Explosives -- Analysis
Triacetone triperoxide (TATP), a cyclic peroxide explosive, is frequently used by terrorists and amateur chemists due to the ease of synthesis and the availability of reagents. TATP is extremely sensitive to shock, heat, and friction thus a safe and rapid method for treating TATP is needed. The major objective of this dissertation was to develop in situ methodologies that could safely degrade TATP in various field situations. Initial studies focused on using zero-valent metals and mechanically alloyed metals to decompose TATP samples in both aqueous and organic solutions. The metal systems tested included zero-valent iron, magnesium, and magnesium bimetal, Mg/Pd. The TATP degradation reaction with the different reactive metal systems followed pseudofirst order reaction kinetics with respect to TATP concentration, and the half-lives for TATP degradation with the different reactive metal systems were calculated to test their effectiveness. The major degradation product for the TATP decomposition was determined as acetone, and carbon material balance was calculated to determine each reactive system’s efficiency. The mechanism of TATP degradation using these reactive metal/bimetal particles was also explored, including reaction pathway, intermediates, and activation energies. In addition to investigating the use of zero-valent metals to degrade TATP, studies were also conducted on the use of certain metal and semimetal ionic species. Antimony (III) ions were found to have the greatest effect of TATP concentration. Various spectroscopic analyses were completed to try to characterize the reaction iv between the Sb3+ and TATP. The Sb3+ was theorized to instantaneously cleave the ring structure of the TATP molecule forming a Sb3+ complex thus Sb3+systems could be used to successfully treat TATP. In order to treat TATP in the field, the metal and bimetal reactive particles were combined with an application technology, liquid membrane systems to form emulsified zero-valent metal (EZVM) systems. EZVM systems containing the reactive metal/bimetal particles were made from an organic outer layer (corn oil), water, and a nonionic surfactant (SPAN 80). The EZVM systems were observed to absorb and dissolve the TATP into the emulsion droplets where TATP degradation then occurred. EZVM systems would be ideal for degrading dry TATP residues that might be found on a carpet, door entrance, steel, concrete, plastics, etc. The other neat metal systems could also be used to degrade aqueous slurries of TATP on different surfaces if an efficient delivery system was used. Other studies focused on the use of microscale mechanically alloyed bimetals, particularly Mg/Pd, Fe/Pd, and Fe/Ni, as alternative remediation methods for the catalytic reduction of environmental contaminants: 2, 4, 6-trinitrotoluene (TNT), and 1, 3, 5- trimethylene-2, 4, 6-trinitramine (RDX) which have been found to contaminate soil and ground/surface water near industrial production sites. All the bimetals tested were shown to reduce TNT and RDX contamination in water samples with varying reactivities under ambient reaction conditions. These metal systems could be combined with EZVM or paste treatment systems (bimetal treatment systems, BTS) for the in situ treatment of these environmental contaminants.
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Geiger, Cherie L.
Doctor of Philosophy (Ph.D.)
College of Sciences
Length of Campus-only Access
Doctoral Dissertation (Open Access)
Dissertations, Academic -- Sciences, Sciences -- Dissertations, Academic
Albo, Rebecca L., "Development Of Reductive Metal Systems For The Degradation Of Energetic Compounds (tatp, Tnt, And Rdx)" (2010). Electronic Theses and Dissertations, 2004-2019. 1552.