Synthesis and protection: a controllable electrochemical approach to polypyrrole-coated copper azide with superior safety for MEMS.

Traditional lead-based primary explosives present challenges in application to micro-energetics-on-a-chip. It is highly desired but still remains challenging to design a primary explosive for the development of powerful yet safe energetic films. Copper-based azides (Cu(N3)2 or CuN3, CA) are expected to be ideal alternatives owing to their properties such as excellent device compatibility, excellent detonation performance, and low environmental pollution. However, the significantly high electrostatic sensitivity of CA limits its use in micro-electro-mechanical systems (MEMS). This study presents an in situ electrochemical approach to preparing and modifying a CA film with excellent electrostatic safety using a Cu chip. Herein, a CA film is prepared by employing Cu nanorod arrays as precursors. Next, polypyrrole (PPy) is directly coated on the surface of the CA materials to produce a CA@PPy composite energetic film using the electrochemical process. The results show that CuN3 is first generated and gradually oxidized to Cu(N3)2, essentially forming enclosed nest-like structures during electrochemical azidation. The microstructure and composition of the product can be regulated by varying the current density and reaction time, which leads to controllable heat output of the CA from 521 to 1948 J g-1. Notably, the composite energetic film exhibits excellent electrostatic sensitivity (2.69 mJ) owing to the excellent conductivity of PPy. Thus, this study offers novel ideas for the further advances of composite energetic materials and applications in MEMS explosive systems.

In Situ Electrochemical Construction of CuN3@CuCl Hybrids for Controllable Energy Release and Self-Passivation Ability.

Advanced energetic materials (EMs) play a crucial role in the advancement of microenergetic systems as actuation parts, igniters, propulsion units, and power. The sustainable electrosynthesis of EMs has gained momentum and achieved substantial improvements in the past decade. This study presents the facile synthesis of a new type of high-performance CuN3@CuCl hybrids via a co-electrodeposition methodology utilizing porous Cu as the sacrificial template. The composition, morphology, and energetic characteristics of the CuN3@CuCl hybrids can be easily tuned by adjusting the deposition times. The resulting hybrids demonstrate remarkable energy output (1120 J·g-1) and good laser-induced initiating ability. As compared with porous CuN3, the uniform doping of inert CuCl enhances the electrostatic safety of the hybridized material without compromising its overall energetic characteristics. Notably, the special oxidizing behavior of CuCl gradually lowers the susceptibility of the hybrid material to laser and electrostatic stimulation. This has significant implications for the passivation or self-destruction of highly sensitive EMs. Overall, this study pioneers a new path for the development of MEMS-compatible EMs, facilitating further microenergetic applications.

Valence-Oriented Electrosynthesis Strategies of Cu-Based 5-Nitrotetrazolate for Environmentally Acceptable Primary Explosives.

The development of green primary explosives has become a "holy grail" of energetic materials research. Cu-based 5-nitrotetrazolate is considered one of the most promising candidates due to its excellent blasting power and environmentally benign nature. However, synthesizing Cu-based 5-nitrotetrazolate controllably and securely remains highly challenging. Herein, room-temperature anodization of metallic Cu and a Cu(I)-imidazole nanowire array on copper substrates in a sodium 5-nitrotetrazolate electrolyte leads to in situ electrosynthesis of Cu(I) 5-nitrotetrazolate (DBX-1, CuNT) and its analogue, Cu(II) 5-nitrotetrazolate [Cu(NT)2], respectively. Both obtained CuNT and Cu(NT)2 films demonstrate remarkable energy output and good laser-induced ignition performance. The thermal stability (Tp = 291 °C) and electrostatic safety (E50 = 2.54 mJ) of CuNT proved to be superior to those of Cu(NT)2 (Tp = 257 °C, and E50 = 0.57 mJ). Remarkably, this study provides an exciting new method for the rational design and development of Cu-based 5-nitrotetrazolate as a primary explosive for advanced initiating applications.

Copper Azide Nanoparticle-Encapsulating MOF-Derived Porous Carbon: Electrochemical Preparation for High-Performance Primary Explosive Film.

It is highly desired but still remains challenging to design a primary explosive-based nanoparticle-encapsulated conductive skeleton for the development of powerful yet safe energetic films employed in miniaturized explosive systems. Herein, a proof-of-concept electrochemical preparation of metal-organic frameworks (MOFs) derived porous carbon embedding copper-based azide (Cu(N3 )2 or CuN3 , CA) nanoparticles on copper substrate is described. A Cu-based MOF, i.e., Cu-BTC is fabricated based on anodized Cu(OH)2 nanorods, as a template, to achieve CA/C film through pyrolysis and electrochemical azidation. Such a CA/C film, which is woven by numerous ultrafine nanofibers, favorably demonstrates excellent energy release (945-2090 J g-1 ), tunable electrostatic sensitivity (0.22-1.39 mJ), and considerable initiation ability. The performance is superior to most reported primary explosives, since the CA nanoparticles contribute to high brisance and the protection of the porous carbon network. Notably, the growth mechanism of the CA/C film is further disclosed by detailed experimental investigation and density functional theory (DFT) calculation. This work will offer new insight to design and develop a CA-based primary explosive film for applications in advanced explosive systems.

Large-Area Nanosphere Self-Assembly Monolayers for Periodic Surface Nanostructures with Ultrasensitive and Spatially Uniform SERS Sensing.

Colloidal lithography provides a rapid and low-cost approach to construct 2D periodic surface nanostructures. However, an impressive demonstration to prepare large-area colloidal template is still missing. Here, a high-efficient and flexible technique is proposed to fabricate self-assembly monolayers consisting of orderly-packed polystyrene spheres at air/water interface via ultrasonic spray. This "non-contact" technique exhibits great advantages in terms of scalability and adaptability due to its renitent interface dynamic balance. More importantly, this technique is not only competent for self-assembly of single-sized polystyrene spheres, but also for binary polystyrene spheres, completely reversing the current hard situation of preparing large-area self-assembly monolayers. As a representative application, hexagonal-packed silver-coated silicon nanorods array (Si-NRs@Ag) is developed as an ultrasensitive surface-enhanced Raman scattering (SERS) substrate with very low limit-of-detection for selective detection of explosive 2,4,6-trinitrotoluene down to femtomolar (10-14 m) range. The periodicity and orderliness of the array allow hot spots to be designed and constructed in a homogeneous fashion, resulting in an incomparable uniformity and reproducibility of Raman signals. All these excellent properties come from the Si-NRs@Ag substrate based on the ordered structure, open surface, and wide-range electric field, providing a robust, consistent, and tunable platform for molecule trapping and SERS sensing for a wide range of organic molecules.

Effect of the Ni and NiO Interface Layer on the Energy Performance of Core/Shell CuO/Al Systems.

The interface layer is responsible for the outward migration of oxygen atoms, which subsequently leads to an adjustment in the energetic performance of nanothermite films. In this study, sandwich-structured CuO@Ni/Al and CuO@NiO/Al nanowire thermite films were successfully prepared to investigate the effects of the interface layer on the heat-release, ignition, and combustion performance. The effects of the Ni and NiO interface layers are extremely different on the heat-release performance and combustion properties of the CuO/Al nanowire thermite film. Herein, the introduced Ni layer decreased the heat release (1979.7 J/g), reactivity (Ea = 177.3 kJ/mol), and maximum pressure (2.32 MPa) compared with the CuO/Al composite. Al/Ni alloys can be formed at the interface to prevent oxygen from diffusing between CuO and Al. Moreover, the incorporation of the Ni interface layer into the CuO/Al systems results in a heat drop due to its heat-absorption capability as well as its blockage of heat transfer from the thermite reaction. The deposition of the NiO layer between CuO and Al leads to an increase in the heat release (3014.2 J/g) and a decrease in the activation energy (Ea = 178.6 kJ/mol). The NiO layer endows the CuO/Al system with a high energy-release rate and chemical reactivity. NiO can participate in a thermite reaction, which promotes the reaction of CuO/Al and induces the condensed phase.

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.

Gap initiation with 20.35 mm: an initiator integrating the Al/CuOx multilayer film and traditional electronic plug to enhance the ignition ability.

In order to enhance the ignition ability and reliability of traditional electronic initiators, a novel electronic initiator has been designed to integrate with a nanothermite multilayer film and an electrode plug. The Al/CuOx nanothermite multilayer film with different thickness is deposited on the surface of the electrode plug by magnetron sputtering which uses Pt-W wire as electronic resistance. The exothermicity of Al/CuOx nanothermite multilayer film is so favourable that the ignition ability of electronic initiator is significantly improved. The full firing-voltage sensitivity of the electronic initiator is 10.8 V. The thickness of Al/CuOx multilayer film has negligible effects on the ignition time and ignition energy, but leads to great impacts on the function time, the maximum length of combustion flame and ignition ability. The electrical ignition experiments have exhibited outstanding ignition ability, since the electronic initiator can easily fire the insensitive ignition composition of boron-potassium nitrate (B-KNO3) tablet in a gap of 20.35 mm. It proves that this novel proposal of remoulding the traditional electronic ignition devices will distinctly improve the ignition ability and reliability of electronic initiator.

Core/shell CuO/Al nanorod thermite film based on electrochemical anodization.

In this study, a new method was reported for the fabrication of the nanostructured CuO/Al thermite film on a Cu substrate. The CuO nanorod (NR) arrays grew vertically from the Cu surfaces by electrochemical anodization processes, followed by the deposition of an Al layer on the CuO NRs via magnetron sputtering to form a core/shell CuO/Al nanothermite film, whose component, structure and morphology were subsequently characterized. In addition, the energy-release characteristics of the obtained nanothermite film were investigated using thermal analyses and laser ignition tests. All evidence demonstrates that the obtained CuO/Al is of a uniform structure and has superb energy performance. Impressively, the resulting material is potentially useful in applications of functional energetic chips due to its easy integration with microelectromechanical systems (MEMS) technologies.

Integration of the 3DOM Al/Co3O4 nanothermite film with a semiconductor bridge to realize a high-output micro-energetic igniter.

Microigniters play an important role for the reliable initiation of micro explosive devices. However, the microigniter is still limited by the low out-put energy to realize high reliability and safety. Integration of energetic materials with microigniters is an effective method to enhance the ignition ability. In this work, a Al/Co3O4 nanothermite film with a three-dimensionally ordered macroporous structure was prepared by the deposition of nanoscale Al layers using magnetron sputtering on Co3O4 skeletons that are synthesized using an inverse template method. Both the uniform structure and nanoscale contact between the Al layers and the Co3O4 skeletons lead to an excellent exothermicity. In order to investigate the ignition properties, a micro-energetic igniter has been fabricated by the integration of the Al/Co3O4 nanothermite film with a semiconductor bridge microigniter. The thermite reactions between the nanoscale Al layer and the Co3O4 skeleton extensively promote the intensity of the spark, the length in duration and the size of the area, which greatly enhance the ignition reliability of the micro-energetic igniter. Moreover, this novel design enables the micro-energetic igniter to fire the pyrotechnic Zr/Pb3O4 in a gap of 3.7 mm by capacitor discharge stimulation and to keep the intrinsic instantaneity high and firing energy low. The realization of gap ignition will surely improve the safety level of initiating systems and have a significant impact on the design and application of explosive devices.

Design and fabrication of energetic metal-organic framework [Cu(ntz)]n films with high energy-density and stability.

In this work, for the first time, we have successfully prepared energetic metal-organic framework [Cu(ntz)]n films by integrating electrochemical deposition and solvothermal growth. With its excellent energy, stability and ignition performances, the [Cu(ntz)]n film has potential application in microelectromechanical systems (MEMS) to achieve functional nanoenergetics-on-a-chip.