Highly reactive metastable intermixed composites (MICs) have attracted much attention in the past decades. The MIC family of materials mainly includes traditional metal-based nanothermites, novel core-shell-structured, 3D ordered macroporous-structured, and ternary nanocomposites. By applying special fabrication approaches, highly reactive MICs with uniformly dispersed reactants, "layer-by-layer" or "core-shell" structures, can be prepared. Thus, the combustion performance can be greatly improved, and the ignition characteristics and safety can be precisely controlled by using a certain preparation strategy. Here, the preparation and characterization of the MICs that have been developed during the past few decades are summarized. Traditional preparation methods for MICs generally include physical mixing, high-energy ball milling, sol-gel synthesis, and vapor deposition, while the novel methods include self-assembly, electrophoretic deposition, and electrospinning. Various preparation procedures and the ignition and combustion performance of different MIC reactive systems are compared and discussed. In particular, the advantages of novel structured MICs in terms of safety and combustion efficiency are clarified, based on which suggestions regarding the possible future research directions are proposed.

Highly Reactive Metastable Intermixed Composites (MICs): Preparation and Characterization

Energetic materials, including explosives, pyrotechnics, and propellants, are widely used in mining, demolition, automobile airbags, fireworks, ordnance, and space technology. Nanoenergetic materials (nEMs) have a high reaction rate and high energy density, which are both adjustable to a large extent. Structural control over nEMs to achieve improved performance and multifunctionality leads to a fascinating research area, namely, nanostructured energetic materials. Among them, core-shell structured nEMs have gained considerable attention due to their improved material properties and combined multiple functionalities. Various nEMs with core-shell structures have been developed through diverse synthesis routes, among which core-shell structured nEMs associated with explosives and metastable intermolecular composites (MICs) are extensively studied due to their good tunability and wide applications, as well as excellent energetic (e.g., enhanced heat release and combustion) and/or mechanical properties. Herein, the preparation methods and fundamental properties of the abovementioned kinds of core-shell structured nEMs are summarized and the reasons behind the satisfactory performance clarified, based on which suggestions regarding possible future research directions are proposed.

Core–Shell Structured Nanoenergetic Materials: Preparation and Fundamental Properties

Comparison study of the ignition and combustion characteristics of directly-written Al/PVDF, Al/Viton and Al/THV composites

The metastable intermixed composite (MIC) is one of the most popular research topics in the field of energetic materials (EMs). The goal is to invent EMs with tunable reactivity and desired energy content. However, it is very difficult to tune the reactivity of MIC due to its high reactivity and sensitivity caused by enlarged specific surface area and intimate contact between the oxidizers and fuels. Herein, we demonstrated a facile fabrication method that can be used to control the reactivity between the nanoaluminum (n-Al) and poly(tetrafluoroethylene) (PTFE) using an in situ-synthesized polydopamine (PDA) binding layer. It was found that PDA can adhere to both n-Al and PTFE particles, resulting in integrated n-Al@PDA/PTFE MICs. In comparison with traditional n-Al/PTFE MICs, the n-Al@PDA/PTFE showed an increased energy release and reduced sensitivity and more importantly tunable reactivity. By regulating the experimental conditions of coating, the thickness of PDA could be well controlled, which makes t...

Tuning the Reactivity of Metastable Intermixed Composite n-Al/PTFE by Polydopamine Interfacial Control

Fluorine-containing oxidizers for metal fuels in energetic formulations

Energetic thin films with high mass loadings of nanosized components have been recently fabricated using electrospray deposition. These films are composed of aluminum nanoparticles (nAl) homogeneously dispersed in an energetic fluoropolymer binder, poly(vinylidene fluoride) (PVDF). The nascent oxide shell of the nAl has been previously shown to undergo a preignition reaction (PIR) with fluoropolymers such as polytetrafluoroethylene (PTFE). This work examines the PIR between alumina and PVDF to further explain the reaction mechanism of the Al/PVDF system. Temperature jump (T-jump) ignition experiments in air, argon, and vacuum environments showed that the nAl is fluorinated by gas phase species due to a decrease in reactivity in a vacuum. Thermogravimetric analysis coupled with differential scanning calorimetry (TGA/DSC) was used to confirm the occurrence of a PIR, and gas phase products during the PIR and fluorination of nAl were investigated with temperature jump time-of-flight mass spectrometry (T-jump ...

Probing the Reaction Mechanism of Aluminum/Poly(vinylidene fluoride) Composites.

Metal iodate oxidizers are synthesized and evaluated as oxidizers in thermite reactions to generate both heat and a biocidal reaction product for bioagent defeat. TGA/DSC/MS and T-jump TOFMS analysis show gas-phase iodine release from metal iodate decomposition at both low and high heating rates. In constant volume combustion tests, Bi(IO3)3/Al thermite outperforms other metal iodate/Al and traditional thermites. Mechanically sound composites with high mass loadings of particulates are formed by direct electrospray of synthesized metal iodates, nanoaluminum fuel, and polyvinylidine fluoride (PVDF) binder/oxidizer, and burn speeds are measured in both air and argon atmospheres.

Direct Deposit of Highly Reactive Bi(IO3)3- Polyvinylidene Fluoride Biocidal Energetic Composite and its Reactive Properties†

This study reports on an on-the-fly green synthesis/dispersion of silver iodide (AgI) nanoparticles from the combustion of AgIO3/carbon black (CB)/nitrocellulose (NC) composites, which could be used as a candidate for a cloud-seeding pyrotechnic. Films were formed by direct electrospray deposition of a mixture of synthesized silver iodate with CB and NC. The decomposition pathways of AgIO3/CB and AgIO3/CB/NC were evaluated by temperature jump time of flight mass spectrometry (T-jump TOFMS) and XRD, showing that AgI particles and CO2 are released from the reaction between AgIO3 and CB without other toxic residuals. The flame propagation velocity of AgIO3/CB/NC films increases with the increasing of particle mass loading of AgIO3 and CB and peaks at 40 wt%, which is much higher than that of an AgI/AP/NC film. The mean diameter of the resultant AgI nanoparticles is from 51 to 97 nm. The mass loading of AgIO3 and CB was found to play a major role in size control of the AgI nanoparticles.

Xiuli Hu

Papers

Probing the Reaction Mechanism of Aluminum/Poly(vinylidene fluoride) Composites.

Direct Deposit of Highly Reactive Bi(IO3)3- Polyvinylidene Fluoride Biocidal Energetic Composite and its Reactive Properties†

On-the-fly green generation and dispersion of AgI nanoparticles for cloud seeding nuclei