Nitroglycerin trapping in melamine matrices.

Melamine (Mel) was used as host matrix for liquid nitroglycerin (NG), to prepare Mel/NG solid powdered compounds containing up to 45 wt% of this explosive. The two preparation processes used for this purpose consisted in evaporating a solution of both components, either in ambient conditions or under reduced pressure by the Spray Flash-Evaporation (SFE) process. In Mel/NG materials, amorphous nitroglycerin is distributed in the crystallized melamine matrix as inclusions, which were found to be smaller in size in the material prepared by the SFE process. Mel/NG materials are not stable over time: they gradually lose the nitroglycerin they contain by evaporation.

Aluminum nanopowder: A substance to be handled with care.

Aluminum nanopowders are increasingly used in various areas of research in materials and physical chemistry. Their unconventional properties are still little understood and make their handling sometimes quite hazardous. In this article, we report the case of apparently benign mixtures of Al with sulfuric acid (H2SO4), which violently explode when they are exposed to a flame. The explosions of 100mg samples were observed by high speed video (60000fr/s). These experiments have showed a three-step mechanism, in which the primary hydrogen combustion ignites and disperses the nano-Al/H2SO4 paste in clusters with high velocities (∼100m/s). The combustion of the paste increases the hydrogen release and initiates the explosion of the H2/air mixture, which propagates at high velocities (760-1060m/s). This effect was not observed with micron-sized Al powders, and it is a good illustration of new hazards with nano-Al. Extreme caution is hence recommended to chemists who handle such materials.

Nanothermite with Meringue-like Morphology: From Loose Powder to Ultra-porous Objects.

The goal of the protocol described in this article is to prepare aluminothermic compositions (nanothermites) in the form of porous, monolithic objects. Nanothermites are combustible materials made up of inorganic fuel and an oxidizer. In nanothermite foams, aluminum is the fuel and aluminum phosphate and tungsten trioxide are the oxidizing moieties. The highest flame propagation velocities (FPVs) in nanothermites are observed in loose powders and FPVs are strongly decreased by pelletizing nanothermite powders. From a physical standpoint, nanothermite loose powders are metastable systems. Their properties can be altered by unintentional compaction induced by shocks or vibrations or by the segregation of particles over time by settling phenomena, which originates from the density differences of their components. Moving from a powder to an object is the challenge that must be overcome to integrate nanothermites in pyrotechnic systems. Nanothermite objects must have both a high open porosity and good mechanical strength. Nanothermite foams meet both of these criteria, and they are prepared by dispersing a nano-sized aluminothermic mixture (Al/WO3) in orthophosphoric acid. The reaction of aluminum with the acid solution gives the AlPO4 "cement" in which Al and WO3 nanoparticles are embedded. In nanothermite foams, aluminum phosphate plays the dual role of binder and oxidizer. This method can be used with tungsten trioxide, which is not altered by the preparation process. It could probably be extended to some oxides, which are commonly used for the preparation of high performance nanothermites. The WO3-based nanothermite foams described in this article are particularly insensitive to impact and friction, which makes them far safer to handle than loose Al/WO3 powder. The fast combustion of these materials has interesting applications in pyrotechnic igniters. Their use in detonators as primers would require the incorporation of a secondary explosive in their composition.

Nanodiamond for tuning the properties of energetic composites.

Bismuth oxide (Bi2O3) particles were coated by detonation nanodiamonds. The resulting nanocomposite materials were mixed with an aluminum nanopowder (≈ 100 nm) to prepare nanothermites, with reduced sensitivity to friction and electrostatic discharge (ESD). The use of nanodiamond for this purpose is reported here for the first time. Their numerous qualities such as their small size, antifriction properties and thermal conductivity make them ideal candidates. Small amounts of detonation nanodiamonds allow obtaining impressive desensitization, making thus modified Bi2O3/Al nanothermite safe to handle. A composition containing around 1 wt.% of nanodiamond has a sensitivity threshold to friction superior to 100 N instead of 5 N for the thermite without nanodiamond. Furthermore, the sensitivity threshold to electrostatic discharge increases to 20 times when the nanodiamond content reaches 1.8 wt.%. The antifriction properties of nanodiamond limit the scratching of Bi2O3 surface by Al particles. The desensitization to ESD is observed for a sufficient coverage of the oxide particles (1.8 wt.% of ND), which restrains the effect of the melt dispersion mechanism of aluminum and prevents the mixing of the oxidizing and the reducing parts of the composites. A good reactivity of the thermite could be maintained for nanodiamond content up to 2.6 wt.%. The carburizing of aluminum coming on contact with nanodiamond during the thermite reaction could be evidenced by X-ray Diffraction and calorimetry measurements and also participates to the desensitization of the nanothermite. This kind of desensitization by using detonation nanodiamond can also be applied to other nanothermites having low sensitivity threshold to friction and ESD.

Sulfates-based nanothermites: an expanding horizon for metastable interstitial composites.

Metal sulfates (Ba, Bi, Ca, Cu, Mg, Mn, Na, Zn, Zr) were used as oxidizers in reactive compositions with Al nanopowder. These new kinds of nanothermites have outstandingly high reaction heats (4-6 kJ g(-1) ) compared to conventional Al/metal oxides (1.5-4.8 kJ g(-1) ) and also have good combustion velocities (200-840 m s(-1) vs 100-2500 m s(-1) ). These compositions are extremely insensitive to friction making their preparation and handling easy and safe. The sulfate hydration water increases the reaction heats and has a significant effect on the sensitivity to impact and to electrostatic discharge. The reaction of Al with water is easier to initiate than the one with sulfate which leads to two possible decomposition modes for samples exposed to an open flame. The pyrotechnical properties observed with sulfates have also been found for other sulfur oxygenates (SO3 (2-) , S2 O3 (2-) , S2 O8 (2-) ) which opens up new horizons in the domain of metastable interstitial composites.

Safer energetic materials by a nanotechnological approach.

Energetic materials - explosives, thermites, populsive powders - are used in a variety of military and civilian applications. Their mechanical and electrostatic sensitivity is high in many cases, which can lead to accidents during handling and transport. These considerations limit the practical use of some energetic materials despite their good performance. For industrial applications, safety is one of the main criteria for selecting energetic materials. The sensitivity has been regarded as an intrinsic property of a substance for a long time. However, in recent years, several approaches to lower the sensitivity of a given substance, using nanotechnology and materials engineering, have been described. This feature article gives an overview over ways to prepare energetic (nano-)materials with a lower sensitivity.

Detonation nanodiamonds for doping Kevlar.

This paper reports on the first attempt to enclose diamond nanoparticles--produced by detonation--into a Kevlar matrix. A nanocomposite material (40 wt% diamond) was prepared by precipitation from an acidic solution of Kevlar containing dispersed nanodiamonds. In this material, the diamond nanoparticles (Ø = 4 nm) are entirely wrapped in a Kevlar layer about 1 nm thick. In order to understand the interactions between the nanodiamond surface and the polymer, the oxygenated surface functional groups of nanodiamond were identified and titrated by Boehm's method which revealed the exclusive presence of carboxyl groups (0.85 sites per nm2). The hydrogen interactions between these groups and the amide groups of Kevlar destroy the "rod-like" structure and the classical three-dimensional organization of this polymer. The distortion of Kevlar macromolecules allows the wrapping of nanodiamonds and leads to submicrometric assemblies, giving a cauliflower structure reminding a fractal object. Due to this structure, the macroscopic hardness of Kevlar doped by nanodiamonds (1.03 GPa) is smaller than the one of pure Kevlar (2.31 GPa). To our knowledge, this result is the first illustration of the change of the mechanical properties induced by doping the Kevlar with nanoparticles.

Tunable generation and adsorption of energetic compounds in the vapor phase at trace levels: a tool for testing and developing sensitive and selective substrates for explosive detection.

Among various methods for landmine detection, as well as soil and water pollution monitoring, the detection of explosive compounds in air is becoming an important and inevitable challenge for homeland security applications, due to the threatening increase in terrorist explosive bombs used against civil populations. However, in the last case, there is a crucial need for the detection of vapor phase traces or subtraces (in the ppt range or even lower). A novel and innovative generator for explosive trace vapors was designed and developed. It allowed the generation of theoretical concentrations as low as 0.24 ppq for hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) in air according to Clapeyron equations. The accurate generation of explosive concentrations at subppt levels was verified for RDX and 2,4,6-trinitrotoluene (TNT) using a gas chromatograph coupled to an electron capture detector (GC-ECD). First, sensing material experiments were conducted on a nanostructured tungsten oxide. The sensing efficiency of this material determined as its adsorption capacity toward 54 ppb RDX was calculated to be five times higher than the sensing efficiency of a 54 ppb TNT vapor. The material sensing efficiency showed no dependence on the mass of material used. The results showed that the device allowed the calibration and discrimination between materials for highly sensitive and accurate sensing detection in air of low vapor pressure explosives such as TNT or RDX at subppb levels. The designed device and method showed promising features for nanosensing applications in the field of ultratrace explosive detection. The current perspectives are to decrease the testing scale and the detection levels to ppt or subppt concentration of explosives in air.

Structural changes of metallic surfaces induced by ultrasound.

The effect of ultrasounds on the surface of metallic plates with cubic faced centered (Al, Ag, Cu) or hexagonal (Zn) structure was studied. Treated surfaces were strongly attacked: a micrometric roughness and a superficial oxidation (characterized by roughness measurements and scanning electron microscopy) were induced. X-ray diffraction analyses showed a preferential reorientation of the maximum density planes for both crystallographic structures.