Laser initiation of PETN in the mode of resonance photoinitiation

Алукер, Э. Д.; Aluker, N. L.; Krechetov, A. G.; Mitrofanov, A. Yu.; Нурмухаметов, Д. Р.; Shvaiko, V. N.

doi:10.1134/s1990793111010027

Cited by 14 publications

(14 citation statements)

References 4 publications

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“…This research provided strong support to an excitonic mechanism of initiation of chemistry that was theoretically proposed earlier [18,19]. Experimentally, it was demonstrated that the laser initiation can be photochemical in nature at least for some systems, such as heavy metal azides and secondary explosives, cyclotrimethylene trinitramine (RDX, C 3 H 6 N 6 O 6 ) [20], pentaerythritol tetranitrate (PETN, C 5 H 8 N 4 O 12 ) [5,21,22,23], and furazan-based molecules [24,25]. In particular, it was observed that the (non-thermal) photoexcitation of PETN molecules does lead to the formation of reactive radicals, and that the further explosive decomposition reaction proceeds by a chain or autocatalytic (chain explosion) mechanism [5,21,22].…”

Section: Introductionmentioning

confidence: 62%

“…Experimentally, it was demonstrated that the laser initiation can be photochemical in nature at least for some systems, such as heavy metal azides and secondary explosives, cyclotrimethylene trinitramine (RDX, C 3 H 6 N 6 O 6 ) [20], pentaerythritol tetranitrate (PETN, C 5 H 8 N 4 O 12 ) [5,21,22,23], and furazan-based molecules [24,25]. In particular, it was observed that the (non-thermal) photoexcitation of PETN molecules does lead to the formation of reactive radicals, and that the further explosive decomposition reaction proceeds by a chain or autocatalytic (chain explosion) mechanism [5,21,22]. Recent quantum-chemical calculations of thermal decomposition of PETN molecules, crystals, and crystal surfaces [26] ruled out a possibility of thermal initiation of PETN observed in those experiments [5,21,22].…”

Section: Introductionmentioning

confidence: 99%

“…In particular, it was observed that the (non-thermal) photoexcitation of PETN molecules does lead to the formation of reactive radicals, and that the further explosive decomposition reaction proceeds by a chain or autocatalytic (chain explosion) mechanism [5,21,22]. Recent quantum-chemical calculations of thermal decomposition of PETN molecules, crystals, and crystal surfaces [26] ruled out a possibility of thermal initiation of PETN observed in those experiments [5,21,22]. The first principles analysis of the ground state reaction mechanisms convincingly demonstrated that the lowest theoretically obtained activation barriers (~35–36 kcal/mol) [26] as well as the experimental range (32.6 to 47.3 kcal/mol) [27,28,29,30,31] were found to be inconsistent with the experimental energy of laser initiation (1.17 eV = 27.0 kcal/mol) [5,21,22].…”

Section: Introductionmentioning

confidence: 99%

“…Recent quantum-chemical calculations of thermal decomposition of PETN molecules, crystals, and crystal surfaces [26] ruled out a possibility of thermal initiation of PETN observed in those experiments [5,21,22]. The first principles analysis of the ground state reaction mechanisms convincingly demonstrated that the lowest theoretically obtained activation barriers (~35–36 kcal/mol) [26] as well as the experimental range (32.6 to 47.3 kcal/mol) [27,28,29,30,31] were found to be inconsistent with the experimental energy of laser initiation (1.17 eV = 27.0 kcal/mol) [5,21,22]. Thus, the drawn conclusions lend some additional support to the notion that an excited state of a PETN molecule, created by the absorption of a photon, rather than by a thermal energy, was the primary act of initiation in laser irradiation experiments [5,22,32].…”

Section: Introductionmentioning

confidence: 99%

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Topography of Photochemical Initiation in Molecular Materials

et al. 2013

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Abstract: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.

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Section: Introductionmentioning

confidence: 62%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Topography of Photochemical Initiation in Molecular Materials

et al. 2013

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“…Second is the impulse initiation mechanism in which the reactions are initiated by a strong laser-generated shock wave in the material [26,27]. Third is the initiation mechanism of optical breakdown and photodecomposition in which the laser energy is absorbed by the molecule and the radiation directly couples to suitable bonds within the structure [28,29]. To date, the initiation mechanism of high-energy materials exposed to NIR laser pulses and the function of metal additions have not yet been interpreted unambiguously.…”

Section: Introductionmentioning

confidence: 99%

Near‐Infrared Laser Initiation Mechanism of Pentaerythritol Tetranitrate Doped with Aluminum Nanoparticles

Ji¹,

Qin²,

Tang³

et al. 2018

Propellants Explo Pyrotec

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Aluminum nanoparticles were added into pentaerythritol tetranitrate (PETN) to decrease the near-infrared (NIR) laser initiation power. The effects of Al nanoparticles on the minimum power of all fire were investigated under 1064 nm laser initiation. The initiation mechanism was studied using differential scanning calorimetry, reflectance spectroscopy, laser-induced breakdown spectroscopy, and shadowgraph technique. Results showed that the addition of Al nanoparticles could prominently decrease the minimum power of all fire of PETN. The PETN doped with 0.5 % Al nanoparticles could be reliably initiated with 40 mJ laser en-ergy (1064 nm, 14 ns). However, the increase in Al nanoparticles increased the minimum power of all fire. A thermal mechanism could be affirmed for the initiation of PETN doped with Al nanoparticles with the NIR laser initiation. First, Al nanoparticles were heated to high temperature to form hotspots by absorbing input NIR laser energy. Then, the PETN surrounded by the hotspots propagated self-sustaining chemical reactions and exploded. With the increase of Al nanoparticles, the increase in thermal conductivity and the decrease of the hot-spots temperature resulted in high laser power to initiate explosives.

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