Fragility and brittleness have always been flaws of delicate three-dimensional aerogel structures. Especially when exposed to harsh conditions (e.g. in aerospace applications), their frailty has limited the broad application of aerogels in such fields. A Chinese team of researchers from the Beijing Jiaotong University has now attended to this matter. By equipping a ZrO₂–SiO₂ aerogel with Polycrystalline ZrO₂ fibers (ZrO_2f), aerogels possessing high thermal and mechanical resilience have been devised. Astonishingly, these monolithic aerogels do not only excel in terms of stability, but also show low bulk densities and thermal conductivities.

The idea of adding a fibrous agent to the aerogel matrix is that, when dispersed evenly throughout the matrix, the fibers act as an additional mechanical backbone. This means that the fibers hinder fracturing and irreversible deformation through fiber-bridging and crack-deflection (see Figure below) when the monolithic structure is being strained. Furthermore, due to the even dispersion of the fibers in the aerogel matrix, the contribution of heat conduction through the fibers is minimized and hence the overall heat conductivity increases only marginally upon addition of the fibrous ZrO₂.

a) Image of ZrO2f/ZrO2-SiO2 aerogel monolith; b)–d) SEM images of fractures of the aerogel composite.

In summary, these effects lead to highly insulating aerogels possessing compressive strengths 3-10 times higher than previously reported. Therefore, applications in very demanding environments are facilitated, which might prove to be significant in aerospace engineering and other fields in which stable and highly insulating materials are essential.

More details: Xianbo Hou, Rubing Zhang and Daining Fang; An ultralight silica-modified ZrO₂–SiO₂ aerogel composite with ultra-low thermal conductivity and enhanced mechanical strength, Scripta Materialia Volume 143, 15 January 2018, Pages 113-116. http://doi.org/10.1016/j.scriptamat.2017.09.028

Researchers from the Kyoto University (Japan) successfully synthesized transparent, machinable, scalable, super-compressible, highly elastic and super-insulating polyvinylpolymethylsiloxane aerogels and xerogels. Remarkably, the study reports that these outstanding features were present not only in aerogels produced using supercritical drying, but in those produced using ambient pressure drying, too.

The sample preparation was achieved by mixing vinylmethyldimethoxysilane (VMDMS) or vinylmethyldiethoxysilane (VMDES) with 1-5 % of di-tert-butyl peroxide (DTBP), to initiate the radical polymerization at 120 °C, yielding a transparent viscous liquid mainly containing polyvinylmethyldimethoxysilane (PVMDMS) or polyvinylmethyldiethoxysilane (PVMDES). Thereafter, BzOH, H₂O and tetramethylammonium hydroxide (TMAOH) were added to the liquid and the mixture was heated to 80 °C for one hour to obtain transparent and flexible gels. Prior to solvent exchange with isopropanol (IPA), the gels were aged between four or five days at 80-100 °C. Removal of the liquid was subsequently accomplished in three different ways (see Figure below): (1) supercritical drying with CO₂; (2) solvent exchange into n-hexane followed by drying at ambient pressure; (3) direct drying from IPA at ambient pressure.

Comparison of different drying methods to obtain PVMDMS or PCMDES aerogels and xerogels.

It was established that key to the intriguing properties of the dried aerogels and xerogels are their homogeneous porous nanostructure, composed of flexible hydrocarbon chains chemically cross-linked with polymethylsiloxanes. Notably, this type of nanostructure structure exhibited low densities (0.16-0.22 g/cm³) and heat conductivities (15.0-15.4 mW/m K), as well as high specific surface areas (900-1000 m²/g), good transparency (>80 % light transmittance), and extraordinary flexibility (see attached video). Additionally, the flexible network structures allowed for a recovery of the evaporation-induced gel shrinkage through a “spring-back” effect (see Figure below), making the supercritical drying step dispensable.

Progression of gel volume during ambient pressure drying. “spring-back” effect yields xerogels of nearly the same volume as the parent gel.

In summary, these findings imply that an ultra-low cost pathway to manufacture aerogels by ambient pressure drying while still preserving extraordinary properties required for applications as superinsulators has been established. This means that one of the main obstacles for the broad application of aerogels — their high manufacturing costs — has been overcome, which might pave the way for their large scale deployment.

More details: Zu et al.; Transparent, Superflexible Doubly Cross-Linked Polyvinylpolymethylsiloxane Aerogel Superinsulators via Ambient Pressure Drying , ACS Nano, January 8, 2018. https://doi.org/10.1021/acsnano.7b07117

Video of aerogel bending test: Click Here

The search for active yet economical water purification strategies is in full swing as increasing industrial activity results in sharp surges in wastewater production, and the ever-growing global population increases demand for clean drinking water.

Commonly, separated, sophisticated absorption processes are deployed to remove either organic or inorganic contaminants from sewage water due to their high efficiency and moderate cost. However, it remains a challenge to devise robust, efficient and economical absorbents for the wide range of trace elements occurring in wastewater. Ideally, novel absorption materials should be able to remove inorganic compounds such as dyes or heavy metals and also be active against harmful viral or bacterial pathogens.

In pursuit of such a material, researchers from Jinan University (China) have synthesized an aerogel structure exhibiting extraordinary dye and heavy metal absorbing properties, by using graphene oxide (GO) and a type of abundant mineral called montmorillonite (MMT). The desired anti-pathogenic activity was realized through equipping the aerogel matrix with a common anti-bacterial agent, resulting in absorbents displaying excellent antibacterial activity against Gram-positive and Gram-negative bacteria.

The aerogel material exhibiting these intriguing properties was manufactured through mixing GO powder, ascorbic acid, and a MMT solution, then inducing gelation through heat treatment at 95 °C. After aging of the hydrogel in a PVA solution for two days, the gel was then freeze dried at -55 °C, resulting in a monolithic aerogel structure, which is shown in the Figure below.

Image of black GO-MMT aerogel placed on top of kapok tree fiber.

Absorption experiments showed that the aerogel absorbents were not only able to remove more than 95 % of methyl orange and methylene blue dyes from aqueous solutions, but also exhibited great properties for the removal of heavy metals from water (e.g. >90 % removal efficiency for chromium ion removal). This activity was found to be stable over numerous absorption/desorption cycles, with sample regeneration being achieved by vigorous shaking. Furthermore, the addition of antibacterial dodecyl dimethyl benzyl ammonium chloride (1227) to the initial precursor solution was found to provide the aerogel with antibacterial activity, which was shown using E. coli and S. aureus bacteria cultures, each losing over 90 % of their cell viability in the presence of the GO-MMT-1227 aerogel material.

Due to these extraordinary findings, the researchers are confident that they have found an efficient, versatile, recyclable, and robust absorbent material, which has the potential to revolutionize water purification. If economical large scale manufacturing and long term stability can be achieved, the novel material might indeed replace state-of-the-art sorbents in wastewater treatment systems.

More details: Yunyun Zhang et al.; The utilization of a three-dimensional reduced graphene oxide and montmorillonite composite aerogel as a multifunctional agent for wastewater treatment, RSC Adv., 2018,8, 4239-4248. https://doi.org/10.1039/C7RA13103H

The enhancing effects of polyaniline (PANi) coatings on ion and electron conductivity are well known (see also here), which is why researchers from the Sun Yat-sen University (China) devised PANi-coated activated carbon/sulfur aerogels (ACA-500-S) in order to improve the electrochemical properties of the un-coated composite. By synthesizing this novel electrode material, the research team hopes to address drawbacks of Li-S batteries (e.g. low ionic conductivity, dissolution of polysulfides in electrolytes).

Carbon/sulfur composite aerogels were produced by heat-melting state-of-the-art activated carbon aerogels (ACA-500) in the presence of elemental sulfur. As shown in the Figure below, the PANi coating was subsequently applied by in-situ chemical oxidative polymerization at low temperatures, yielding the final ACA-500-S@PANi electrode material. Investigation of the sample morphology via FESEM and TEM revealed that the manufacturing technique led to a homogeneous distribution of sulfur and PANi on the aerogel surface. Because of the even dispersion of the active agents on the aerogel matrix, enhanced electrochemical performance was expected from the ACA-500-S@PANi composite.

Schematic of synthesizing process of ACA-500-S@PANi aerogels from state-of-the-art activated carbon aerogels (ACA-500)

This expectation was confirmed in ensuing experiments, which compared the specific capacity, capacity discharge, and capacity retention of the ACA-500-S and ACA-500-S@PANi materials. It was shown that the latter material outperformed the carbon/sulfur aerogel in all regards, which was attributed to the synergistic effect of the carbon aerogel matrix and the PANi coating on ion and electron conductivity as well as electrode stability. More specifically, the researchers discovered that the ACA-500-S@PANi structure presented high reversible capacities at low (at 0.2 C: 1208 mAh g⁻¹) and high (at 3.0 C: 542 mAh g⁻¹) discharge rates. Furthermore, long term cycling at 1.0 C demonstrated that it exhibits a notable initial discharge capacity of 926 mAh g^-1 and outstanding capacity retention of over 65 % at a low capacity decay rate of 0.48 ‰ per cycle.

Because of these findings, the researchers are confident that the novel aerogel composite will be able to boost the performance of lithium-sulfur batteries, meeting the increasing demand for batteries exhibiting a high energy density and long life span at low cost.

More details: Tang et al.; Polyaniline-Coated Activated Carbon Aerogel/Sulfur Composite for High- performance Lithium-Sulfur Battery, Nanoscale Research Letters 2017. https://doi.org/10.1186/s11671-017-2372-6