<p dir="ltr">Efficiently identifying commercial and improvised explosives is a crucial prerequisite for disarming and disposing of these dangerous materials. In conjunction with traditional techniques (e.g., ion mobility spectrometry and mass spectrometry), electrochemical sensors can function as low-form factor and inexpensive options to quickly identify chemical threats. In particular, organic electrochemical transistors (OECTs) have many attractive properties, and they have become viable options for biosensing. OECTs employ a simple geometry consisting of a conducting polymer active layer and an electrolyte controlled by a gate electrode. In turn, this provides a means for the solution-phase detection in short times. Here, the OECT architecture was extended to the challenge of explosive trace detection. These sensors were adapted to detect several families of explosives (i.e., acid-salts, nitroaromatics, nitroamines, nitrate-esters, and peroxides). Many of these sensors incorporated molecularly imprinted polymers (MIPs) to improve chemical selectivity. These MIPs were shown to introduce size exclusive properties to the OECTs, which can be leveraged to detect acid salts explosives. MIPs that were complementary to nitrated explosives (nitroaromatics, nitroamines, and nitrate-esters) also were prepared. These MIPs can adsorb their respective explosive decreasing their polymer porosity and ion-transport. Finally, a stand-alone OECT design was applied to detect peroxide-based explosives. These explosives were decomposed to hydrogen peroxide intermediates. The evolved hydrogen peroxide was then identified as it was electro-oxidized at the gate electrode. After establishing the viability of the discussed techniques, two new directions for designing OECT sensors were proposed. Finally, these two outlooks were combined as a potential strategy for directly detecting peroxide-based explosives. While only a small subset of explosives was considered, the strategies applied were not unique to these specific targets. Indeed, these OECTs detecting principles could be applied to a broader scope of explosives detection as well as novel chemical sensing horizons.</p>

This work explores the computational modeling of electromechanical problems using peridynamics and in particular, its application in studying the potential of carbon nanotube (CNT) reinforced nanocomposites for the purpose of sensing deformation and damage in materials. Peridynamics, a non-local continuum theory which was originally formulated for modeling problems in solid mechanics, has been extended in this research to electromechanical fields and applied to study the electromechanical properties of CNT nanocomposites at multiple length scales. Piezoresistivity is the coupling between the electrical properties of a material and applied mechanical loads, more specifically the change in resistance in response to deformation. This can include both, a geometric effect due to change in dimensions as well as the change in resistivity of the material itself. Nanocomposites referred to in this work are materials which consist of CNTs dispersed in a binding polymer matrix. The origins of the extraordinary piezoresistive properties of nanocomposites lie at the nanoscale where the non-local phenomenon of electron hopping plays a significant role in establishing the properties of the nanocomposite along with CNT network formation and inherent piezoresistivity of CNTs themselves. Electron hopping or tunneling allows for a current to flow between neighboring CNTs even when they are not in contact, provided the energy barrier for electrons to hop is small enough. This phenomenon is highly nonlinear with respect to the intertube distance and is also dependent on other factors such as the potential barrier of the polymer matrix. To investigate this in more detail, peridynamic simulations are first employed to study the piezoresistivity at the CNT bundle scale by considering a nanoscale representative volume element (RVE) of CNTs within polymer matrix, and by explicitly modeling electron hopping effects. This is done by introducing electron hopping bonds and it is shown that the conductivity and the non-local length scale parameter in peridynamics (the horizon) can be derived from a purely physics based model rather than assuming an ad-hoc value. Piezoresistivity can be characterized as a function of the deformation and damage within the material and thereby used as an in-situ indicator of the structural health of the material. As such, a material system for which real time in-situ monitoring may be useful is polymer bonded explosives. While these materials are designed for detonation under conditions of a strong shock, they can be damaged or even ignited under certain low magnitude impact scenarios such as during accidental drop or transportation. Since these materials are a heterogeneous system consisting of explosive grains within a polymer matrix binder, it is proposed that CNTs can be dispersed within the binder medium leading to an inherently piezoresistive hybrid nanocomposite bonded explosive material (NCBX) material which can then be monitored for a continuous assessment of deformation and damage within the material. To explore the potential use of CNT nanocomposites for this novel application, peridynamic simulations are carried out at the microscale level, first under quasistatic conditions and subsequently under dynamic conditions to allow the propagation of elastic waves. Peridynamics equations, which can be discretized to obtain a meshless method are particularly suited to this problem as the explicit modeling of crack initiation and propagation at the microscale is essential to understanding the properties of this material. Moreover, many other parameters such as electrical conductivity of the grain and the properties of the grain-binder interface are studied to understand their effect on the piezoresistive response of the material. For example, it is found that conductivity of the grain plays a major role in the piezoresistive response since it affects the preferential pathways of current density depending on the relative ease of flow through grain vs. binder. The results of this work are promising and are two fold. Peridynamics is found to be an effective method to model such materials, both at the nanoscale and the microscale. It alleviates some of difficulties faced by traditional finite element methods in the modeling of damage in materials and can be extended to coupled fields with relative ease. Secondly, simulations presented in this work show that there is much promise in this novel application of nanocomposites in the field of structural health monitoring of polymer bonded explosives. / Ph. D. / CNT reinforced nanocomposites are known to possess extraordinary mechanical, thermal and especially piezoresistive properties. Piezoresistivity is the change in resistivity of a material in response to mechanical deformation, which can possibly be used as a tool to monitor the structural health of a material. One such set of materials are polymer bonded explosives (PBXs), a heterogeneous composite system consisting of explosive grains dispersed within a binding matrix. These materials are susceptible to mechanical insults during transportation and handling, which can damage the material at the microstructural level, decreasing the reliability and usability and may even lead to accidental detonation. It is proposed that doping the binder phase with CNTs will form inherently piezoresistive NCBX materials, whose resistivity can be monitored for microstructural changes. This may help detect and discern these damage processes that can occur on at sub-macroscale length scales, which may pass unnoticed to the naked eye or even to other non-destructive methods which may not be able to detect internal changes in the material. The current work explores the structural health monitoring (SHM) capability of NCBX materials through a recently developed computational method, peridynamics. These materials are virtually tested under various loading conditions through peridynamics simulations and compared to experimental data. The results of this work are two fold; peridynamics is found to be an effective tool to study coupled phenomena such as piezoresistivity and nancomposite piezoresistivity is well suited to monitor microstructural changes in NCBX materials. This is a first step in establishing computational models for SHM in PBX materials and can be used in various other applications ubiquitous in the engineering world such as aircrafts, spacecrafts, bridges, dams among many others.

Reactive material liners paired with high explosives can significantly increase blast effects. This research aims to study the properties that primarily control the interaction between reactive materials (RM) and high explosives (HE). This will facilitate blast performance optimization for the RM and HE combinations. A laser spectroscopic sensor will be utilized to measure the performance of these RM and HE combinations. Laser absorption spectroscopy (LAS) is a technique that measures the chemical concentration of a medium through the intensity change of the laser beam. The laser diagnostic instrument is composed of two tunable diode lasers, one centered at 2.48 μm and the other at 2.55 μm. The sensor is designed to measure H2O species concentration in the blast wave using the beer-lambert law. It will also measure the temperature of the blast with a high temperature sensitivity in the 1000 K to 2600 K range. The temperature and concentration data will be used to assess the combustion performance of the blast. The data was collected at a 200 MHz sampling frequency through a fiber-coupled optical probe designed to shield the sensitive optical equipment. The resulting blast temperature and molar concentration of H2O will be used to determine the optimal RM liner and HE pairings in the MMRT chamber. This research will enable the AFRL to expand their understanding of the RM and HE pairings.

A tetrazole is a 5-membered ring containing 4 nitrogens and 1 carbon. Due to its energetic potential and structural similarity to carboxylic acids, this ring system has a wide number of applications. In this thesis, a new and safe sustainable process to produce tetrazoles was designed that acheived high yields under mild conditions. Also, a technique was developed to form a trityl-protected tetrazole in situ. The rest of this work involved the exploitation of the energetic potential of tetrazoles. This moiety was successfully applied in polymers, ionic liquids, foams, and gels. The overall results from these experiments illustrate the fact that tetrazoles have the potential to serve as a stable alternative to the troublesome azido group common in many energetic materials. Due to these applications, the tetrazole moiety is a very important entity.

Indiana University-Purdue University Indianapolis (IUPUI) / Solid phase micro-extraction is a powerful and versatile technique, well-suited to the analysis of numerous samples of forensic interest. The exceptional sensitivity of the SPME platform, combined with its adaptability to traditional GC-MS systems and its ability to extract samples with minimal work-up, make it appropriate to applications in forensic laboratories. In a series of research projects, solid phase micro-extraction was employed for the analysis of explosives, commercial tire treatments, and entomological specimens. In the first project, the volatile organic compounds emanating from two brands of pseudo-explosive training aids for use in detector dog imprinting were determined by SPME-GC-MS, and the efficacy of these training materials was tested in live canine trials. In the second project, the headspace above various plasticizers was analyzed comparative to that of Composition C-4 in order to draw conclusions about the odor compound, 2- ethyl-1-hexnaol, with an eye toward the design of future training aids. In the third, automobile tires which had participated in professional race events were analyzed for the presence of illicit tire treatments, and in the fourth, a novel SPME-GC-MS method was developed for the analysis of blowfly (Diptera) liquid extracts. In the fifth and final project, the new method was put to the task of performing a chemotaxonomic analysis on pupa specimens, seeking to chemically characterize them according to their age, generation, and species.

Current models for predicting the environmental fate of munitions constituents (MC) in soils are based mostly on chemical distribution parameters and neglect the larger considerations of other soil parameters. We are working towards a new approach based on the whole soil activity for predicting the long-term residence time and fate of MC in soils with connection to agronomic soil fertility concepts. These relationships are demonstrated by correlating experiments involving full physical and chemical characterization of eight taxonomically distinct soils, with batch reactor studies determining MC degradation potential. Soils were incubated in a slurry for 10 days in a closed reactor system with temperature, pH, and Eh readings recorded every 24 h. Air and slurry samples were taken eight times within the 168 h incubation period. Carbon dioxide, TNT, and nutrient solution concentrations were assessed to obtain a full picture of soil chemistry changes associated with microbial activity in response to additions of TNT. Multivariate analysis was used to determine the main factors impacting degradation rate. Principle Components Analysis (PCA) statistically classified the soils based on the variance of their soil property data. Partial Least Squares Analysis (PLS) showed that TNT degradation was possibly correlated with soil fertility characteristics. Although this is an exploratory study, results show promise in moving towards a more effective way of predicting TNT environmental fate in soils.

This thesis presents a robust method for estimating the relaxations of a metallic object from its electromagnetic induction (EMI) response. The EMI response of a metallic object can be accurately modeled by a sum of real decaying exponentials. However, it is diffcult to obtain the model parameters from measurements when the number of exponentials in the sum is unknown or the terms are strongly correlated. Traditionally, the time constants and residues are estimated by nonlinear iterative search that often leads to unsatisfactory results. In this thesis, a constrained linear method of estimating the parameters is formulated by enumerating the relaxation parameter space and imposing a nonnegative constraint on the parameters. The resulting algorithm does not depend on a good initial guess to converge to a solution. Using tests on synthetic data and laboratory measurement of known targets the proposed method is shown to provide accurate and stable estimates of the model parameters.

The development of new innovations in explosives was an important part of the industrialization process from the mid-nineteenth century. The establishment of the world´s first nitroglycerin factory – Nitroglycerin Aktiebolaget (NA) in Stockholm in 1864 started a process replacing gunpowder with nitroglycerin and from 1868 by the safer invention dynamite. This affected both the long-term relationships between the mining industry and the powder mills and the demand from new industries for efficient and safe explosives. Even though the explosives industry was a small industry, it was of great importance for many other industries and for economic transformation. With dynamite and its successors, society also faced new risks. As a result, an extensive legislation was developed at an early stage which was supplemented with further supervision from a government authority in various organizations from 1895. The aim of the thesis is to investigate and analyze the major decision-making processes of the Swedish civilian explosives industry during the period 1858-1950. The purpose of the work is to contribute to gaining knowledge about how the society´s regulation of different industries has evolved and how state and private actors have acted in the development of new regulations. The work is structured around three main questions. The first question is about how the Swedish explosives industry developed during the period. How did the technological development of the industry and the explosives look like and had this any impact on the questions the actors within the industry drove? The second question is about how the dynamite industry was regulated. What did the regulations contain and how was the control organized? How did rights and obligations look like and how was the industry affected by this? The third question concerns the regulatory process itself. How and why did the regulations change and which actors were involved in the various changes? How did the Government and the actors act and can we see shifts over time between their different roles and interests? The study concludes that NA was the actor that, by using different methods, managed to gain the greatest influence over the regulatory process. Although the traditional established powder mill industry competed with NA at an early stage, it was nevertheless the initial, high-tech company that was involved in creating new national regulations in negotiation with the regulating authorities. This was a process of regulatory capture where NA, by combining both direct and indirect capture methods, managed to gain influence over regulations in the long run. A parallel but slightly different characteristic of this regulatory capture process is risk minimization for the public. Despite the occurrence of regulatory capture the regulations developed in a kind of a co-regulation system where the regulators became dependent on NA to provide the technical and practical expertise needed to build the necessary regulatory framework.

Blasting is a critical part of most mining operations. The primary function of blasting is to fragment and move rock. For decades, attempts have been made at increasing the efficiency of blasting to reduce costs and increase production. Most of these attempts involve trial and error techniques that focus on changing a single output. These techniques are costly and time consuming and it has been shown that as one output is optimized other outputs move away from their optimum level. To truly optimize a blasting program, the transfer of explosive energy into individual components must be quantified. Explosive energy is broken down into five primary components: rock fragmentation, heave, ground vibration, air blast, and heat. Fragmentation and heave are considered beneficial components while the remaining are considered waste. Past energy partitioning research has been able to account for less than 30% of a blast’s total explosive energy. The purpose of this dissertation was to account for a greater percentage of the explosive energy available during a blast. These values were determined using measurement techniques not previously applied to energy partitioning research. Four small-scale test series were completed, each designed to isolate individual energy components. Specific energy components measured include borehole chambering, elastic deformation (ground vibration), translational and rotational kinetic energy (heave), and air overpressure (air blast). This research was able to account for 73% of the total explosive energy. Borehole chambering (13%), rotational kinetic energy (25%), translational kinetic energy (5%), and air overpressure (28%) were determined to be the largest components. Prior research efforts have largely ignored rotational kinetic energy and have only been able to offer predictions for the values of borehole chambering and air overpressure energies. This dissertation accounted for a significantly higher percentage of total available explosive energy than previous research efforts using novel measurement techniques. It was shown that borehole chambering, heave, and air blast are the largest energy components in a blast. In addition to quantifying specific energy partitions, a basic goal programming objective function was proposed, incorporating explosive energy partitioning and blasting parameters into a framework that can be used for future energy optimization.

Drug trafficking and smuggling is an ongoing challenge for law enforcement agencies. Cocaine smuggling is a high-value pursuit for smugglers and has been attempted using a variety of concealment methods including the use of bottled liquids, canned milk, wax and suspensions in cans of beer. In particular, traffickers have used clothing impregnated with cocaine for smuggling. Handling, transportation or re-packaging of drugs of abuse and explosives will inevitably leave residual material on the clothing and other possessions of the involved persons. The nails and skin of the person may also be contaminated through the handling of these substances. This research study describes the development of Raman spectroscopic techniques for the detection of drugs of abuse and explosives on biomaterials of forensic relevance including undyed natural and synthetic fibres and dyed textile specimens, nail and skin. Confocal Raman microscopy has been developed and evaluated for the detection and identification of particulates of several drugs of abuse and explosives on different substrates. The results show that excellent spectroscopic discrimination can be achieved between single particles and substrate materials, giving a ubiquitous non-destructive approach to the analysis of pico-gram quantities of the drugs and explosives in-situ. Isolating the particle in this way corresponds with an analytical sensitivity comparable with the most sensitive analytical techniques currently available e.g. the highly sensitive, yet destructive ionization desorption mass spectrometry. With the confocal Raman approach, this work demonstrates that definitive molecular-specific information can be achieved within seconds without significant interference from the substrate. The potential for the application of this technique as a rapid preliminary, forensic screening procedure is obvious and attractive to non-specialist operators as it does not involve prior chemical pretreatment ii or detachment of the analyte from the substrate. As a result, evidential materials can be analysed without compromising their integrity for future investigation. Also, the applications of benchtop and portable Raman spectroscopy for the in-situ detection of drugs of abuse in clothing impregnated with the drugs have been demonstrated. Raman spectra were obtained from a set of undyed natural and synthetic fibres and dyed textiles impregnated with these drugs. The spectra were collected using three Raman spectrometers; one benchtop dispersive spectrometer coupled to a fibre-optic probe and two portable spectrometers. High quality spectra of the drugs could be acquired in-situ within seconds and without any sample preparation or alteration of the evidential material. A field-portable Raman spectrometer is a reliable instrument that can be used by emergency response teams to rapidly identify unknown samples. This method lends itself well to further development for the in-situ examination by law enforcement officers of items associated with users, handlers and suppliers of drugs of abuse in the forensics arena. In the last section of this study, a portable prototype Raman spectrometer ( DeltaNu Advantage 1064) equipped with 1064 nm laser excitation has been evaluated for the analysis of drugs of abuse and explosives. The feasibility of the instrument for the analysis of the samples both as neat materials and whilst contained in plastic and glass containers has been investigated. The advantages, disadvantages and the analytical potential in the forensics arena of this instrument have been discussed.