Iron and Copper Doped Zinc Oxide Nanopowders as a Sensitizer of Industrial Energetic Materials to Visible Laser Radiation.

The development of methods ensuring reliable control over explosive chemical reactions is a critical task for the safe and efficient application of energetic materials. Triggering the explosion by laser radiation is one of the promising methods. In this work, we demonstrate a technique of applying the common industrial high explosive pentaerythritol tetranitrate (PETN) as a photosensitive energetic material by adding zinc oxide nanopowders doped with copper and iron. Nanopowders of ZnO:Fe and ZnO:Cu able to absorb visible light were synthesized. The addition of one mass percent nanopowders in PETN decreased the threshold energy density of its initiation through Nd:YAG laser second harmonic (2.33 eV) by more than five times. The obtained energetic composites can be reliably initiated by a CW blue laser diode with a wavelength of 450 nm and power of 21 W. The low threshold initiation energy and short irradiation exposure of the PETN-ZnO:Cu composite makes it applicable in laser initiation devices. PETN-ZnO:Cu also can be initiated by an infrared laser diode with a wavelength of 808 nm. The proposed photochemical mechanism of the laser-induced triggering of the explosion reaction in the studied energetic composites was formulated. The results demonstrate the high promise of using nanomaterials based on zinc oxide as a sensitizer of industrial energetic materials to visible laser radiation.

Achieving tunable chemical reactivity through photo-initiation of energetic materials at metal oxide surfaces.

Known applications of high energy density materials are impressively vast. Despite this, we argue that energetic materials are still underutilized for common energy purposes due to our inability to control explosive chemical reactions releasing energy from these materials. The situation appears paradoxical as energetic materials (EM) possess massive amounts of energy and, hence, should be most appropriate for applications in many energy-intensive processes. Here, we discover how chemical decomposition reactions can be stimulated with laser excitation and therefore, highly controlled by selectively designing energetic material - metal oxide interfaces with an example of pentaerythritol tetranitrate (PETN)-MgO and trinitrotoluene (TNT)-MgO composite samples. Density functional theory and embedded cluster method calculations were combined with measurements of the optical absorption spectra and laser initiation experiments. We found that the first (1064 nm, 1.17 eV), second (532 nm, 2.33 eV), and third (355 nm, 3.49 eV) laser harmonics, to all of which pure energetic materials are transparent, can be effectively used to trigger explosive reactions in the PETN-MgO samples. We propose a consistent electronic mechanism that explains how specific sub-band optical transitions initiate decomposition chemistry. Also, this selectivity reveals a fundamental difference between materials chemistry at interfaces as we show on examples of PETN and TNT energetic materials.

Photochemistry of the α-Al2O3-PETN Interface.

Optical absorption measurements are combined with electronic structure calculations to explore photochemistry of an α-Al2O3-PETN interface formed by a nitroester (pentaerythritol tetranitrate, PETN, C5H8N4O12) and a wide band gap aluminum oxide (α-Al2O3) substrate. The first principles modeling is used to deconstruct and interpret the α-Al2O3-PETN absorption spectrum that has distinct peaks attributed to surface F°-centers and surface-PETN transitions. We predict the low energy α-Al2O3 F°-center-PETN transition, producing the excited triplet state, and α-Al2O3 F°-center-PETN charge transfer, generating the PETN anion radical. This implies that irradiation by commonly used lasers can easily initiate photodecomposition of both excited and charged PETN at the interface. The feasible mechanism of the photodecomposition is proposed.

Topography of photochemical initiation in molecular materials.

We propose a fluctuation model of the photochemical initiation of an explosive chain reaction in energetic materials. In accordance with the developed model, density fluctuations of photo-excited molecules serve as reaction nucleation sites due to the stochastic character of interactions between photons and energetic molecules. A further development of the reaction is determined by a competition of two processes. The first process is growth in size of the isolated reaction cell, leading to a micro-explosion and release of the material from the cell towards the sample surface. The second process is the overlap of reaction cells due to an increase in their size, leading to the formation of a continuous reaction zone and culminating in a macro-explosion, i.e., explosion of the entire area, covering a large part of the volume of the sample. Within the proposed analytical model, we derived expressions of the explosion probability and the duration of the induction period as a function of the initiation energy (exposure). An experimental verification of the model was performed by exploring the initiation of pentaerythritol tetranitrate (PETN) with the first harmonic of YAG: Nd laser excitation (1,064 nm, 10 ns), which has confirmed the adequacy of the model. This validation allowed us to make a few quantitative assessments and predictions. For example, there must be a few dozen optically excited molecules produced by the initial fluctuations for the explosive decomposition reaction to occur and the life-time of an isolated cell before the micro-explosion must be of the order of microseconds.