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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Laponite-Incorporated UiO-66-NH2-Polyethylene Oxide Composite Membranes for Protection against Chemical Warfare Agent Simulants

A strategy is developed to enhance the barrier protection of polyethylene oxide (PEO)-metal–organic framework (MOF) composite films against chemical warfare agent simulants. To achieve enhanced protection, an impermeable high-aspect-ratio filler in the form of Laponite RD (LRD) clay platelets was incorporated into a composite PEO film containing MOF UiO-66-NH 2 . The inclusion of the platelets aids in mitigating permeation of inert hydrocarbons (octane) and toxic chemicals (2-chloroethyl ethyl sulfide, 2-CEES) of dimensions/chemistry similar to prominent vesicant threats while still maintaining high water vapor transport rates (WVTR). By utilizing small-angle neutron scattering, small-angle X-ray scattering, and wide-angle X-ray scattering, the LRD platelet alignment of the films was determined, and the structure of the films was correlated with performance as a barrier material. Performance of the membranes against toxic chemical threats was assessed using permeation testing of octane and 2-CEES, a common simulant for the vesicant mustard gas, and breathability of the membranes was assessed using WVTR measurements. To assess their robustness, chemical exposure (in situ diffuse reflectance infrared Fourier transform spectroscopy) and mechanical (tensile strength) measurements were also performed. It was demonstrated that the barrier performance of the film upon inclusion of the LRD platelets exceeds that of other MOF-polymer composites found in the literature and that this approach establishes a new path for improving permselective materials for chemical protection applications.

36 MATERIALS SCIENCE↗
DOE OSTI2023

High reactivity of mesoporous CeO 2 to dissociate chemical warfare agent sarin

We perform spectroscopic surface characterization on mesoporous ceria (CeO 2 ) under exposure of sarin gas, also known as GB. We find mesoporous CeO 2 displays extraordinary reactivity towards GB dissociation under high vacuum. The spectroscopic results combined with density functional theory (DFT) calculations suggest that the cleavage of the P–F and P–OR bonds are both possible pathways for GB to dissociate on the CeO 2 surfaces. The modeling reveals differences in dissociation pathways of GB on the crystallographic (111)- and (110)-surfaces of ceria. Here we also report some dissociation of GB on mesoporous CeO 2 under ambient conditions. The finding that mesoporous CeO 2 can degrade GB under mild conditions is encouraging and implies the strong potential of ceria-based materials to be applied in combating chemical warfare agents related to the GB series.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Practical benzylation of N,N -substituted ethanolamines related to chemical warfare agents for analysis and detection by Electron Ionization Gas Chromatography-Mass Spectrometry

The benzylation of three, low-molecular weight N,N-disubstituted ethanolamines related to chemical warfare agents (CWAs) to furnish derivatives with improved Gas Chromatography-Mass Spectrometry (GC-MS) profiles is described. Due to their low molecular weight and polar nature, N,N-disubstituted ethanolamines are notoriously difficult to detect by routine GC-MS analyses during Organisation for the Prohibition of Chemical Weapons (OPCW) proficiency tests (PTs), particularly in scenarios when they are present at low levels (~1-10 ppm) amidst more abundant interferences. Our studies revealed that the optimal derivatization conditions involved the treatment of the ethanolamine with benzyl bromide in the presence of an inorganic base (e.g., Na 2 CO 3 ) in dichloromethane at 55 °C for 2 hours. This optimized set of conditions were then successfully applied to the derivatization of N,N-dimethylethanolamine, N,N-diethylethanolamine and N,N-diisopropylethanolamine present separately at 1 and 10 μg/mL concentrations in a glycerol-rich matrix sample featured in the 48 th OPCW PT. The benzylated derivatives of the three ethanolamines possessed retention times long enough to clear the massive glycerol-containing matrix interferences. In conclusion, the protocol herein is introduced as an alternative method for derivatization of these CWA and pharmaceutically important species and should find broad applicability in laboratories where their routine forensic analysis is carried out.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Application of artificial neural network to prompt gamma neutron activation analysis for chemical warfare agents identification

The Portable Isotopic Neutron Spectroscopy (PINS) is a commercialized system developed by Idaho National Laboratory (INL) to examine chemical warfare agents (CWA) non-destructively, utilizing Prompt Gamma Neutron Activation Analysis (PGNAA) techniques. The PINS system takes advantage of a high-resolution gamma-ray spectrum from a mechanically-cooled high-purity germanium (HPGe) detector, and gamma-ray peak analysis provides input to its chemical identification logic with a probabilistic decision tree (PDT). The effectiveness of the chemical identification algorithm is determined by the availability of a wide range of data to train the algorithm to identify chemical-fills with accuracy. INL has a collection of gamma-ray spectra of various chemical-fills from the field-deployed PINS systems over the years, and it was envisaged to leverage such a database with the Artificial Neural Network (ANN) technique. Therefore, an ANN-based chemical identification algorithm was developed as an independent verification of the current algorithm. The ANN-based algorithm’s performance was evaluated against the U.S. Army blind test data, and results were presented and discussed in this study.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2019

Electronic Warfare Software

This poster is about an electronic warfare software that allows the USAF to simulate signal propagation for the purpose of mission planning.

42 ENGINEERING↗
DOE OSTI2016

Effective methylation of phosphonic acids related to chemical warfare agents mediated by trimethyloxonium tetrafluoroborate for their qualitative detection and identification by gas chromatography-mass spectrometry

The effective methylation of phosphonic acids related to chemical warfare agents (CWAs) employing trimethyloxonium tetrafluoroborate (TMO·BF 4 ) for their qualitative detection and identification by gas chromatography-mass spectrometry (GC-MS) is presented. The methylation occurs in rapid fashion (1 h) and can be conveniently carried out at ambient temperature, thus providing a safer alternative to the universally employed diazomethane-based methylation protocols. Optimization of the methylation parameters led us to conclude that methylene chloride was the ideal solvent to carry out the derivatization, and that even though methylated products can be observed surfacing after only 1 h, additional time was not found to be detrimental but beneficial to the process particularly when dealing with analytes at low concentrations (~10 μg mL -1 ). Due to its insolubility in methylene chloride, TMO·BF 4 conveniently settles to the bottom during the reaction and does not produce additional interfering by-products that may further complicate the GC-MS analysis. We demonstrated the method to successfully methylate a variety of Schedule 2 phosphonic acids, including their half esters, resulting in derivatives that were readily detected and identified using the instrument's spectral library. Most importantly, the method was shown to simultaneously methylate a mixture of the organophosphorus-based nerve agent hydrolysis products: pinacolyl methylphosphonate (PMPA), cyclohexyl methylphosphonate (CyMPA) and ethyl methylphosphonate (EMPA) (at a 10 μg mL - 1 concentration each) in a fatty acid ester-rich organic matrix (OPCW-PT-O 3 ) featured in the 38th Organisation for the Prohibition of Chemical Weapons (OPCW) Proficiency Test. Additionally, the protocol was found to effectively methylate N,N-diethylamino ethanesulfonic acid and N,N-diisopropylamino ethanesulfonic acid that are products arising from the oxidative degradation of the V-series agents VR and VX respectively. This work described herein represents the first report on the use of TMO·BF 4 as a viable, stable and safe agent for the methylation of phosphonic acids and their half esters and within the context of an OPCW Proficiency Test sample analysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Grafting-To and From for Multiplexed Chemical-Warfare-Agent Responsive Polymer Brushes

Surface-tethered polymers have important applications in functional polymer coatings, particularly for the development of chemically responsive surfaces. Here, we combined the traditional grafting-to and grafting-from methods to create a new surface grafting strategy, termed grafting-to and from, using surface-initiated ring-opening metathesis polymerization (SI-ROMP). In this method, poly(pentafluorophenyl methacrylate) is grafted to an amine terminated surface. Surplus reactive esters after reaction with surface amines render this polymer a connecting or tie layer that can be further reacted to provide dense ROMP initiation sites. This amplification of grafting sites results in thick and environmentally stable polymer brushes upon SI-ROMP. With the goal of developing polymer-grafted breathable membranes that autonomously react to multiple chemical warfare agents (CWAs), we demonstrate the benefit of this method by employing amine reactive monomers in the grafting-from step. This enables diverse postsynthetic functionalization for the facile screening of chemical motifs to enhance response capabilities to mustard blister agents. Surface-tethered triarylmethanol-containing polymers with four distinct functional groups are prepared and challenged with the vapor of 2-chloroethyl ethyl sulfide (CEES), a simulant of mustard agent, in humid air. Importantly, hydroxyl groups effectively improve CWA response and the resulting polymer brushes show chain collapse after both CEES and diethylchlorophosphate (DCP) treatment. Our results illustrate that the grafting-to and from method can be used to grow functional and robust polymer coatings for various applications.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Spectroscopic and Computational Investigation of Room-Temperature Decomposition of a Chemical Warfare Agent Simulant on Polycrystalline Cupric Oxide

Certain organophosphorus molecules are infamous due to their use as highly toxic nerve agents. The filtration materials currently in common use for protection against chemical warfare agents were designed before organophosphorus compounds were used as chemical weapons. A better understanding of the surface chemistry between simulant molecules and the individual filtration-material components is a critical precursor to the development of more effective materials for filtration, destruction, decontamination, and/or sensing of nerve agents. Here in this paper, we report on the surface adsorption and reactions of a sarin simulant molecule, dimethyl methylphosphonate (DMMP), with cupric oxide surfaces. In situ ambient pressure X-ray photoelectron and infrared spectroscopies are coupled with density functional calculations to propose mechanisms for DMMP decomposition on CuO. We find extensive room temperature decomposition of DMMP on CuO, with the majority of decomposition fragments bound to the CuO surface. We observe breaking of PO-CH 3 , P-OCH 3 , and P-CH 3 bonds at room temperature. On the basis of these results, we identify specific DMMP decomposition mechanisms not seen on other metal oxides. Participation of lattice oxygen in the decomposition mechanism leads to significant changes in chemical and electronic surface environment, which are manifest in the spectroscopic and computational data. This study establishes a computational baseline for the study of highly toxic organophosphorous compounds on metal oxide surfaces.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Mechanism and Kinetics for Reaction of the Chemical Warfare Agent Simulant, DMMP( g ), with Zirconium(IV) MOFs: An Ultrahigh-Vacuum and DFT Study

The mechanism and kinetics of interactions between dimethyl methylphosphonate (DMMP), a key chemical warfare agent (CWA) simulant, and Zr 6 -based metal organic frameworks (MOFs) have been investigated with in situ infrared spectroscopy (IR), X-ray photoelectron spectroscopy (XPS), powder X-ray diffraction (PXRD), and DFT calculations. DMMP was found to adsorb molecularly to UiO-66 through the formation of hydrogen bonds between the phosphoryl oxygen and the free hydroxyl groups associated with Zr 6 nodes on the surface of crystallites and not within the bulk MOF structure. Unlike UiO-66, the infrared spectra for UiO-67 and MOF-808, recorded during DMMP exposure, suggest that uptake occurs through both physisorption and chemisorption. The XPS spectra of MOF-808 zirconium 3d electrons reveal a charge redistribution following exposure to DMMP. In addition, analysis of the phosphorus 2p electrons following exposure and thermal annealing to 600 K indicates that two types of stable phosphorus-containing species exist within the MOF. DFT calculations, used to guide the IR band assignments and to help interpret the XPS features, suggest that uptake is driven by nucleophilic addition of an OH group to DMMP with subsequent elimination of a methoxy substituent to form strongly bound methyl methylphosphonic acid (MMPA). The rates of product formation indicate that there are likely two distinct uptake processes, requiring rate constants that differ by approximately an order of magnitude. However, the rates of molecular uptake were found to be nearly identical to the rates of reaction, which strongly suggests that the reaction rates are diffusion-limited. Here, the final products were found to inhibit further reactions within the MOFs, and these products could not be thermally driven from the MOFs prior to decomposition of the MOFs themselves.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Insights into Catalytic Hydrolysis of Organophosphate Warfare Agents by Metal–Organic Framework NU-1000

Metal–organic frameworks (MOFs) have been reported to be versatile catalysts because of their amenability to modular design and tunability. Recently, a series of zirconium-based MOFs have been used to catalyze the hydrolytic destruction of chemical warfare agents (CWAs) that contain phosphate ester bonds. Here, we adopt density functional theory calculations to study the hydrolysis of the CWA simulant methylparaoxon on the Zr-based MOF NU-1000. Our calculated energy barriers are in quantitative agreement with previous experimental kinetics data. Comparison between uncatalyzed aqueous hydrolysis and the MOF-catalyzed reaction reveals the origin of the catalytic effects of NU-1000 and shows a resemblance to enzymatic catalysis of similar reactions. Finally, the effect of node distortion on the catalytic mechanism is also examined, and the results are consistent with experimental findings, where the distorted node of NU-1000 shows an increase in the rate of methylparaoxon hydrolysis compared to the completely hydrated regular form of NU-1000.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

How Useful Are Common Simulants of Chemical Warfare Agents at Predicting Adsorption Behavior?

We report that nanoporous materials such as metal–organic frameworks (MOFs) have attractive properties for selective capture of chemical warfare agents (CWAs). For obvious reasons, most research on adsorption of CWAs is performed with simulant molecules rather than real agents. This paper examines how effectively common CWA simulants mimic the adsorption properties of sarin and soman. To this end, we perform molecular simulations in the dilute adsorption limit for four simulants [dimethyl methylphosphonate (DMMP), diethyl chlorophosphate (DCP), diisopropyl fluorophosphate, and dimethyl p-nitrophenyl phosphate (DMNP)] and sarin and soman in a set of 2969 MOFs with experimentally known crystal structures. To establish the robustness of the conclusions with respect to the force field used in these simulations, each system was examined with two independent force fields, a “generic” force field and a density functional theory (DFT)-derived force field we established based on extensive dispersion-corrected DFT calculations of adsorption in the well-known MOF UiO-66. Our results show that when judging the performance of adsorbents using the heat of adsorption, DCP and DMMP are the best simulants for the adsorption of sarin, while DMNP is the best simulant for soman. The adsorption properties of DCP or DMMP show a strong correlation with sarin over a range of MOFs, but the correlation between DMNP and soman is considerably weaker. Finally, comparisons of results with both force fields indicate that our main conclusions are robust with respect to the force field used to define adsorbate–MOF interactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Accelerating countermeasure candidate discovery for A-series chemical warfare agent exposure

The recent alleged use of A-series chemical warfare agents (CWAs) highlights the urgent need to better understand their inhibition of cholinesterase enzymes and the reported shortcomings of traditional oxime countermeasures. Here, using high-throughput (HT) mass spectrometry (MS) technologies, we characterized the largely unknown inhibition kinetics of A-series CWAs on human acetylcholinesterase (hAChE) and its reactivation by oximes, achieving label-free quantitation at rates of up to 7,000 reactions per hour. Our findings indicate i) A-series agents exhibit inhibitory potencies similar to traditional CWAs like sarin and VX, and ii) bipyridinium-based oximes can reactivate A-series-adducted hAChE in vitro, challenging prior reports on oxime efficacy. These results underscore the need for continued exploration of countermeasure candidates against A-series CWAs and demonstrate the potential of HT-MS for rapidly and safely characterizing emerging toxic chemicals.

acetylcholinesterase↗
DOE OSTI2020

Internal Standards for Quantitative Analysis of Chemical Warfare Agents by the GC/MS Method: Nerve Agents

General conditions and requirements for an internal standard useful in the determination of chemical warfare agents (CWAs) by the method of gas chromatography coupled with mass detection (GC/MS) were defined. The determination is based on a GC/MS analysis of a mixture of a CWA with an internal standard, conversion of the TIC chromatogram to a chromatogram extracted at a particular m / z ratio, and calculation of the CWA concentration from the internal standard concentration, response factor, and chromatographic peak areas. Available internal standards were identified, and they were verified for seven organophosphorus nerve-paralysing agents. Corresponding response factors were determined as a ratio of gradients of the linear functions of the peak area and compound concentration. Linearity, repeatability, and accuracy of the measurements were evaluated. The determination can be performed on all GC/MS systems of the Fire Rescue Service of the Czech Republic (FRS), where no CWA standards are available.

Capoun, Tomas↗
DOE OSTI2019

Thermodynamic Studies on a Hydrogen Bonded Acidic (HBA) 3,5-bis(trifluoromethyl)phenol-Functionalized Polymer as a Gas Chromatography Stationary Phase for Selectively Speciating Chemical Warfare Agents

We used for the first time hydrogen bonded acidic (HBA) polymer, poly{methyl[3-(2-hydroxyl, 4,6-bistrifluoromethyl)phenyl]propylsiloxane } , (DKAP), as stationary phase for gas chromatography (GC) of chemical warfare agent (CWA) organophosphate (OP), surrogates, dimethylmethylphosphonate (DMMP), diisopropylmethylphosphonate (DIMP), diethylmethylphosphonate (DEMP), and trimethylphosphate (TMP), with high sensitivity and selectivity. Adsorption of OPs to DKAP was one-to-several orders of magnitude higher relative to commercial polar, mid-polar, and nonpolar stationary phases. We also performed for the first-time thermodynamic studies on the adsorption of OP vapors and obtained quantitative binding energy data for interactions with various stationary phases. These data help to identify the correct pair of hetero-polar columns for a two-dimensional system, employing nonpolar stationary phase as GC1, rejecting interfering molecules, and DKAP as GC2 stationary phase, for selective, sensitive, and rapid field detection of CWAs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Stability Study for Ultra-Dilute Chemical Warfare Agent Standards

Ultra-dilute (10 ppm) chemical warfare agent (CWA) standards are being supplied to the Environmental Response Laboratory Network (ERLN) laboratories to allow the use of authentic standards to assist in analyses required in the aftermath of a terrorist attack with CWAs. It is critical for the ERLN laboratories to be able to work with authentic CWA standards to allow the unambiguous identification and quantification of CWAs. The ultra dilute standards are synthesized in-house for use in analytical method development by the ERLN laboratories. However, data regarding the long-term stability of the ultra-dilute standards are lacking. For this reason, a study was undertaken to monitor the concentrations of CWAs in ultra-dilute standards as a function of time, under normal conditions of storage and use. The data collected in such a study could then be used to estimate reliable holding times for the ultra-dilute standards.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

How Quantum Sensing Will Help Solve GPS Denial in Warfare

The U.S. military’s ability to posture, deter, and prevail in future conflicts may rest on the quantum sensing position, navigation, and timing (PNT) capabilities that are currently being developed. Heavy reliance on GPS signals for PNT has become a critical vulnerability for the U.S. military. Meanwhile, the conflict in Ukraine has demonstrated that GPS denial and electronic warfare (EW) is now a key component of modern combat and satellite-guided munitions are reportedly being rendered ineffective. The Department of Defense (DOD) is focusing on upgrading GPS to use stronger, military-specific signals, which will still be vulnerable to EW and anti-satellite capabilities. A more diverse and resilient alternate-PNT strategy is needed to ensure mission success.

45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEF↗
NASA NTRS1988

Chemical warfare protection for the cockpit of future aircraft

Currently systems are being developed which will filter chemical and biological contaminants from crew station air. In order to maximize the benefits of these systems, a method of keeping the cockpit contaminant free during pilot ingress and egress is needed. One solution is to use a rectangular plastic curtain to seal the four edges of the canopy frame to the canopy sill. The curtain is stored in a tray which is recessed into the canopy sill and unfolds in accordion fashion as the canopy is raised. A two way zipper developed by Calspan could be used as an airlock between the pilot's oversuit and the cockpit. This system eliminates the pilot's need for heavy and restrictive CB gear because he would never be exposed to the chemical warfare environment.

Pickl, William C.↗
NASA NTRS1995

Application of Ni-63 photo and corona discharge ionization for the analysis of chemical warfare agents and toxic wastes

Over the past decade, advances in instrumental design and refinements in the understanding of ion molecule reactions at atmospheric pressure enabled the application of Ion Mobility Spectrometry (IMS) as a simple inexpensive and sensitive analytical method for the detection of organic trace compounds. Positive and negative gas-phase ions for ion mobility spectrometry have been produced by a variety of methods, including photo-ionization, laser multi photon ionization, surface ionization, corona discharge ionization. The most common ion source used in ion mobility spectrometry is a radioactive Ni-63 foil which is favored due to simplicity, stability, convenience, and high selectivity. If reactant ions like (H2O(n)H)(+) or (H2O(n)O2)(-) dominate in the reaction region, nearly all kinds of compounds with a given proton or electron affinity; are ionized. However, the radioactivity of the Ni-63 foil is one disadvantage of this ion source that stimulates the development and application of other ionization techniques. In this paper, we report analyses of old chemical warfare agents and toxic wastes using Bruker RAID ion mobility spectrometers. Due to the modular construction of the measuring cell, the spectrometers can be equipped with different ion sources. The combined use of Ni-63, photo- and corona discharge ionization allows the identification of different classes of chemical compounds and yields in most cases comparable results.

Stach, J.↗