Additive manufacturing of silica aerogels.

Owing to their ultralow thermal conductivity and open pore structure1-3, silica aerogels are widely used in thermal insulation4,5, catalysis6, physics7,8, environmental remediation6,9, optical devices10 and hypervelocity particle capture11. Thermal insulation is by far the largest market for silica aerogels, which are ideal materials when space is limited. One drawback of silica aerogels is their brittleness. Fibre reinforcement and binders can be used to overcome this for large-volume applications in building and industrial insulation5,12, but their poor machinability, combined with the difficulty of precisely casting small objects, limits the miniaturization potential of silica aerogels. Additive manufacturing provides an alternative route to miniaturization, but was "considered not feasible for silica aerogel"13. Here we present a direct ink writing protocol to create miniaturized silica aerogel objects from a slurry of silica aerogel powder in a dilute silica nanoparticle suspension (sol). The inks exhibit shear-thinning behaviour, owing to the high volume fraction of gel particles. As a result, they flow easily through the nozzle during printing, but their viscosity increases rapidly after printing, ensuring that the printed objects retain their shape. After printing, the silica sol is gelled in an ammonia atmosphere to enable subsequent processing into aerogels. The printed aerogel objects are pure silica and retain the high specific surface area (751 square metres per gram) and ultralow thermal conductivity (15.9 milliwatts per metre per kelvin) typical of silica aerogels. Furthermore, we demonstrate the ease with which functional nanoparticles can be incorporated. The printed silica aerogel objects can be used for thermal management, as miniaturized gas pumps and to degrade volatile organic compounds, illustrating the potential of our protocol.

Chemistry of Chitosan Aerogels: Three-Dimensional Pore Control for Tailored Applications.

Chitosan is an abundant biopolymer derived from food waste with attractive properties, particularly its high biocompatibility and easy chemical processability. Here, we review the rapidly expanding literature on chitosan-based porous materials with a focus on the gelation mechanisms, the three-dimensional multiscale structural control, and the diverse chemical functionality not accessible by other biopolymers. The properties vary widely: from supercritically dried, mesoporous chitosan aerogels to very light, freeze-dried macroporous scaffolds. Porous chitosan displays impressive performance at the laboratory scale, but the highly (meso)porous nature amplifies not only the beneficial functionality of chitosan, but also its drawbacks, resulting in serious barriers to industrialization. In order to facilitate technology transfer, we critically discuss the practical feasibility of chitosan aerogels in potential applications compared to conventional and other biopolymer-based porous or nonporous materials.

Formation of Nanofibrous Structure in Biopolymer Aerogel during Supercritical CO2 Processing: The Case of Chitosan Aerogel.

Supercritical drying is widely considered as the gold standard to produce aerogels that preserve the microstructure of the gels, but we have found this is not always the case. Chitosan aerogel, one of the emerging biopolymer aerogels, was prepared by chemical cross-linking gelation, followed by solvent exchange with methanol and supercritical drying using CO2. Small-angle X-ray scattering analysis shows that the structure of the wet gel, which consists of Gaussian chains of individual molecular strands, converts into a nanofibrous network during CO2 processing. In situ observation reveals a drastic shrinkage of the gel in CO2, demonstrating that physical coagulation caused by the low affinity between chitosan and CO2 is the main structure-forming step. These results challenge the common perception of supercritical drying: it is no longer an inactive drying method, but rather an active nanostructure forming a tool to produce porous biopolymer materials with tailored structure and properties.

Fate of MgSiO3 melts at core-mantle boundary conditions.

One key for understanding the stratification in the deep mantle lies in the determination of the density and structure of matter at high pressures, as well as the density contrast between solid and liquid silicate phases. Indeed, the density contrast is the main control on the entrainment or settlement of matter and is of fundamental importance for understanding the past and present dynamic behavior of the deepest part of the Earth's mantle. Here, we adapted the X-ray absorption method to the small dimensions of the diamond anvil cell, enabling density measurements of amorphous materials to unprecedented conditions of pressure. Our density data for MgSiO3 glass up to 127 GPa are considerably higher than those previously derived from Brillouin spectroscopy but validate recent ab initio molecular dynamics simulations. A fourth-order Birch-Murnaghan equation of state reproduces our experimental data over the entire pressure regime of the mantle. At the core-mantle boundary (CMB) pressure, the density of MgSiO3 glass is 5.48 ± 0.18 g/cm(3), which is only 1.6% lower than that of MgSiO3 bridgmanite at 5.57 g/cm(3), i.e., they are the same within the uncertainty. Taking into account the partitioning of iron into the melt, we conclude that melts are denser than the surrounding solid phases in the lowermost mantle and that melts will be trapped above the CMB.

Biopolymer Aerogels and Foams: Chemistry, Properties, and Applications.

Biopolymer aerogels were among the first aerogels produced, but only in the last decade has research on biopolymer and biopolymer-composite aerogels become popular, motivated by sustainability arguments, their unique and tunable properties, and ease of functionalization. Biopolymer aerogels and open-cell foams have great potential for classical aerogel applications such as thermal insulation, as well as emerging applications in filtration, oil-water separation, CO2 capture, catalysis, and medicine. The biopolymer aerogel field today is driven forward by empirical materials discovery at the laboratory scale, but requires a firmer theoretical basis and pilot studies to close the gap to market. This Review includes a database with over 3800 biopolymer aerogel properties, evaluates the state of the biopolymer aerogel field, and critically discusses the scientific, technological, and commercial barriers to the commercialization of these exciting materials.

SiO_{2} Glass Density to Lower-Mantle Pressures.

The convection or settling of matter in the deep Earth's interior is mostly constrained by density variations between the different reservoirs. Knowledge of the density contrast between solid and molten silicates is thus of prime importance to understand and model the dynamic behavior of the past and present Earth. SiO_{2} is the main constituent of Earth's mantle and is the reference model system for the behavior of silicate melts at high pressure. Here, we apply our recently developed x-ray absorption technique to the density of SiO_{2} glass up to 110 GPa, doubling the pressure range for such measurements. Our density data validate recent molecular dynamics simulations and are in good agreement with previous experimental studies conducted at lower pressure. Silica glass rapidly densifies up to 40 GPa, but the density trend then flattens to become asymptotic to the density of SiO_{2} minerals above 60 GPa. The density data present two discontinuities at ∼17 and ∼60 GPa that can be related to a silicon coordination increase from 4 to a mixed 5/6 coordination and from 5/6 to sixfold, respectively. SiO_{2} glass becomes denser than MgSiO_{3} glass at ∼40 GPa, and its density becomes identical to that of MgSiO_{3} glass above 80 GPa. Our results on SiO_{2} glass may suggest that a variation of SiO_{2} content in a basaltic or pyrolitic melt with pressure has at most a minor effect on the final melt density, and iron partitioning between the melts and residual solids is the predominant factor that controls melt buoyancy in the lowermost mantle.

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.

Strong, Thermally Superinsulating Biopolymer-Silica Aerogel Hybrids by Cogelation of Silicic Acid with Pectin.

Silica aerogels are excellent thermal insulators, but their brittle nature has prevented widespread application. To overcome these mechanical limitations, silica-biopolymer hybrids are a promising alternative. A one-pot process to monolithic, superinsulating pectin-silica hybrid aerogels is presented. Their structural and physical properties can be tuned by adjusting the gelation pH and pectin concentration. Hybrid aerogels made at pH 1.5 exhibit minimal dust release and vastly improved mechanical properties while remaining excellent thermal insulators. The change in the mechanical properties is directly linked to the observed "neck-free" nanoscale network structure with thicker struts. Such a design is superior to "neck-limited", classical inorganic aerogels. This new class of materials opens up new perspectives for novel silica-biopolymer nanocomposite aerogels.

The poor reliability of thermal conductivity data in the aerogel literature: a call to action!

Aerogels are an exciting class of materials with record-breaking properties including, in some cases, ultra-low thermal conductivities. The last decade has seen a veritable explosion in aerogel research and industry R&D, leading to the synthesis of aerogels from a variety of materials for a rapidly expanding range of applications. However, both from the research side, and certainly from a market perspective, thermal insulation remains the dominant application. Unfortunately, continued progress in this area suffers from the proliferation of incorrect thermal conductivity data, with values that often are far outside of what is possible within the physical limitations. This loss of credibility in reported thermal conductivity data poses difficulties in comparing the thermal performance of different types of aerogels and other thermal superinsulators, may set back further scientific progress, and hinder technology transfer to industry and society. Here, we have compiled 519 thermal conductivity results from 87 research papers, encompassing silica, other inorganic, biopolymer and synthetic polymer aerogels, to highlight the extent of the problem. Thermal conductivity data outside of what is physically possible are common, even in high profile journals and from the world's best universities and institutes. Both steady-state and transient methods can provide accurate thermal conductivity data with proper instrumentation, suitable sample materials and experienced users, but nearly all implausible data derive from transient methods, and hot disk measurements in particular, indicating that under unfavorable circumstances, and in the context of aerogel research, transient methods are more prone to return unreliable data. Guidelines on how to acquire reliable thermal conductivity data are provided. This paper is a call to authors, reviewers, editors and readers to exercise caution and skepticism when they report, publish or interpret thermal conductivity data.

Hyperbranched, Functional Polyethoxysiloxanes: Tunable Molecular Building Blocks.

Functional silanes are multifaceted cross-linkers, compatibilizers, coupling agents, and surface modifiers. Herein, we present organofunctional polysiloxane building blocks that offer great versatility in terms of molecular weight, degree of condensation, and the choice and loading of organic substituent groups. The organofunctional polyethoxysilanes (funPEOS) are prepared in a one-pot, two-step process: synthesis of the PEOS carrier/substrate, followed by grafting a functional silane "shell", both based on condensation with acetic anhydride. The reaction was optimized at the lab scale and scaled up to a 7 L reactor. The acetylation, condensation, and hyperbranched structure of the carrier were confirmed by 29Si NMR, while 29Si-29Si 2D INADEQUATE NMR provides strong evidence for the grafting of functional silanes onto the carrier (Q-T coupling). IR, 1H, and 13C NMR spectroscopy demonstrate that the functional groups remain intact. The molar mass can be tailored by stoichiometric control of the acetic anhydride to silane monomer ratio (M n 3500-20,000 g/mol). The compounds are stable organic liquids with a long shelf life. Selected applications are presented: scratch-resistant coatings with water contact angles of ∼90°, stable water emulsions, and surfactant-free, mesoporous silica foams.

Additive Manufacturing of Nanocellulose Aerogels with Structure-Oriented Thermal, Mechanical, and Biological Properties.

Additive manufacturing (AM) is widely recognized as a versatile tool for achieving complex geometries and customized functionalities in designed materials. However, the challenge lies in selecting an appropriate AM method that simultaneously realizes desired microstructures and macroscopic geometrical designs in a single sample. This study presents a direct ink writing method for 3D printing intricate, high-fidelity macroscopic cellulose aerogel forms. The resulting aerogels exhibit tunable anisotropic mechanical and thermal characteristics by incorporating fibers of different length scales into the hydrogel inks. The alignment of nanofibers significantly enhances mechanical strength and thermal resistance, leading to higher thermal conductivities in the longitudinal direction (65 mW m-1 K-1) compared to the transverse direction (24 mW m-1 K-1). Moreover, the rehydration of printed cellulose aerogels for biomedical applications preserves their high surface area (≈300 m2 g-1) while significantly improving mechanical properties in the transverse direction. These printed cellulose aerogels demonstrate excellent cellular viability (>90% for NIH/3T3 fibroblasts) and exhibit robust antibacterial activity through in situ-grown silver nanoparticles.

Carbon Nanostructures-Silica Aerogel Composites for Adsorption of Organic Pollutants.

Silica aerogels are a class of materials that can be tailored in terms of their final properties and surface chemistry. They can be synthesized with specific features to be used as adsorbents, resulting in improved performance for wastewater pollutants' removal. The purpose of this research was to investigate the effect of amino functionalization and the addition of carbon nanostructures to silica aerogels made from methyltrimethoxysilane (MTMS) on their removal capacities for various contaminants in aqueous solutions. The MTMS-based aerogels successfully removed various organic compounds and drugs, achieving adsorption capacities of 170 mg⋅g-1 for toluene and 200 mg⋅g-1 for xylene. For initial concentrations up to 50 mg⋅L-1, removals greater than 71% were obtained for amoxicillin, and superior to 96% for naproxen. The addition of a co-precursor containing amine groups and/or carbon nanomaterials was proven to be a valuable tool in the development of new adsorbents by altering the aerogels' properties and enhancing their adsorption capacities. Therefore, this work demonstrates the potential of these materials as an alternative to industrial sorbents due to their high and fast removal efficiency, less than 60 min for the organic compounds, towards different types of pollutants.

Silica-Resorcinol-Melamine-Formaldehyde Composite Aerogels as High-Performance Thermal Insulators.

Here, we report the gelation and supercritical drying of ethanol-based silica-resorcinol-melamine-formaldehyde (RMF) composite aerogels with relative concentrations of initial reagents ranging from neat silica to neat RMF alcogels. The as-prepared materials are subsequently supercritically dried with carbon dioxide. Their properties include a thermal conductivity in the 15-20 mW·m-1·K-1 range even with a silica content as low as 20%wt. The possible reasons behind this interesting insulation performance and the mechanisms leading to the underlying gel structure are discussed in depth. A focus is made on the different gelation modes happening between the RMF and silica phases, from a coating of silica surfaces with RMF species to discontinuous RMF particles within a silica backbone and a continuous RMF backbone with isolated silica particles. The implications in terms of mechanical properties and thermal conductivity are elaborated upon. The initial ratio of silica-RMF species in this ethanol-based synthesis affects the micro- and macrostructure of the composites, resulting in materials with drastically different pore structures and thus an interesting array of possibilities for a new class of silica-organic composite aerogels, based on a sol-gel process.

Superinsulating nanocellulose aerogels: Effect of density and nanofiber alignment.

Cellulose aerogels are potential alternatives to silica aerogels with advantages in cost, sustainability and mechanical properties. However, the density dependence of thermal conductivity (λ) for cellulose aerogels remains controversial. Cellulose aerogels were produced by gas-phase pH induced gelation of TEMPO-oxidized cellulose nanofibers (CNF) and supercritical drying. Their properties are evaluated by varying the CNF concentration (5-33 mg·cm-3) and by uniaxial compression (9-115 mg·cm-3). The aerogels are transparent with specific surface areas of ~400 m2·g-1, mesopore volumes of ~2 cm3·g-1 and a power-law dependence of the E-modulus (α ~ 1.53, and the highest reported E of ~1 MPa). The dataset confirms that λ displays a traditional U-shaped density dependence with a minimum of 18 mW·m-1·K-1 at 0.065 g·cm-3. For a given density, λ is ~5 mW·m-1·K-1 lower for compressed aerogels due to the alignment of nanofibers, confirmed by small angle X-ray scattering (SAXS).

Biomimetic Light-Driven Aerogel Passive Pump for Volatile Organic Pollutant Removal.

Inspired by the solar-light-driven oxygen transportation in aquatic plants, a biomimetic sustainable light-driven aerogel pump with a surface layer containing black manganese oxide (MnO2 ) as an optical absorber is developed. The flow intensity of the pumped air is controlled by the pore structure of nanofilbrillated cellulose, urea-modified chitosan, or polymethylsilsesquioxane (PMSQ) aerogels. The MnO2 -induced photothermal conversion drives both the passive gas flow and the catalytic degradation of volatile organic pollutants. All investigated aerogels demonstrate superior pumping compared to benchmarked Knudsen pump systems, but the inorganic PMSQ aerogels provide the highest flexibility in terms of the input power and photothermal degradation activity. Aerogel light-driven multifunctional gas pumps offer a broad future application potential for gas-sensing devices, air-quality mapping, and air quality control systems.

Transparent, Aldehyde-Free Chitosan Aerogel.

Aldehyde-free, transparent chitosan aerogel is reported. The aerogel was prepared by thermal decomposition of urea to induce gelation of a chitosan solution, followed by solvent exchange to ethanol, and supercritical drying. Low urea concentrations (≤ 25 g L-1) result in transparent and highly mesoporous aerogels, while higher urea concentrations (≥ 30 g L-1) produce opaque, more macroporous aerogels. The high surface areas of > 400 m2 g-1, large mesopore volumes up to 3.5 cm3 g-1, and optical transparency of the low-urea aerogels indicate a high structural homogeneity at the mesoscale, and the properties comparable to previously reported transparent chitosan aerogels prepared with formaldehyde crosslinking. The macroscopic size changes of the wet gels indicate that microstructure formation is controlled by the timing of chitosan coagulation, which depends among others on urea concentration. The aldehyde-free, microstructure-tunable process provides a new series of transparent biopolymer aerogels with "true aerogel" mesoporous structures.

A Systematic Study on Bio-Based Hybrid Aerogels Made of Tannin and Silica.

Tannin-silica hybrid materials are expected to feature excellent mechanic-chemical stability, large surface areas, high porosity and possess, after carbothermal reduction, high thermal stability as well as high thermal conductivity. Typically, a commercially available tetraethoxysilane is used, but in this study, a more sustainable route was developed by using a glycol-based silica precursor, tetrakis(2-hydroxyethyl)orthosilicate (EGMS), which is highly water-soluble. In order to produce highly porous, homogeneous hybrid tannin-silica aerogels in a one-pot approach, a suitable crosslinker has to be used. It was found that an aldehyde-functionalized silane (triethoxysilylbutyraldehyde) enables the covalent bonding of tannin and silica. Solely by altering the processing parameters, distinctly different tannin-silica hybrid material properties could be achieved. In particular, the amount of crosslinker is a significant factor with respect to altering the materials' properties, e.g., the specific surface area. Notably, 5 wt% of crosslinker presents an optimal percentage to obtain a sustainable tannin-silica hybrid system with high specific surface areas of roughly 800-900 m2 g-1 as well as a high mesopore volume. The synthesized tannin-silica hybrid aerogels permit the usage as green precursor for silicon carbide materials.

Ureido Functionalization through Amine-Urea Transamidation under Mild Reaction Conditions.

Ureido-functionalized compounds play an indispensable role in important biochemical processes, as well as chemical synthesis and production. Isocyanates, and KOCN in particular, are the preferred reagents for the ureido functionalization of amine-bearing compounds. In this study, we evaluate the potential of urea as a reagent to graft ureido groups onto amines at relatively low temperatures (<100 °C) in aqueous media. Urea is an inexpensive, non-toxic and biocompatible potential alternative to KOCN for ureido functionalization. From as early as 1864, urea was the go-to reagent for polyurea polycondensation, before falling into disuse after the advent of isocyanate chemistry. We systematically re-investigate the advantages and disadvantages of urea for amine transamidation. High ureido-functionalization conversion was obtained for a wide range of substrates, including primary and secondary amines and amino acids. Reaction times are nearly independent of substrate and pH, but excess urea is required for practically feasible reaction rates. Near full conversion of amines into ureido can be achieved within 10 h at 90 °C and within 24 h at 80 °C, and much slower reaction rates were determined at lower temperatures. The importance of the urea/amine ratio and the temperature dependence of the reaction rates indicate that urea decomposition into an isocyanic acid or a carbamate intermediate is the rate-limiting step. The presence of water leads to a modest increase in reaction rates, but the full conversion of amino groups into ureido groups is also possible in the absence of water in neat alcohol, consistent with a reaction mechanism mediated by an isocyanic acid intermediate (where the water assists in the proton transfer). Hence, the reaction with urea avoids the use of toxic isocyanate reagents by in situ generation of the reactive isocyanate intermediate, but the requirement to separate the excess urea from the reaction product remains a major disadvantage.

The partial (1)H NMR spectra of Al-OH and molecular H(2)O in hydrous aluminosilicate glasses: Component-Resolved analysis of (27)Al-(1)H cross polarization and (1)H spin-echo MAS NMR spectra.

The Component-Resolved methodology was applied to (1)H spin-echo and (27)Al-(1)H cross polarization (CP) MAS NMR data of aluminosilicate glasses. The method was able to resolve two components with different T2 relaxation rates, hydroxyl groups (OH) and molecular water (H(2)O(mol)), from the spin-echo data and to determine partial spectra and the relative abundances of OH and H(2)O(mol). The algorithm resolved two to three components with different (27)Al-(1)H CP dynamics from the (27)Al-(1)H cross polarization data; the obtained partial NMR spectra for Al-OH are in excellent agreement with those obtained previously from the difference spectra between spectra with various contact times and confirm previous quantitative results and models for the Al-OH, Si-OH and H(2)O(mol) speciation (Malfait and Xue, 2010).