The Detection of Iridium Using Laser-Induced Breakdown Spectroscopy

Although one thinks of a thruster as utilizing both a fuel and an oxidizer, as well as an ignition source to release molecular energy, thrusters exist that combine the fuel and oxidizer in a single fluid. These monopropellant thrusters can utilize either an ignition source or a catalyst to release the molecular energy stored within the propellant. Monopropellant thrusters are especially attractive for space flight systems because they only require a single propellant line which reduces systems weight and complexity. Some monopropellant thrusters, including legacy hydrazine thrusters, and newer thrusters using hydrazine replacements, that utilize a heterogeneous catalyst have experienced performance anomalies due to the degradation of the catalyst bed. At the Air Force Research Laboratory, current state-of-health diagnostic techniques ate being developed to better understand this catalyst bed degradation for the new hydrazine replacement monopropellant, AF-M315E. Laser-induced Breakdown Spectroscopy (LIBS) is being used to detect and quantify active catalyst materials in the exhaust plume, such as iridium. Previous work has been unsuccessful in detecting iridium. However, by shortening the delay settings on the camera detector, the spectrometer used in LIBS will be able to pick up more of the emissions from the laser-ablated sample, leading to the detection of iridium. DISTRIBUTION A: Approved for public release: distribution unlimited

Report on New Capabilities for the Purple Development Environment

As part of the deliverables for the Development Environment for Purple, additional capabilities to improve the tools offerings and to address unique Purple system requirements, such as increased processor count, were expected. This report details some of the new capabilities that have been incorporated into the development environment tools for Purple. The shift on Purple to 64-bit applications (from 32-bit on White) initially broke many debugging and memory tools. Most tools were updated to support 64 bit well before Purple was delivered to LLNL, but the company that provided the popular heavy-weight 32-bit AIX memory tool, ZeroFault, was reluctant to port to 64 bit due to perceived lack of market. LLNL tried offering financial incentives to the ZeroFault developers, which were turned down, but eventually they did give vague promises to try to port to AIX 64-bit mode when they got time. The ZeroFault developers have been making intermittent and very slow progress over the last two plus years, but despite getting close, have not released a version of ZeroFault that yet meets our needs for 64-bit applications. However, given the critical need for memory tools and the uncertainty of ZeroFault development, other memory tool options were actively pursued and delivered

Report on Challenges and Resolutions for the Purple Development Environment

Previous AIX development environment experience with ASC White and Early Delivery systems UV and UM was leveraged to provide a smooth and robust transition to the Purple development environment. Still, there were three major changes that initially caused serious problems for Purple users. The first was making 64-bit builds of executables the default instead of 32-bit. The second was requiring all executables to use large page memory. The third was the phase-out of the popular, but now defunct, third-party C++ compiler KCC, which required the migration of many codes to IBM's xlC C++ compiler. On Purple, the default build environment changed from 32-bit builds to 64-bit builds in order to enable executables to use the 4GB per processor (32GB per node) memory available, and in order for the MPI library to do collective optimizations that required the larger 64-bit address space. The 64-bit build environment was made default by setting the IBM environment variable OBJECT{_}MODE to 64 and wrapping third-party software (mainly the gnu compilers) in order to make them handle OBJECT{_}MODE properly. Because not all applications could port to 64-bit right away, (usually due to third-party constraints, such as python not supporting 64-bit AIX builds until very recently), 32-bit builds of the major common third-party libraries also had be supported. This combined 32/64 bit build support was accomplished fairly seamlessly using the AIX feature that allows both 32-bit and 64-bit versions of the code to appear in the same library file, and documentation with clear examples helped our library developers generate the required combined 32-bit and 64-bit libraries for Purple. In general, the port to 64-bit AIX executables went smoothly. The most common problem encountered with 64-bit was that many C codes didn't prototype malloc everywhere, via ''include <stdlib.h>'', which caused invalid pointers to be returned by unprototyped malloc calls. This was usually seen in old crusty C libraries, leading to segfault on first use of the invalid pointer. Users had not encountered this prototype issue on other 64-bit Operating Systems (Tru64 and SUN) because those vendors worked around this issue by ''auto-prototyping'' malloc for the user. IBM instead required a compiler option to be thrown for autoprototyping. This issue was resolved with user education, and often a quick recognition of the symptoms by support personnel. This addresses a requirement for a report on problems encountered with the tools and environment, and the resolution or status

Heats of vaporization of room temperature ionic liquids by tunable vacuum ultraviolet photoionization

The heats of vaporization of the room temperature ionic liquids (RTILs) N-butyl-N-methylpyrrolidinium bistrifluorosulfonylimide, N-butyl-N-methylpyrrolidinium dicyanamide, and 1-butyl-3-methylimidazolium dicyanamide are determined using a heated effusive vapor source in conjunction with single photon ionization by a tunable vacuum ultraviolet synchrotron source. The relative gas phase ionic liquid vapor densities in the effusive beam are monitored by clearly distinguished dissociative photoionization processes via a time-of-flight mass spectrometer at a tunable vacuum ultraviolet beamline 9.0.2.3 (Chemical Dynamics Beamline) at the Advanced Light Source synchrotron facility. Resulting in relatively few assumptions, through the analysis of both parent cations and fragment cations, the heat of vaporization of N-butyl-N-methylpyrrolidinium bistrifluorosulfonylimide is determined to be Delta Hvap(298.15 K) = 195+-19 kJ mol-1. The observed heats of vaporization of 1-butyl-3-methylimidazolium dicyanamide (Delta Hvap(298.15 K) = 174+-12 kJ mol-1) and N-butyl-N-methylpyrrolidinium dicyanamide (Delta Hvap(298.15 K) = 171+-12 kJ mol-1) are consistent with reported experimental values using electron impact ionization. The tunable vacuum ultraviolet source has enabled accurate measurement of photoion appearance energies. These appearance energies are in good agreement with MP2 calculations for dissociative photoionization of the ion pair. These experimental heats of vaporization, photoion appearance energies, and ab initio calculations corroborate vaporization of these RTILs as intact cation-anion ion pairs

Isoconversional kinetic analysis applied to five phosphoniumcation-based ionic liquids

Thermal degradation of five phosphonium cation-based ionic liquids ([P66614][BEHP], [P66614][(iC8)2PO2],[P66614][NTf2], [P44414][DBS] and [P4442][DEP]) was studied using dynamic methodology (25–600◦C at 5,10 and 20◦C/min) in both inert (nitrogen) and reactive (oxygen) atmospheres. In addition, isothermalexperiments (90 min at 200, 225 and 250◦C) were carried out with [P66614][(iC8)2PO2]. Results indicatethat thermal stability is clearly dominated by the coordination ability of the anion, with [P66614][NTf2] out-performing the other ones in both pyrolytic and oxidising conditions. Although the thermal degradationmechanism is affected by atmospheric conditions, the degradation trend remains practically constant.As the dynamic methodology usually overestimates the long-term thermal stability, an isoconversionalmethodology is better for predicting the long-term thermal stability of these ionic liquids in order to beused as base oil or additive in lubricants formulation. Finally, the model-free methodology can predict atlower costs the ILs performance in isothermal conditions

Soft Ionization of Thermally Evaporated Hypergolic Ionic Liquid Aerosols

Isolated ion pairs of a conventional ionic liquid, 1-Ethyl-3-Methyl-Imidazolium Bis(trifluoromethylsulfonyl)imide ([Emim+][Tf2N?]), and a reactive hypergolic ionic liquid, 1-Butyl-3-Methyl-Imidazolium Dicyanamide ([Bmim+][Dca?]), are generated by vaporizing ionic liquid submicron aerosol particles for the first time; the vaporized species are investigated by dissociative ionization with tunable vacuum ultraviolet (VUV) light, exhibiting clear intact cations, Emim+ and Bmim+, presumably originating from intact ion pairs. Mass spectra of ion pair vapor from an effusive source of the hypergolic ionic liquid show substantial reactive decomposition due to the internal energy of the molecules emanating from the source. Photoionization efficiency curves in the near threshold ionization region of isolated ion pairs of [Emim+][Tf2N?]ionic liquid vapor are compared for an aerosol source and an effusive source, revealing changes in the appearance energy due to the amount of internal energy in the ion pairs. The aerosol source has a shift to higher threshold energy (~;;0.3 eV), attributed to reduced internal energy of the isolated ion pairs. The method of ionic liquid submicron aerosol particle vaporization, for reactive ionic liquids such as hypergolic species, is a convenient, thermally ?cooler? source of isolated intact ion pairs in the gas phase compared to effusive sources

Heats of vaporization of room temperature ionic liquids by tunable vacuum ultraviolet photoionization

The heats of vaporization of the room temperature ionic liquids (RTILs) N-butyl-N-methylpyrrolidinium bistrifluorosulfonylimide, N-butyl-N-methylpyrrolidinium dicyanamide, and 1-butyl-3-methylimidazolium dicyanamide are determined using a heated effusive vapor source in conjunction with single photon ionization by a tunable vacuum ultraviolet synchrotron source. The relative gas phase ionic liquid vapor densities in the effusive beam are monitored by clearly distinguished dissociative photoionization processes via a time-of-flight mass spectrometer at a tunable vacuum ultraviolet beamline 9.0.2.3 (Chemical Dynamics Beamline) at the Advanced Light Source synchrotron facility. Resulting in relatively few assumptions, through the analysis of both parent cations and fragment cations, the heat of vaporization of N-butyl-N-methylpyrrolidinium bistrifluorosulfonylimide is determined to be Delta Hvap(298.15 K) = 195+-19 kJ mol-1. The observed heats of vaporization of 1-butyl-3-methylimidazolium dicyanamide (Delta Hvap(298.15 K) = 174+-12 kJ mol-1) and N-butyl-N-methylpyrrolidinium dicyanamide (Delta Hvap(298.15 K) = 171+-12 kJ mol-1) are consistent with reported experimental values using electron impact ionization. The tunable vacuum ultraviolet source has enabled accurate measurement of photoion appearance energies. These appearance energies are in good agreement with MP2 calculations for dissociative photoionization of the ion pair. These experimental heats of vaporization, photoion appearance energies, and ab initio calculations corroborate vaporization of these RTILs as intact cation-anion ion pairs