Toward non-invasive detection of concealed energetic materials in-field under ambient-light conditions

Spatially offset Raman spectroscopy (SORS) is demonstrated for the non-contact detection of energetic materials concealed within non-transparent, diffusely scattering containers. A modified design of an inverse SORS probe has been developed and tested. The SORS probe has been successfully used for the detection of various energetic substances inside different types of plastic containers. The tests have been successfully conducted under incandescent and fluorescent background lights as well as under daylight conditions, using a non-contact working distance of 6 cm. The interrogation times for the detection of the substances were less than 1 minute in each case, highlighting the suitability of the device for near real-time detection of concealed hazards in the field. The device has potential applications in forensic analysis and homeland security investigations.

Raman spectroscopy techniques for detection of energetic materials at high and low concentration

This thesis presents the development of a rapid, sensitive and reproducible spectroscopic method for the detection of TNT in forensic and environmental applications. Simple nano sensors prepared by cost effective methods were utilized as sensitive platforms for the detection of TNT by surface enhanced Raman spectroscopy. The optimization of the substrate and the careful selection of a suitable recognition molecule contributed to the significant improvements of sensitive and selective targeting over current detection methods. The work presented in this thesis paves the way for effective detection and monitoring of explosives residues in law enforcement and environmental health applications.

Calculations of bond dissociation energies and dipole moments in energetic materials using density-functional methods

We compare the effectiveness of six exchange/correlation functional combinations (Becke/Lee, Yang and Parr; Becke-3/Lee, Yang and Parr; Becke/Perdew-Wang 91; Becke-3/Perdew-Wang 91; Becke/Perdew 86; Becke-3/Perdew 86) for computing C-N, O-O and N-NO2 dissociation energies and dipole moments of five compounds. The studied compounds are hexabydro-1,3,5-trinitro-1,3,5-triazine (RDX), dimethylnitramine, cyanogen, nitromethane and ozone. The Becke-3/Perdew 86 in conjunction with 6-31G

Experimental Setup for Assessing the Energetic Materials Deflagration Propagation under High Temperature and High Pressure Conditions

The technology of "explosion in fractures" is one of new synthetic engineering methods used in low permeability reservoirs. The most important problem arose from the technology is to assess the deflagration propagation capability of milky explosives in rock fractures. In order to investigate detailed this problem in the laboratory, an experimental setup was designed and developed in which different conditions can be simulated. The experimental setup mainly includes two parts. One is the experimental part and the other is the measurement part. In the experimental setup, the narrow slots with different width can be simulated; meanwhile, different initial pressures and initial temperatures can be loaded on the explosives inside the narrow slots. The initial pressure range is from 0-60 MPa, and the initial temperatures range is from room temperature to 100 V. The temperature and the velocity of deflagration wave can be measured; meanwhile the corresponding pressure in the narrow slot is also measured. In the end, some typical measurement results are briefly presented and discussed.

Powder and propellants : energetic materials at Indian Head, Maryland, 1890-1990 /

Shipping list no.: 90-601-P.

ENERGETIC BIOCIDAL MATERIALS AND SPORE NEUTRALIZATION

The objective of this dissertation is to explore a more accurate and versatile approach to investigating the neutralization of spores suffered from ultrafast heating and biocide based stresses, and further to explore and understand novel methods to supply ultrafast heating and biocides through nanostructured energetic materials A surface heating method was developed to apply accurate (± 25 ˚C), high heating rate thermal energy (200 - 800 ˚C, ~103 - ~105 ˚C/s). Uniform attachment of bacterial spores was achieved electrophoretically onto fine wires in liquids, which could be quantitatively detached into suspension for spore enumeration. The spore inactivation increased with temperature and heating rate, and fit a sigmoid response. The neutralization mechanisms of peak temperature and heating rate were correlated to the DNA damage at ~104 ˚C/s, and to the coat rupture by ultrafast vapor pressurization inside spores at ~105 ˚C/s. Humidity was found to have a synergistic effect of rapid heating and chlorine gas to neutralization efficiency. The primary neutralization mechanism of Cl2 and rapid heat is proposed to be chlorine reacting with the spore surface. The stress-kill correlation above provides guidance to explore new biocidal thermites, and to probe mechanisms. Results show that nano-Al/K2S2O8 released more gas at a lower temperature and generated a higher maximum pressure than the other nano-Al/oxysalts. Given that this thermite formulation generates the similar amount of SO2 as O2, it can be considered as a potential candidate for use in energetic biocidal applications. The reaction mechanisms of persulfate and other oxysalts containing thermites can be divided into two groups, with the reactive thermites (e.g. Al/K2S2O8) that generate ~10× higher of pressure and ~10× shorter of burn time ignited via a solid-gas Al/O2 reaction, while the less reactive thermites (e.g. Al/K2SO4) following a condensed phase Al/O reaction mechanism. These different ignition mechanisms were further re-evaluated by investigating the roles of free and bound oxygen. A constant critical reaction rate for ignition was found which is independent to ignition temperature, heating rate and free vs. bound oxygen.

Energetic Polymers

High energy materials are essential ingredients in both rocket and explosive formulations. These can be vulnerable due to maltreatment. During gulf war, several catastrophic accidents have been reported from their own payload munitions. The role of energetic binders here was to wrap the explosive formulations to convert it into insensitive munitions. With the aid of energetic binders, the explosive charges are not only protected from tragic accidents due to fire, bullet impact, adjacent detonation, unplanned transportation, but also form total energy output presumption. The use of energetic binders in rocket propellants and explosive charges has been increased after the Second World War. Inert binders in combination with energetic materials, performed well as binders but they diluted the final formulation. Obviously the total energy output was reduced. Currently, the research in the field of energetic polymers is an emerging area, since it plays crucial role in insensitive munitions. The present work emphasises on the synthesis and characterization of oxetanes, oxiranes and polyphosphazene based energetic polymers. The thesis is structured into six chapters. First part of chapter 1 deals with brief history of energetic polymers. The second part describes a brief literature survey of energetic polymers based on oxetanes and oxiranes. Third and fourth parts deal with energetic plasticizers and energetic polyphosphazenes. Finally, the fifth part deals with the various characterization techniques adopted for the current study and sixth part includes objectives of the present work.

A New Ignition Criterion Based Upon a Critical Thermal Energy Density

It has long been known that various ignition criteria of energetic materials have been limited in applicability to small regions. In order to explore the physical nature of ignition, we calculated how much thermal energy per unit mass of energetic materials was absorbed under different external stimuli. Hence, data of several typical sensitivity tests were analyzed by order of magnitude estimation. Then a new concept on critical thermal energy density was formulated. Meanwhile, the chemical nature of ignition was probed into by chemical kinetics.

含能材料装药的损伤及力学性能研究进展

研究含能材料的损伤和力学性能对于指导含能材料配方和结构件设计，以及对含能材料进行安全性评估和寿命预测等都具有重要的意义。损伤一方面使含能材料的力学性能劣化，另一方面还影响含能材料的感度、燃烧甚至爆炸性能。本文对含能材料损伤和力学性能的研究现状进行了综述和归纳。对含能材料损伤的产生、实验模拟、主要损伤模式，损伤对含能材料的感度和燃烧性能等的影响，炸药单相材料的性质，影响含能材料力学性能的因素以及损伤本构关系等进行了介绍。对其中的一些关键问题和热点问题进行了分析，并对今后需要开展的工作发表了一些看法。

Propagation of Explosion Wave in Hard-Soft-Hard Layered Media

The paper presents a reasonable analysis for dynamic response and failure process of a plane multi-layered media, which are subjected to a blast loading. This blast loading is induced by a cylindric explosive put on the center of top surface of the layered media. With the help of numerical simulation technique provided by LS-DYNA software, the whole process of explosion wave propagation and attenuation can be revealed. The feature of local failure around the blasting site is also discussed in some detail. Our focus will be on the explosion wave attenuation for the hard-soft-hard sandwich layers. As seen in the paper, the computational results are delivered in a feasible way by comparing with experimental data.

Ionic Liquid-Based Routes to Conversion or Reuse of Recycled Ammonium Perchlorate

New, potentially green, and efficient synthetic routes for the remediation and/or re-use of perchlorate-based energetic materials have been developed. Four simple organic imidazolium- and phosphonium-based perchlorate salts/ionic liquids have been synthesized by simple, inexpensive, and nonhazardous methods, using ammonium perchlorate as the perchlorate source. By appropriate choice of the cation, perchlorate can be incorporated into an ionic liquid which serves as its own electrolyte for the electrochemical reduction of the perchlorate anion, allowing for the regeneration of the chloride-based parent ionic liquid. The electrochemical degradation of the hazardous perchlorate ion and its conversion to harmless chloride during electrolysis was studied using IR and Cl-35 NMR spectroscopies.

Explosion risk in coke, coal and sulphur storage

The self-ignition of all kind of powdery substances is a topic studied over the years, especially if the dusty substance is coal or substances related with coal because it may be a cause of energetic materials and human losses. But it is important to note that this is not the only risk in industrial plants that generate or store solid substances. Every combustible powders are potentially explosive and they may cause serious consequences if all the necessary factors are developed. Due to this potentially risk, it is essential a good characterization and knowledge of all the parameters involved in those processes.

Determination of the JWL constants for ANFO and emulsion explosives from cylinder test data

The Jones-Wilkins-Lee (JWL) equation of state parameters for ANFO and emulsion-type explosives have been obtained from cylinder test expansion measurements. The calculation method comprises a new radial expansion function, with a non-zero initial velocity at the onset of the expansion in order to comply with a positive Gurney energy at unit relative volume, as the isentropic expansion from the CJ state predicts. The equations reflecting the CJ state conditions and the measured expansion energy were solved for the JWL parameters by a non-linear least squares scheme. The JWL parameters of thirteen ANFO and emulsion type explosives have been determined in this way from their cylinder test expansion data. The results were evaluated through numerical modelling of the tests with the LS-DYNA hydrocode; the expansion histories from the modelling were compared with the measured ones, and excellent agreement was found.

Facile synthesis and proposed mechanism of α,ω‐oxetanyl-telechelic poly(3-nitratomethyl-3-methyl oxetane) by an SN2(i) nitrato displacement method in basic media

The synthesis of a novel heterocyclic–telechelic polymer, α,ω-oxetanyl-telechelic poly(3-nitratomethyl-3-methyl oxetane), is described. Infrared spectroscopy (IR), gel permeation chromatography (GPC), and nuclear magnetic resonance (NMR) spectroscopy have been used to confirm the successful synthesis, demonstrating the presence of the telechelic-oxetanyl moieties. Synthesis of the terminal functionalities has been achieved via displacement of nitrato groups, in a manner similar to that employed with other leaving groups such as azido, bromo, and nitro, initiated by nucleophiles. In the present case, displacement occurs on the ends of a nitrato-functionalized polymer driven by the formation of sodium nitrate, which is supported by the polar aprotic solvent N,N-dimethyl formamide. The formation of an alkoxide at the polymer chain ends is favored and allows internal back-biting to the nearest carbon bearing the nitrato group, intrinsically in an SN2(i) reaction, leading to α,ω-oxetanyl functionalization. The telechelic-oxetanyl moieties have the potential to be cross-linked by chemical (e.g., acidic) or radiative (e.g., ultraviolet) curing methods without the use of high temperatures, usually below 100°C. This type of material was designed for future use as a contraband simulant, whereby it would form the predominant constituent of elastomeric composites comprising rubbery polymer with small quantities of solids, typically crystals of contraband substances, such as explosives or narcotics. This method also provides an alternative approach to ring closure and synthesis of heterocycles.