to 50 °C compared to 255 W kg−1 for silica gel for a finned tube heat exchanger of comparable fin spacing. For a temperature step from 60 °C to 30 °C, the monolithic activated carbon exhibited a higher peak specific cooling power (389 W kg−1) compared to silica gel (240 W kg−1). In situ infrared thermography revealed superior thermal transport properties of the monolithic carbons compared to commercial silica gel.

Superhydrophobic and Flexible Aerogels

Aerogels with reduced fragility and increased hydrophobicity have significant potential to expand their use as lightweight structural, insulating or shock absorbing materials especially in aeronautics, microelectronics, and sensing applications. In addition, there is a potential for extremely hydrophobic aerogels in oil-spill clean-up applications. This chapter describes synthesis, physico-chemical properties, and applications of flexible superhydrophobic silica aerogels that is to say silica aerogels with typical water contact angles >150° and high mechanical flexibility. Such materials are accessible via a two-step sol–gel process from methyl-trialkoxysilane precursors. Extreme hydrophobicity has been obtained with measured water contact angles as high as 175°. The criticality of the water droplet size on a superhydrophobic aerogel was determined to be 2.7 mm. The velocity of the water droplet on such a superhydrophobic surface has been observed to be 1.44 m/s for 55° inclination, which is close to the free fall velocity (~1.5 m/s). Elastic and rheological properties of as-prepared aerogels are also described in this chapter. Young’s modulus of the aerogels is determined by uniaxial compression test measurements. Apart from synthesis and characterization, emphasis is placed on their potential use as shock absorbing materials and efficient absorbents of oil and organic compounds in general.