Hexamethylene triperoxide diamine (HMTD) is a well known amine peroxide that starts to decompose at ambient
temperature. At 40°C HMTD began to break up into volatile pungent compounds, including trimethyl amine. The
production of these compounds could be useful for the vapor detection of HMTD by common techniques such as
GC-MS and IMS. GC-MS analysis was performed and several volatile amines could be detected including initial
reagents, such as hexamine. IMS produced an alarm indicating the presence of other compounds. Open-Air
Chemical Ionization (OACI)-Time of Flight (TOF)-Mass Spectroscopy was the most useful technique for the
analysis of HMTD. Even at high temperatures (250°C), it was possible to detect the molecular ion at m/z 209.078.
Other fragments observed in the mass spectrum were the loss of formaldehyde at m/z 179.069 and the loss of
hydrogen peroxide at m/z 145.060. A mixture of 30 ppb of HMTD and triacetone triperoxide (TATP) was
successfully analyzed by OACI-TOF-MS, thus demonstrating its feasibility for trace analysis of organic peroxides
and related compounds.
Characterization of hexamethelene triperoxide diamine (HMTD), tetramethylene diperoxide dicarbamide (TMDD)
and tetramethylene diperoxide acetamide (TMDA) has been carried out using Direct Analysis in Real Time/Time of
Flight Mass Spectrometry (DART-TOF/MS). The study also centered in the detection of their precursors such as
hexamine and formaldehyde. Analysis of the compounds by GC-MS was also conducted. HMTD shows a clear peak
at 209 m/z that allowed its detection in standard solutions and lab made standards. TATP samples with deuterium
enrichment are being analyzed to compare results that could differentiate from HMTD and similar substances. All
samples were characterized by Raman and FT-IR to confirm the DART results. Some of the vibrations observed
were in the ν(O-O), ν(N-C), ν(N-H), ν(C-O), δ(CH3-C) and δ(C-O). Development methodology for trace detection
was compared with GC/MS and HPLC-MS results previously presented for HMTD and TATP.
Deep Ultra Violet Raman Spectroscopy (DUV-RS) is an emerging tool for vibrational spectroscopy analysis and can be used in Point Detection mode to detect explosive components of landmines and Improvised Explosive Devices (IED). Interactions of explosives with different substrates can be measured by using quantitative vibrational signal shift information of scattered Raman light associated with these interactions. In this research, grounds were laid for detection of explosives using UV-Raman Spectroscopy equipped with 244 nm laser excitation line from a 488 nm frequency doubled Coherent FreD laser. In other experiments, samples of 2,4-DNT were allowed to interact with Ottawa Sand and were studied using DUV-RS. Characteristic vibrational signals of energetic compounds were analyzed in the ranges: 400-1200 cm-1, 1200-1800 cm-1, and 2800-3500 cm-1. In addition these Raman spectra were compared with dispersive spectra that were acquired using Raman Microscopy equipped with 514.5 nm (VIS) 785 nm (NIR) and 1064 nm (NIR) excitation lasers.
Synthesis and characterization of hexamethelene triperoxide diamine (HMTD), tetramethylene diperoxide dicarbamide (TMDD) and tetramethylene diperoxide acetamide (TMDA) using GC-MS, HPLC-MS, FT-IR and Raman Microscopy has been carried out. The study also centered in the synthesis and characterization of other cyclic amine peroxides, including and different forms of caged peroxides from other diaminoalkanes. Interest also was given to the secondary products of all syntheses and the effect of temperature in the composition mixtures of the preparations. Differentiation spectroscopy and spectrometry studies were also conducted. In these studies the differences in the ν(O-O), ν(N-C), ν(N-H), ν(C-O), δ(CH3-C) and δ(C-O) bands for Raman and IR were established. For the GC/MS spectrometric studies retention times and fragmentation patterns for GC-MS and GC-FT-IR useful in amine peroxide differentiation were also established.
Cyclic organic peroxides are sensitive to the presence of water and other contaminants that can deactivate the substance or make it less sensitive to chock, spark or other detonating mechanism. In the case of radiation such as laser action the opposite seems to happen, making the peroxides more sensitive to laser breakdown and local burning. In recent studies, TATP has been induced to sublimate faster during Raman analysis when it had contaminants or water, however, some studies have shown that TATP does not reacts when it is wet. This study is focused on determining if the presence of water and other contaminants affects peroxide stability and the detection by current technologies, such as IMS and vibrational spectroscopy. During the study, TATP and HMTD have been synthesized by different methods using certified chemicals and common household products. The research also focused on the effect of metal salts in the syntheses and the effect of temperature in the composition of the products. Differences in the location, shape, relative intensity, and in some cases appearance of new bands possibly due to Redox and complex formation reactions were evident. Bands corresponding to ν(O-O), ν(C-O), δ(CH3-C) and δ(C-O) were located and assigned for Raman and IR spectroscopies.
Peroxide-based explosives have become of increased interest mainly because they are easily prepared and are not detected by traditional detection devices. The thermal behavior of triacetone triperoxide (TATP), a cyclic peroxide explosive was characterized by Differential Scanning Calorimetry (DSC) and Thermal Gravimetric Analysis (TGA). Dynamic and isothermal methods were used to characterize the sublimation process and to measure the vapor pressure at a temperature range under exothermic decomposition. The enthalpy of sublimation and kinetic parameters were estimated from direct mass loss rate measurements. Melting point, decomposition temperature and enthalpies of transitions were determined and compared to other known materials. The values were also compared to other recently reported values. The results of this study will help in the development of standoff detection technologies for improvised explosive devices using peroxide based materials.
The characterization of Tetracetone Tetraperoxide (TRATRP), Triacetone Triperoxide (TATP), Diacetone Diperoxide (DADP), Tricyclohexylidene Triperoxide and Dibenzo Diperoxide using GC-MS, GC-FTIR, FTIR, FT-NMR and Raman Spectroscopy is reported. These compounds were synthesized, purified and characterized in the laboratory in order to develop methodologies for their trace detection. During this study, TATP has been synthesized by different methods obtaining high purity and good yields, even using common household products. DADP synthetic routes reported in the literature were verified. The methods described, including those that produce mixtures with TATP and other peroxides forms were also tested. This study will also focused in the preparation of other cyclic peroxides, including Hexamethelene Triperoxide Diamine (HMTD) and different forms of cyclic peroxides from ketones. This issue of thermodynamic versus kinetic control of secondary products of all syntheses and the effect of temperature in the distribution sub products of the syntheses was also addressed. A vibrational differentiation study of was carried out. Differences were found computationally in the υ(O-O), υ(C-O), δ(CH3-C) and δ(C-O) for Raman and IR bands and retention time and fragment patron for GC-MS and GC-FT-IR.
Non nitrogen containing, organic peroxides explosives Triacetone triperoxide and diacetone diperoxide have been prepared in the laboratory in order to study various aspects of their synthesis and their experimental and theoretical spectroscopic characteristics. By using different proportions of acetone/hydrogen peroxide (Ac/H2O2), sulfuric, hydrochloric and methanosulfuric acids as catalyzers, it was possible to obtain both compounds in a rapid and simple form. Raman, IR spectroscopy, and GC-MS were used in order to determine the precursors, intermediates and final analytes. Experiments and theoretical studies using density functional theory (DFT) have been used in the elucidation step of the mechanism of the synthesis of the so called "transparent" explosives. The B3LYP functional with the 6-31G** basis set was used to carry out the electronic structure calculation of the intermediates and internal rotations and vibrations of TATP. Raman spectra of solid TATP and FTIR spectra of gas TATP, were recorded in order to assign the experimental spectra. Although full agreement with experiment was not obtained, spectral features of the main TATP bands were assigned.
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