Exfoliated Magnesium Diboride (MgB2) Nanosheets as Solid Fuels.

Magnesium diboride (MgB2) has been explored as an alternative fuel to boron (B) due to its high energy density and the additive effect of magnesium (Mg) to promote B combustion. However, the primary oxidation of MgB2 does not occur unless it decomposes at a high temperature (830 °C), which makes ignition difficult and the reaction slow. Recently, two-dimensional (2D) exfoliated MgB2 nanosheets have attracted increasing attention due to their unique properties and potential applications in various fields. In this study, we investigate the potential of 2D exfoliated MgB2 nanosheets as solid fuels for overcoming the challenges of MgB2 combustion. We analyzed their oxidation behavior and energetic performance through material characterization and combustion tests under slow- and fast-heating conditions and compared their performance with those of bulk MgB2, B nanoparticles, and a B/Mg nanoparticle mixture. This study highlights the potential of MgB2 nanosheets as promising solid fuels with superior energetic properties.

Perfluoroalkyl-Functionalized Graphene Oxide as a Multifunctional Additive for Promoting the Energetic Performance of Aluminum.

Aluminum (Al) is a widely used metal fuel for energetic applications ranging from space propulsion and exploration, and materials processing, to power generation for nano- and microdevices due to its high energy density and earth abundance. Recently, the ignition and combustion performance of Al particles were found to be improved by graphene-based additives, such as graphene oxide (GO) and graphene fluoride (GF), as their reactions provide heat to accelerate Al oxidation, gas to reduce particle agglomeration, and fluorine-containing species to remove Al2O3. However, GF is not only expensive but also hydrophobic with poor mixing compatibility with Al particles. Herein, we report a multifunctional graphene-based additive for Al combustion, i.e., perfluoroalkyl-functionalized graphene oxide (CFGO), which integrates the benefits of GO and GF in one material. We compared the effects of CFGO to GO and GF on the ignition and combustion properties of nAl particles using thermogravimetric analysis, differential scanning calorimetry, temperature-jump ignition), Xe flash ignition, and constant-volume combustion test. These experiments confirm that CFGO generates fluorine-containing species, heat, and gases, which collectively lower the ignition threshold, augment the energy release rate, and reduce the combustion product agglomeration of nanosized Al particles, outperforming both GO and GF as additives. This work shows the great potential of using multifunctionalized graphene as an integrated additive for enhancing the ignition and combustion of metals.

Effect of Fluoroalkylsilane Surface Functionalization on Boron Combustion.

Boron has been regarded as a promising high-energy fuel due to its high volumetric and gravimetric heating values. However, it remains challenging for boron to attain its theoretical heat of combustion because of the existence of its native boron oxide layer and its high melting and boiling temperatures that delay ignition and inhibit complete combustion. Boron combustion is known to be enhanced by physically adding fluorine-containing chemicals, such as fluoropolymer or metal fluorides, to remove surface boron oxides. Herein, we chemically functionalize the surface of boron particles with three different fluoroalkylsilanes: FPTS-B (F3-B), FOTS-B (F13-B), and FDTS-B (F17-B). We evaluated the ignition and combustion properties of those three functionalized boron particles as well as pristine ones. The boron particles functionalized with the longest fluorocarbon chain (F17) exhibit the most powerful energetic performance, the highest heat of combustion, and the strongest BO2 emission among all samples. These results suggest that the surface functionalization with fluoroalkylsilanes is an efficient strategy to enhance boron ignition and combustion.

Blocking chemical warfare agent simulants by graphene oxide/polymer multilayer membrane based on hydrogen bonding and size sieving effect.

Chemical warfare agents (CWAs) are toxic materials that cause death by contact with the skin or by respiration. Although studies on detoxification of CWAs have been intensively conducted, studies that block CWAs permeation are rare. In this study, for blocking CWAs, a multilayer thin film composed of linear polyethylenimine (LPEI) and graphene oxide (GO) is simply prepared through a spray-assisted Layer-by-Layer (LbL) assembly process. LPEI could change its morphology dependent on pH, which is known as a representative hydrogen donor and acceptor. By controlling the shape of the polymer chain, a heterogenous film could have a loose or dense inner structure. CWAs mainly move through diffusion and have hydrogen bonding sites. Therefore, the heterogeneous film can limit CWAs movement based on controlling pathways and hydrogen bonds within the film. The protective effect of this membrane is investigated using dimethyl methylphosphonate (DMMP), a nerve gas simulant. DMMP vapor transmittance rate (DVTR) and N2 permeance of LPEI/GO are 67.91 g/m2 day and 34,293.04 GPU. It means that the protection efficiency is 72.65%. Although this membrane has a thin thickness (100 nm), it shows a high protective effect with good breathability. And water/DMMP selectivity of the membrane is 66.63. Since this multilayer membrane shows efficient protection performance with a simple preparation method, it has a high potential for applications such as protective suits and masks.

UiO-66-NH2 and Zeolite-Templated Carbon Composites for the Degradation and Adsorption of Nerve Agents.

Composites of metal-organic frameworks and carbon materials have been suggested to be effective materials for the decomposition of chemical warfare agents. In this study, we synthesized UiO-66-NH2/zeolite-templated carbon (ZTC) composites for the adsorption and decomposition of the nerve agents sarin and soman. UiO-66-NH2/ZTC composites with good dispersion were prepared via a solvothermal method. Characterization studies showed that the composites had higher specific surface areas than pristine UiO-66-NH2, with broad pore size distributions centered at 1-2 nm. Owing to their porous nature, the UiO-66-NH2/ZTC composites could adsorb more water at 80% relative humidity. Among the UiO-66-NH2/ZTC composites, U0.8Z0.2 showed the best degradation performance. Characterization and gas adsorption studies revealed that beta-ZTC in U0.8Z0.2 provided additional adsorption and degradation sites for nerve agents. Among the investigated materials, including the pristine materials, U0.8Z0.2 also exhibited the best protection performance against the nerve agents. These results demonstrate that U0.8Z0.2 has the optimal composition for exploiting the degradation performance of pristine UiO-66-NH2 and the adsorption performance of pristine beta-ZTC.

Fabrication of Graphene Based Durable Intelligent Personal Protective Clothing for Conventional and Non-Conventional Chemical Threats.

Conventional or non-conventional chemical threat is gaining huge attention due to its unpredictable and mass destructive effects. Typical military protective suits have drawbacks such as high weight, bulky structure, and unpredictable lifetime. A durable, light, and scalable graphene e-fabric was fabricated from CVD-grown graphene by a simple co-lamination method. The sheet resistance was below 1 kΩ/sq over the wide surface area even after 1000 bending cycles. A graphene triboelectric nanogenerator showed the peak VOC of 68 V and the peak ICC of 14.4 µA and 1 µF capacitor was charged successfully in less than 1 s. A wearable chemical sensor was also fabricated and showed a sensitivity up to 53% for nerve chemical warfare agents (GD). DFT calculations were conducted to unveil the fundamental mechanisms underlying the graphene e-fabric sensor. Additionally, protection against chemical warfare agents was tested, and a design concept of graphene-based intelligent protective clothing has been proposed.

Zr(OH)4/GO Nanocomposite for the Degradation of Nerve Agent Soman (GD) in High-Humidity Environments.

Zirconium hydroxide, Zr(OH)4 is known to be highly effective for the degradation of chemical nerve agents. Due to the strong interaction force between Zr(OH)4 and the adsorbed water, however, Zr(OH)4 rapidly loses its activity for nerve agents under high-humidity environments, limiting real-world applications. Here, we report a nanocomposite material of Zr(OH)4 and graphene oxide (GO) which showed enhanced stability in humid environments. Zr(OH)4/GO nanocomposite was prepared via a dropwise method, resulting in a well-dispersed and embedded GO in Zr(OH)4 nanocomposite. The nitrogen (N2) isotherm analysis showed that the pore structure of Zr(OH)4/GO nanocomposite is heterogeneous, and its meso-porosity increased from 0.050 to 0.251 cm3/g, compared with pristine Zr(OH)4 prepared. Notably, the composite material showed a better performance for nerve agent soman (GD) degradation hydrolysis under high-humidity air conditions (80% relative humidity) and even in aqueous solution. The soman (GD) degradation by the nanocomposite follows the catalytic reaction with a first-order half-life of 60 min. Water adsorption isotherm analysis and diffuse reflectance infrared Fourier transform (DRIFT) spectra provide direct evidence that the interaction between Zr(OH)4 and the adsorbed water is reduced in Zr(OH)4/GO nanocomposite, indicating that the active sites of Zr(OH)4 for the soman (GD) degradation, such as surface hydroxyl groups are almost available even in high-humidity environments.