Publications

Abstract not provided.

Abstract not provided.

Abstract not provided.

The objective of this short-term LDRD project was to acquire the tools needed to use our chemical imaging precision mass analyzer (ChIPMA) instrument to analyze tissue samples. This effort was an outgrowth of discussions with oncologists on the need to find the cellular origin of signals in mass spectra of serum samples, which provide biomarkers for ovarian cancer. The ultimate goal would be to collect chemical images of biopsy samples allowing the chemical images of diseased and nondiseased sections of a sample to be compared. The equipment needed to prepare tissue samples have been acquired and built. This equipment includes an cyro-ultramicrotome for preparing thin sections of samples and a coating unit. The coating unit uses an electrospray system to deposit small droplets of a UV-photo absorbing compound on the surface of the tissue samples. Both units are operational. The tissue sample must be coated with the organic compound to enable matrix assisted laser desorption/ionization (MALDI) and matrix enhanced secondary ion mass spectrometry (ME-SIMS) measurements with the ChIPMA instrument Initial plans to test the sample preparation using human tissue samples required development of administrative procedures beyond the scope of this LDRD. Hence, it was decided to make two types of measurements: (1) Testing the spatial resolution of ME-SIMS by preparing a substrate coated with a mixture of an organic matrix and a bio standard and etching a defined pattern in the coating using a liquid metal ion beam, and (2) preparing and imaging C. elegans worms. Difficulties arose in sectioning the C. elegans for analysis and funds and time to overcome these difficulties were not available in this project. The facilities are now available for preparing biological samples for analysis with the ChIPMA instrument. Some further investment of time and resources in sample preparation should make this a useful tool for chemical imaging applications.

Through the use of simultaneous thermogravimetry modulated beam mass spectrometry, optical microscopy, hot-stage time-lapsed microscopy, and scanning electron microscopy measurements, the physical and chemical processes that control the thermal decomposition of 1,3,5-trinitrohexahydro-s-triazine (RDX) below its melting point (160-189°C) have been identified. Two gas-phase reactions of RDX are predominant during the early stages of an experiment. One involves the loss of HONO and HNO and leads to the formation of H 2O, NO, NO 2, and oxy-s-triazine (OST) or s-triazine. The other involves the reaction of NO with RDX to form NO 2 and 1-nitroso-3,5-dinitrohexahydro-s-triazine (ONDNTA), which subsequently decompose's to form a set of products of which CH 2O and N 2O are the most abundant. Products from the gas-phase RDX decomposition reactions, such as ONDNTA, deposit on the surface of the RDX particles and lead to the development of a new set of reaction pathways that occur on the surface of the RDX particles. The initial surface reactions occur on surfaces of those RDX particles in the sample that can accumulate the greatest amount of products from the gas-phase reactions. Initial surface reactions are characterized by the formation of islands of reactivity on the RDX surface and lead to the development of an orange-colored nonvolatile residue (NVR) film on the surface of the RDX particles. The NVR film is most likely formed via the decomposition of ONDNTA on the surface of the RDX particles. The NVR film is a nonstoichiometric and dynamic material, which reacts directly with RDX and ONDNTA, and is composed of remnants from RDX and ONDNTA molecules that have reacted with the NVR. Reactions involving the NVR become dominant during the later stage of the decomposition process. The NVR reacts with RDX to form ONDNTA via abstraction of an oxygen atom from an NO 2 group. ONDNTA may undergo rapid loss of N 2 and NO 2 with the remaining portion of the molecule being incorporated into the dynamic NVR. The dynamic NVR also decomposes and leads to the formation of H 2O, CH 2O, N 2O, NH 2CHO, (CH 3) 2NCHO, (CH 3) 2NNO, C 2H 2N 2O, and (CH 3) 3N or CH 3NCH 2CH 3. The competition between reaction of the dynamic NVR with RDX and its own thermal decomposition manifests itself in a rapid increase in the rate of evolution of the NVR decomposition products as the amount of RDX remaining in the sample nears depletion. The reactions between the NVR film and RDX on the surface of the RDX particles leads to a localized environment that creates a layer of molten RDX on the surface of the particles where reactions associated with the liquid-phase decomposition of RDX may occur. The combination of these reaction processes leads to an acceleration of the reaction rate in the later stage of the decomposition process and creates an apparent reaction rate behavior that has been referred to as autocatalytic in many previous studies of RDX decomposition. A reaction scheme summarizing the reaction pathways that contribute to the decomposition of RDX below its melting point is presented. © 2005 American Chemical Society.

Abstract not provided.

Several ingredients being considered by the U.S. Army for the development of new insensitive munitions have been examined. One set of ingredients consists of 2,4-dinitrophenylhydrazine (DNPH) and hexahydro-1,3,5-trinitro-s-triazine (RDX). In this set, the decomposition of the mixture was examined to determine whether adding DNPH to RDX would generate a sufficient quantity of gas to rupture the case of a munition prior to the onset of the rapid reaction of RDX, thus mitigating the violence of reaction. The second set of ingredients consists of three different reduced sensitivity RDX (RS-RDX) powders manufactured by SNPE and Dyno-Nobel. In this set, the objective was to determine properties of RS-RDX powders that may distinguish them from normal RDX powder and may account for their reduced shock sensitivity. The decomposition reactions and sublimation properties of these materials were examined using two unique instruments: the simultaneous thermogravimetric modulated beam mass spectrometry (STMBMS) instrument and the Fourier Transform ion cyclotron resonance (FTICR) mass spectrometry instrument. These instruments provide the capability to examine the details of decomposition reactions in energetic materials. DNPH does not appear to be a good candidate to mitigate the violence of the RDX reaction in a munition. DNPH decomposes between 170 C and 180 C. When mixed with RDX it decomposes between 155 C and 170 C. It decomposes to form 1,3-dintrobenzene (DNB), ammonia, water and nitrogen. Of these compounds only nitrogen and ammonia are capable of generating high pressures within a munition. When DNPH is mixed with RDX, the DNB formed in the decomposition of DNPH interacts with RDX on the surface of the RDX powder leading to a higher rate of formation of CH2O and N2O. The CH2O is consumed by reaction with DNPH to form 2-methylene-1-(2,4-dintrophenyl)hydrazine. As a result, DNPH does not generate a large quantity of gas that will lead to rupture of a munition case. Another compound to consider as an additive is 2-oxo-1,3,5-trinitro-1,3,5-triazacyclohexane (K-6), which generates more gas in the required temperature range. Examination of several different RS-RDX materials has shown that their sublimation rates and decomposition behavior differ from Holston grade RDX. The results suggest that insensitive RDX materials from both SNPE and Dyno-Nobel may have a shell-like structure of RDX on the surface of the particles that is less stable and more reactive than the material in the core of the particles. The origin of this shell-like RDX structure is uncertain, but may be due to some aspect of the manufacturing process. It is possible that this less stable RDX on the surface of the particles may be more fluid than the interior of the particles, allowing more slip between the surface of the particles under impact or shock. This may play a role in the reduced shock sensitivity of the insensitive RDX materials. The results of over 50 experiments with DNPH, mixtures of DNPH and RDX and insensitive RDX are presented. The results characterize the decomposition behavior of each of these materials.

Abstract not provided.