Strategies have been developed to determine the kinetics and mechanisms of degradation of energetic molecules in water up to 500 deg C. FTIR and FT-Raman spectroscopy enable in situ studies to be made and provide a wide spectral window in which many species can be followed simultaneously. Numerous spectroscopic and cell design hurdles have been encountered and surmounted so far. Cell designs and a process flow system that should provide clean kinetic studies are nearly completed at this time....
Topics: DTIC Archive, Brill, Thomas B, DELAWARE UNIV NEWARK DEPT OF CHEMISTRY, *RAMAN SPECTROSCOPY,...
The rapid thermal decomposition characteristics of alkylammonium nitrate salts in which the alkyl group is a hydrocarbon cage are described. Cubylammonium nitrate, cubane-1, 4-diammonium dinitrate, and penta undecane-4- exo-e-endo diammonium dinitrate were studied. Comparisons are made to the behavior of other alkylammonium nitrate salts upon fast thermolysis. Keywords: Energetic materials, Rapid scan fourier transform infrared spectroscopy, Thermal decomposition.
Topics: DTIC Archive, Brill, Thomas B, DELAWARE UNIV NEWARK DEPT OF CHEMISTRY, *DETECTION, *SPECTROSCOPY,...
Infrared studies of the solid-melt phases of a homologous series of organobis (ammonium nitrate) salts (1,2- ethanediammonium dinitrate through 1,6- hexanediammonium dinitrate) are described. Fast thermolysis experiment involving selected organoammonium and orgaodiammonium nitrate salts are also described. Conclusions related to the solid phase and thermolysis studies are presented.
Topics: DTIC Archive, Brill, Thomas B, DELAWARE UNIV NEWARK DEPT OF CHEMISTRY, *FOURIER SPECTROSCOPY,...
The effect of inorganic species alone and on organic reactions at hydrothermal conditions was being investigated. The method involves the use of real-time IR spectroscopy in a windowed flow reactor. The specific studies were directed at the water gas shift reaction below the critical temperature of water; the kinetics of decomposition of nickel tetracarbonyl, sodium tetracarbonylcobaltate, and cyclopentadienyl cobalt dicarbonyl at hydrothermal conditions; decarboxylation and defluorination of...
Topics: DTIC Archive, Brill, Thomas B, DELAWARE UNIV NEWARK DEPT OF CHEMISTRY, *KINETICS, *CARBOXYLIC...
Strategies have been developed to determine the kinetics and mechanisms of degradation of energetic molecules in water up to 500 deg C. FTIR and Fr-Raman spectroscopy enable studies to be made and provide a wide spectral window in which many species can be followed simultaneously. Numerous spectroscopic and cell design hurdles have been encountered and surmounted so far. Cell designs and a process flow system that should provide clean kinetic studies are nearly completed at this time....
Topics: DTIC Archive, Brill, Thomas B, DELAWARE UNIV NEWARK DEPT OF CHEMISTRY, *DEGRADATION, *WATER, *HIGH...
The breakdown of the crystal lattice of ammonium perchlorate in the 300-625 K range has been studied by laser Raman spectroscopy. Detailed examination of the external and internal modes of the ion reveals that the onset of essentially unhindered tumbling of the ClO4(-) ion seems to be intimately tied to the decomposition of AP. The effect of K(+) as an isomorphous dopant in the crystal lattice is to permit the ClO4(-) ion to tumble at a lower temperature (0.8% K(+) produces a 60-70 K lowering...
Topics: DTIC Archive, Brill,Thomas B., DELAWARE UNIV NEWARK DEPT OF CHEMISTRY, *Ammonium perchlorate,...
A critical examination of the kinetics and mechanisms of nitroaromatic explosives is made. The initiation reaction mechanisms differ with temperature. Shock initiation conditions produce mostly C-NO, bond homolysis. Impact initiation produces a mixture of C-NO2 homolysis and reactions of the non-energetic substituents on the ring. Time-to-explosion for times longer than about 0.1 seconds is controlled mostly by catalysis from the decomposition products of the parent molecule. The explosive...
Topics: DTIC Archive, Brill, Thomas B, DELAWARE UNIV NEWARK, *THERMAL PROPERTIES, *EXPLOSIVES, *KINETICS,...
Determination of the pressure-temperature phase diagram of the beta-to-delta polymer conversion of HMX has been completed. Enthalpy, entropy values were determined as was the effect of particle size. Variations in the nature of decomposition were found to be the source of the observed slope breaks and the particle size effect. The mechanism of motion in beta-HMX up to the phase transition temperature was found to involve disruption of the pivoting motion about the most stabilizing...
Topics: DTIC Archive, Brill,Thomas B, DELAWARE UNIV NEWARK DEPT OF CHEMISTRY, *DYNAMICS, *COMPOSITE...
High heating rate thermoylsis studies of energetic materials using rapid-scan Fourier transform infrared spectroscopy as the diagnostic technique have yielded considerable information on the origins of the pressure dependence of the process and structure/property/reactivity relationships. The pressure dependence of the observed gas products up to 1000 psi was shown for the first time to originate from heterogeneous gas/condensed phase reactions. The formation of NH3 from alkylammonium nitrate...
Topics: DTIC Archive, Brill, Thomas B, DELAWARE UNIV NEWARK DEPT OF CHEMISTRY, *NITRAMINES, *ENERGETIC...
Rapid-scan infrared spectroscopy studies of the high rate thermolysis of energetic molecules containing CNO2, NNO2, ONO2, N3, NO3(-), IR spectroscopy, DSC, solid-state NMR and X-ray crystallography have been conducted. Structure/property/reactivity relationships have been established for the formation of NO2 and HONO. Understanding of some of the factors influencing the formation of CH2O, N2O and NO has also been acquired. The influence of the static applied pressure on the first observed...
Topics: DTIC Archive, Brill,Thomas B, DELAWARE UNIV NEWARK DEPT OF CHEMISTRY, *INFRARED SPECTROSCOPY,...
The structure of RDX has been compared by the use of Fourier transform infrared spectroscopy in the gas phase, melt phase, solution phase, and the solid Beta and alpha phases. The gas, melt, and solid Beta-RDX phases have not been studied previously. The RDX molecule has essentially C sub 3V molecular structure in all environments except the stable solid Alpha-RDX phase. The RDX and HMX melts were found to be comprised almost entirely of intact nitramine molecules, but decomposition before...
Topics: DTIC Archive, Brill, Thomas B., DELAWARE UNIV NEWARK DEPT OF CHEMISTRY, *EXPLOSIVES, *MOLECULAR...
This research program was devoted to the study of high-nitrogen compounds that have been of worldwide interest as gas generators, explosives, and propellants. The focus was specifically on substituted tetrazole and furazan ring compounds. The Russian FLAME database reveals that many of these compounds have high burning rates. In the United States these compounds are of interest to AFRL, Los Alamos National Laboratory, and the Thiokol Corporation as highly energetic materials. The research...
Topics: DTIC Archive, Brill, Thomas B, DELAWARE UNIV NEWARK DEPT OF CHEMISTRY, *COMBUSTION, *CHEMICAL...
The high heating rate thermal decomposition of HAN and LP1845 was conducted using the FTIR/temperature profiling technique. The crystal structure of pure HAN was obtained. Models of the behavior of these materials during decomposition were developed. Very concentrated aqueous metal nitrate salt solutions were also investigated at high temperature and pressure by Raman spectroscopy to gain an understanding of the properties of HAN under similar conditions. To determine the feasibility of...
Topics: DTIC Archive, Brill, Thomas B, DELAWARE UNIV NEWARK DEPT OF CHEMISTRY, *SPECTROSCOPY, *PYROLYSIS,...
Combustion Characteristics of Crystalline Oxidizers: Time-of-flight and high resolution mass spectrometry of UHP-AP and its deuterated derivative were examined in an effort to identify some of the key decomposition species. Of particular interest is the sure detection of HNO, the hydrides of nitrogen and the oxides of chlorine. HNO (mass 31) was found as a minor component at temperatures above 80 C. It is considered highly improbable that HNO could have occurred by reactions other than surface...
Topics: DTIC Archive, Brill,Thomas B., DELAWARE UNIV NEWARK DEPT OF CHEMISTRY, *COMBUSTION, *PYROLYSIS,...
A study of the molecular dynamics of the solid phase of HMX and RDX was undertaken to learn the effects of thermal and pressure stress on these nitramines. Raman, nuclear quadrupole resonance, and nuclear magnetic resonance spectroscopy, mass spectrometry, X-ray methods and computer graphics were or are being employed. A complete analysis of the four polymorphs of HMX as a function of temperature and pressure by using Raman spectroscopy was made. A pressure- temperature phase diagram of the...
Topics: DTIC Archive, Brill, Thomas B., DELAWARE UNIV NEWARK DEPT OF CHEMISTRY, *DYNAMICS, *COMPOSITE...
The objective of this project was to identify the dominant thermal decomposition and secondary reaction pathways that exist in the surface zone of a burning propellant. T-jump/FTIR spectroscopy and SMATCH/FTIR spectroscopy are new diagnostic techniques that were designed for this project. They enable a film of material to be heated at a high rate in such a manner as to simulate a thin volume element of the surface during combustion. The semiglobal thermal decomposition reactions and the first...
Topics: DTIC Archive, Brill, Thomas B, DELAWARE UNIV NEWARK DEPT OF CHEMISTRY, *SURFACES, *CHEMISTRY,...
Chemical mechanisms and kinetics are described for the surface reaction zone of materials of interest in solid rocket propellants. The technique used is flash thermolysis of films by T-jump-Fourier transform infrared spectroscopy. The potential for burn rate modification by a wide variety of related nitrogen heterocyclics was uncovered. The kinetics of decomposition of HMX, RDX and NTO were evaluated and critically analyzed. It was found that a kinetic compensation effect exists. Lower values...
Topics: DTIC Archive, Brill, Thomas B., DELAWARE UNIV NEWARK DEPT OF CHEMISTRY, *CHEMICAL REACTIONS,...
