Denis Spitzer

Understanding ultrafine nanodiamond formation using nanostructured explosives

The detonation process is able to build new materials with a bottom-up approach. Diamond, the hardest material on earth, can be synthesized in this way. This unconventional synthesis route is possible due to the presence of carbon inside the high-explosive molecules: firing high-explosive mixtures with a negative oxygen balance in a non-oxidative environment leads to the formation of nanodiamond particles. Trinitrotoluene (TNT) and hexogen (RDX) are the explosives primarily used to synthesize nanodiamonds. Here we show that the use of nanostructured explosive charges leads to the formation of smaller detonation nanodiamonds, and it also provides new understanding of nanodiamond formation-mechanisms. The discontinuity of the explosive at the nanoscale level plays the key role in modifying the diamond particle size, and therefore varying the size with microstructured charges is impossible.

Continuous engineering of nano-cocrystals for medical and energetic applications

Cocrystals, solid mixtures of different molecules on molecular scale, are supposed to be tailor made materials with improved employability compared to their pristine individual components in domains such as medicine and explosives. In medicine, cocrystals are obtained by crystallization of active pharmaceutical ingredients with precisely chosen coformers to design medicaments that demonstrate enhanced stability, high solubility, and therefore high bioavailability and optimized drug up-take. Nanoscaling may further advance these characteristica compared to their micronsized counterparts – because of a larger surface to volume ratio of nanoparticles. In the field of energetic materials, cocrystals offer the opportunity to design smart explosives, combining high reactivity with significantly reduced sensitivity, nowadays essential for a safe manipulation and handling. Furthermore, cocrystals are used in ferroelectrics, non-linear material response and electronic organics. However, state of the art batch processes produce low volume of cocrystals of variable quality and only have produced micronsized cocrystals so far, no nano-cocrystals. Here we demonstrate the continuous preparation of pharmaceutical and energetic micro- and nano-cocrystals using the Spray Flash Evaporation process. Our laboratory scale pilot plant continuously prepared up to 8 grams per hour of Caffeine/Oxalic acid 2:1, Caffeine/Glutaric acid 1:1, TNT/CL-20 1:1 and HMX/Cl-20 1:2 nano- and submicronsized cocrystals.

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.

Local detection of nitrogen-vacancy centers in a nanodiamond monolayer.

Nitrogen-vacancy defect centers (NV) contained in nanodiamonds (NDs) are a promising candidate in quantum information processing and single photon sources due to the capability of controlling their assembly on various surfaces. However, their detection with traditional optical techniques becomes challenging when probing high NV densities at the nanometer scale. Here, we combine scanning probe techniques to characterize in a monolayer the structural and electronic properties of bucky-diamonds with sizes below 10 nm. We further observe by light-assisted Kelvin- and scanning tunneling spectroscopy a clear signature of negatively charged subsurface NV centers in NDs at the nanoscale where conventional techniques are limited.

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.

Two-dimensional nanodiamond monolayers deposited by combined ultracentrifugation and electrophoresis techniques

Dense detonation nanodiamonds deposit has been obtained through a coupled process: Electrophoretic deposition was applied to an ultracentrifugated detonation nanodiamonds suspension. The resulting coating exhibits nearly complete 5 nm thick monolayer coverage of the substrate. The described process is a soft and easily tunable approach, particularly suitable for the development of sensors or the growth of high performance nanodiamond films. The proximity of the adsorbed nanoparticles on the substrate was demonstrated by scanning probe techniques, such as atomic force microscopy and scanning tunneling microscopy.

Reactive characterization of nanothermites

Conventional thermal analysis techniques (TG and DSC) give valuable information on the activation energy and the reactivity of energetic materials such as organic explosives. Here, we discuss the use of these methods for characterizing nanothermites, energetic compositions made of metallic oxides and a fuel (often a reducing metal). The experimental limitations of these analysis techniques are identified. It is difficult to ignite nanothermites with slow heating rates as those used in DSC. This is due to the inorganic nature of the thermite components and because the reaction involves interparticular heat and matter transfers. In addition, during the progressive decomposition of nanothermites, there is no change in mass, so it cannot be observed by thermogravimetric analysis. The use of laser ignition to prime the abrupt combustion of nanothermite pellets allows determining the ignition energy and analyzing the propagation of the combustion front. It also provides qualitative data that can be used to understand the combustion mechanism and to correlate it to the microstructure of the nanothermites. By analyzing several examples, we will show that the coupling of high speed video to existing thermal analysis techniques could significantly extend their utilization range for the characterization of new energetic materials.

Modulation of the Reactivity of a WO3/Al Energetic Material with Graphitized Carbon Black as Additive

Although pyrotechnic performance is fundamental, the strong mechanical and electrostatic intrinsic sensitivities of nanothermite energetic composites represent an obstacle to their development. The addition of a ternary component to the classical binary energetic composite appears to be a promising idea to overcome the problem. A carbon black additive (V3G) was used on a WO3/Al nanothermite. The effect of the pristine and modified carbon particles on the mechanical and electrical sensitivities of the composites was measured together with the pyrotechnic properties. The results show a complete desensitization to friction with a ball-milled carbon when the combustion velocity is slightly reduced.

Energetic nanocomposites for detonation initiation in high explosives without primary explosives

The mixing of aluminum nanoparticles with a metal containing oxidizer (here, WO3 or Bi2(SO4)3) gives reactive materials called nanothermites. In this research, nanothermites were combined with high explosive nanoparticles (RDX) to prepare energetic nanocomposites. These smart nanomaterials have higher performances and are much less hazardous than primary explosives. Their flame propagation velocity can be tuned from 0.2 to 3.5 km/s, through their explosive content. They were used to initiate the detonation of a high explosive, the pentaerythritol tetranitrate. The pyrotechnic transduction of combustion into detonation was achieved with short length systems (<2 cm) and small amounts of energetic nanocomposites (∼100 mg) in semi-confined systems.

Biophotonic ring resonator for ultrasensitive detection of DMMP as a simulant for organophosphorus agents.

Combining photonic integrated circuits with a biologically based sensing approach has the ability to provide a new generation of portable and low-cost sensor devices with a high specificity and sensitivity for a number of applications in environmental monitoring, defense, and homeland security. We report herein on the specific biosensing under continuous air flow of DMMP, which is commonly used as a simulant and a precursor for the synthesis of Sarin. The proposed technology is based on the selective recognition of the targeted DMMP molecule by specifically modified proteins immobilized on photonic structures. The response of the biophotonic structures shows a high stability and accuracy over 3 months, allowing for the detection in diluted air of DMMP at concentration as low as 35 μg/m(3) (6.8 ppb) in less than 15 min. The performance of the developed technology satisfies most current homeland and military security requirements.