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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

<b>Flexible Energetics Trace Detection Schemes Utilizing Organic Electrochemical Transistors</b>

Aaron Benjamin Woeppel (18284320) 01 April 2024 (has links)
<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>
2

Screening and Quantitation of Volatiles from Explosive Initiators and Plastic Bonded Explosives (PBX)

Alexis J Hecker (18405276) 03 June 2024 (has links)
<p dir="ltr">The detection of explosives and explosive devices based upon the volatile compounds they emit is a long-standing tool for law enforcement and physical security. Towards that end, solid-phase microextraction (SPME) combined with gas chromatography-mass spectrometry (GC-MS) has become a crucial analytical tool for the identification of volatiles emitted by explosives. Previous SPME studies have identified many volatile compounds emitted by common explosive formulations that serve as the main charge in explosive devices. However, limited research has been conducted on initiators like fuses, detonating cords, and boosters. In this study, a variety of SPME fiber coatings (i.e., polydimethylsiloxane (PDMS), polydimethylsiloxane/divinylbenzene (PDMS/DVB), divinylbenzene/carboxen/polydimethylsiloxane (DVB/CAR/PDMS), carboxen/polydimethylsiloxane (CAR/PDMS), and polyacrylate (PA)) were employed for the extraction and analysis of volatiles from Composition C-4 (cyclohexanone, 2-ethyl-1-hexanol, and 2,3-dimethyl-2,3-dinitrobutane (DMNB)) and Red Dot double-base smokeless powder (nitroglycerine, phenylamine). The results revealed that a PDMS/DVB fiber was optimal. Then, an assortment of explosive items (i.e., detonation cord, safety fuse, slip-on booster, and shape charge) were analyzed with a PDMS/DVB fiber. A variety of volatile compounds were identified, including plasticizers (tributyl acetyl citrate, N-butylbenzenesulfonamide), taggants (DMNB), and degradation products (2-ethyl-1-hexanol). </p><p dir="ltr">Taggants, like DMNB, are one of the pivotal components added to explosives. These distinctive chemical markers, deliberately introduced during manufacturing to facilitate the identification of explosives, are commonly detected using SPME GC- MS, but their quantitation remains underexplored. To address this, we investigated total vaporization headspace (TV- HS) GC- MS for quantifying taggants in the headspace of Composition C4. Factors effecting the extraction of DMNB, such as shape and age of the sample, and surface depletion, were also examined. The results revealed that the shape of the sample did not affect the amount of DMNB in the headspace but the older the sample, the more DMNB was detected in the headspace. Surface depletion was also seen in samples that were exposed to air for more than one week. Then calibration curves with calibrants of DMNB in acetone were established for quantitation. The average concentration of DMNB in the headspace was determined to be 125 parts per million (ppm).</p><p><br></p>

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