Nanoenergetic Composites with Fluoropolymers: Transition from Powders to Structures.

Over the years, nanoenergetic materials have attracted enormous research interest due to their overall better combustion characteristics compared to their micron-sized counterparts. Aluminum, boron, and their respective alloys are the most extensively studied nanoenergetic materials. The majority of the research work related to this topic is confined to the respective powders. However, for practical applications, the powders need to be consolidated into reactive structures. Processing the nanoenergetic materials with polymeric binders to prepare structured composites is a possible route for the conversion of powders to structures. Most of the binders, including the energetic ones, when mixed with nanoenergetic materials even in small quantities, adversely affects the ignitability and combustion performance of the corresponding composites. The passivating effect induced by the polymeric binder is considered unfavorable for ignitability. Fluoropolymers, with their ability to induce pre-ignition reactions with the nascent oxide shell around aluminum and boron, are recognized to sustain the ignitability of the composites. Initial research efforts have been focused on surface functionalizing approaches using fluoropolymers to activate them further for energy release, and to improve the safety and storage properties. With the combined advent of more advanced chemistry and manufacturing techniques, fluoropolymers are recently being investigated as binders to process nanoenergetic materials to reactive structures. This review focuses on the major research developments in this area that have significantly assisted in the transitioning of nanoenergetic powders to structures using fluoropolymers as binders.

Cryogel-Templated Fabrication of n-Al/PVDF Superhydrophobic Energetic Films with Exceptional Underwater Ignition Performance.

The rapid heat loss and corrosion of nano-aluminum limits the energy performance of metastable intermolecular composites (MICs) in aquatic conditions. In this work, superhydrophobic n-Al/PVDF films were fabricated by the cryogel-templated method. The underwater ignition performance of the energetic films was investigated. The preparation process of energetic materials is relatively simple, and avoids excessively high temperatures, ensuring the safety of the entire experimental process. The surface of the n-Al/PVDF energetic film exhibits super-hydrophobicity. Because the aluminum nanoparticles are uniformly encased in the hydrophobic energetic binder, the film is more waterproof and anti-aging. Laser-induced underwater ignition experiments show that the superhydrophobic modification can effectively induce the ignition of energetic films underwater. The results suggest that the cryogel-templated method provides a feasible route for underwater applications of energetic materials, especially nanoenergetics-on-a-chip in underwater micro-scale energy-demanding systems.

Enhanced Energetic Performance of Aluminum Nanoparticles by Plasma Deposition of Perfluorinated Nanofilms.

The performance of Al as nanoenergetic material in solid fuel propulsion or additive in liquid fuels is limited by the presence of the native oxide layer at the surface, which represents a significant weight fraction, does not contribute to heat release during oxidation, and acts as a diffusion barrier to Al oxidation. We develop an efficient technique in which the oxide layer is effectively turned into an energetic component via a reaction with fluorine that is coated in the form of a fluorocarbon nanofilm on the Al surface by plasma-enhanced chemical vapor deposition. Perfluorodecalin vapors are introduced in a low-pressure plasma reactor to produce nanofilms on the surface of Al nanoparticles, whose thickness is controlled with nanolevel precision as demonstrated by high-resolution transmission electron microscopy images. Coated particles show superior heat release, with a maximum enhancement of 50% at a thickness of 10 nm. This significant improvement is attributed to the chemical interaction between Al2O3 and F to form AlF3, which removes the oxide barrier via an exothermic reaction and contributes to the amount of heat released during thermal oxidation. The chemistry and mechanism of the enhancement effect of the plasma nanofilms are explained with the help of X-ray photoelectron spectroscopy, X-ray diffraction, high-angle annular dark-field scanning transmission electron microscopy-energy dispersive spectroscopy, thermogravimetric analysis, and differential scanning calorimetry.

Surface-Functionalized Boron Nanoparticles with Reduced Oxide Content by Nonthermal Plasma Processing for Nanoenergetic Applications.

The development of an in situ nonthermal plasma technology improved the oxidation and energy release of boron nanoparticles. We reduced the native oxide layer on the surface of boron nanoparticles (70 nm) by treatment in a nonthermal hydrogen plasma, followed by the formation of a passivation barrier by argon plasma-enhanced chemical vapor deposition (PECVD) using perfluorodecalin (C10F18). Both processes occur near room temperature, thus avoiding aggregation and sintering of the nanoparticles. High-resolution transmission electron microscopy (HRTEM), high-angular annular dark-field imaging (HAADF)-scanning TEM (STEM)-energy dispersive spectroscopy (EDS), and X-ray photoelectron spectroscopy (XPS) demonstrated a significant reduction in surface oxide concentration due to hydrogen plasma treatment and the formation of a 2.5 nm thick passivation coating on the surface due to PECVD treatment. These results correlated with the thermal analysis results, which demonstrated a 19% increase in energy release and an increase in metallic boron content after 120 min of hydrogen plasma treatment and 15 min of PECVD of perfluorodecalin. The PECVD coating provided excellent passivation against air and humidity for 60 days. We conclude in situ nonthermal plasma reduction and passivation lead to the amelioration of energy release characteristics and the storage life of boron nanoparticles, benefits conducive for nanoenergetic applications.

Highly Flexible and Patternable Multiwalled-Carbon Nanotube/Nitrocellulose Hybrid Conducting Paper Electrodes as Heating Platforms for Effective Ignition of Nanoenergetic Materials.

In this study, a highly flexible, patternable multiwalled-carbon nanotube (MWCNT) paper electrode was specially designed and fabricated. The addition of a nitrocellulose (NC) polymer binder at less than the critical amount (≤2 wt %) was found to be effective for maintaining both the flexibility and electrical conductance of the resulting MWCNT paper electrode. The fabricated MWCNT paper electrode was then employed as a heating platform to ignite Al/CuO nanoparticle-based nanoenergetic materials (nEMs). The nEM layer was drop-cast on the surface of the MWCNT paper electrode with specially patterned shapes using a plotter, and its ignition was evaluated by applying various voltages through the MWCNT paper electrode. To increase the adhesion between the nEM layer and MWCNT paper electrode and to decrease the sparking sensitivity of the nEM layer, it was essential to incorporate NC in the nEM matrix. However, the combustion and explosion properties of nEM layers deteriorated with the addition of NC, enabling the estimation of the optimum amount of NC to be incorporated. The fabricated igniter can be employed in various thermal engineering applications, such as in the ignition of explosives and propellants, and in pyrotechnics. To demonstrate this, a compact, flexible, and patternable igniter composed of the NC/nEM layer (NC/nEM = 2:8 wt %) on an MWCNT paper electrode was used to successfully ignite solid propellants for launching a small rocket.

A Facile Preparation and Energetic Characteristics of the Core/Shell CoFe2O4/Al Nanowires Thermite Film.

In this study, CoFe2O4 is selected for the first time to synthesize CoFe2O4/Al nanothermite films via an integration of nano-Al with CoFe2O4 nanowires (NWs), which can be prepared through a facile hydrothermal-annealing route. The resulting nanothermite film demonstrates a homogeneous structure and an intense contact between the Al and CoFe2O4 NWs at the nanoscale. In addition, both thermal analysis and laser ignition test reveal the superb energetic performances of the prepared CoFe2O4/Al NWs nanothermite film. Within different thicknesses of nano-Al for the CoFe2O4/Al NWs nanothermite films investigated here, the maximum heat output has reached as great as 2100 J·g-1 at the optimal thickness of 400 nm for deposited Al. Moreover, the fabrication strategy for CoFe2O4/Al NWs is also easy and suitable for diverse thermite systems based upon other composite metal oxides, such as MnCo2O4 and NiCo2O4. Importantly, this method has the featured advantages of simple operation and compatibility with microsystems, both of which may further facilitate potential applications for functional energetic chips.

Core-Shell Structured Nanoenergetic Materials: Preparation and Fundamental Properties.

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.

Enhancing the Reactivity of Al/CuO Nanolaminates by Cu Incorporation at the Interfaces.

In situ deposition of a thin (∼5 nm) layer of copper between Al and CuO layers is shown to increase the overall nanolaminate material reactivity. A combination of transmission electron microscopy imaging, in situ infrared spectroscopy, low energy ion scattering measurements, and first-principles calculations reveals that copper spontaneously diffuses into aluminum layers (substantially less in CuO layers). The formation of an interfacial Al:Cu alloy with melting temperature lower than pure Al metal is responsible for the enhanced reactivity, opening a route to controlling the stochiometry of the aluminum layer and increasing the reactivity of the nanoenergetic multilayer systems in general.