The main cause of spacecraft failures is due to the harsh space environment; therefore, rigorous testing of materials used in modern spacecraft is imperative to ensure proper operation during the life span of the mission. Enhancing the capabilities of ground-based test facilities allows for more accurate measurements to be taken as it better simulates the environment to which spacecraft will be exposed. The range of temperature measurements has been significantly extended for an existing space environment simulation test chamber used in the study of electron emission, sample charging and discharge, electrostatic discharge and arcing, electron transport, and luminescence of spacecraft materials. This was accomplished by incorporating a new two-stage, closed-cycle helium cryostat, which has an extended sample temperature range from 450 K, with long-term controlled stability of -7Pa) that can simulate diverse space environments. These existing capabilities include controllable vacuum and ambient neutral gases conditions (< 10-7 to 10-1 Pa), electron fluxes (5 eV to 30 KeV monoenergetic, focused, pulsed sources ranging from 10-4 to 1010 nA-cm-2), ion fluxes (<0.1 to 5keV monoenergetic sources for inert and reactive gases with pulsing capabilities), and photon irradiation (numerous continuous and pulsed monochromatic and broadband IR/VIS/UV [0.5 to 7 eV] sources). The original sample mount accommodates one to four samples of 1 cm to 2.5 cm diameter in a low-temperature carousel, which allows rapid sample exchange and controlled exposure of the individual samples. Multiple additional sample mounts have been added to allow for standalone use for constant voltage measurements, radiation induced and conductivity tests, as well as extended capabilities for electron-induced luminescent measurements to be conducted using various material sample thickness in the original existing space environment simulation test chamber.

Clostridium sporogenes PA 3679 spores were inoculated into a meat-vegetable mixture before extrusion, cooking, and vacuum packaging into "stewsticks" to simulate Clostridium botulinum growth. The experiment was a 3 x 5 x 2 x 3 factorial which determined the influence of pH, water activity, initial spore load, and storage period on spore survival. Spore levels decreased throughout storage for all treatments. Spore levels decreased linearly (P = 0.02) as water activity increased, in samples that were heated to kill vegetative cells and activate spores. Other significant interactions of heat-treated samples were observed with inoculum level (P < 0.01) and storage time (P < 0.01). Spore levels in stored products were also significantly affected by water activity* inoculum level (P = 0.03), pH * time, water activity* time (P = 0.01), inoculum level * time (P < 0.01), and water activity * inoculum levels * time (P < 0.01). The interaction between pH * water activity * time tended towards significance (P = 0.06). Most probable number estimates in nonheated samples accounted for naturally occurring viable cells and spores, and added spores and were significantly affected by the main effects of inoculum level (P < 0.01) and time (P < 0.01). The two-way interactions of water activity * inoculum level (P = 0.04), pH * inoculum level (P < 0.01),water activity * time (P < 0.01), and three-way interaction of pH * inoculum level * time (P = 0.03) were significant. Spore levels approached 102, or less (compared to an inoculum level of 106 spores per gram) due to the effects of many treatments. Some stewstick packages were observed to become "gassy" or "loose" during storage. Subsequently the stewstick packages were used to isolate microorganisms that were able to grow at water activities of 0.96-0.86, in glycerol-adjusted Rogosa agar, and were acid tolerant to pH 4.4-4.2. One produced gas in pure culture, and some produced indole. These bacteria were not destroyed by heating to 74°C for at least 30 minutes, and lowered the pH in the stewstick during storage. In conclusion, in all stewstick samples, regardless of pH or Aw, inoculated clostridial spore levels decreased during storage, apparently because spores germinated and vegetative cells subsequently died. Thus, if stewsticks are cooked to 74°C throughout, have a Aw ≤ 0.86 and pH ≤ 4.8, they appear to be safe.

Developing a fundamental understanding of the interactions of chemical warfare agents (CWAs) with surfaces is essential for the rational design of new sorbents, sensors, and decontamination strategies. The interactions of chemical warfare agent simulants, molecules which retain many of the same chemical or physical properties of the agent without the toxic effects, with amorphous silica were conducted to investigate how small changes in chemical structure affect the overall chemistry. Experiments investigating the surface chemistry of two classes of CWAs, nerve and blister agents, were performed in ultrahigh vacuum to provide a well-characterized system in the absence of background gases. Transmission infrared spectroscopy and temperature-programmed desorption techniques were used to learn about the adsorption mechanism and to measure the activation energy for desorption for each of the simulant studied. In the organophosphate series, the simulants diisopropyl methylphosphonate (DIMP), dimethyl methylphosphonate (DMMP), trimethyl phosphate (TMP), dimethyl chlorophosphate (DMCP), and methyl dichlorophosphate (MDCP) were all observed to interact with the silica surface through the formation of a hydrogen bond between the phosphoryl oxygen of the simulant and an isolated hydroxyl group on the surface. In the limit of zero coverage, and after defect effects were excluded, the activation energies for desorption were measured to be 57.9 ± 1, 54.5 ± 0.3, 52.4 ± 0.6, 48.4 ± 1, and 43.0 ± 0.8 kJ/mol for DIMP. DMMP, TMP, DMCP, and MDCP respectively. The adsorption strength was linearly correlated to the magnitude of the frequency shift of the ν(SiO-H) mode upon simulant adsorption. The interaction strength was also linearly correlated to the calculated negative charge on the phosphoryl oxygen, which is affected by the combined inductive effects of the simulants' different substituents. From the structure-function relationship provided by the simulant studies, the CWA, Sarin is predicted to adsorb to isolated hydroxyl groups of the silica surface via the phosphoryl oxygen with a strength of 53 kJ/mol. The interactions of two common mustard simulants, 2-chloroethyl ethyl sulfide (2-CEES) and methyl salicylate (MeS), with amorphous silica were also studied. 2-CEES was observed to adsorb to form two different types of hydrogen bonds with isolated hydroxyl groups, one via the S moiety and another via the Cl moiety. The desorption energy depends strongly on the simulant coverage, suggesting that each 2-CEES adsorbate forms two hydrogen bonds. MeS interacts with the surface via a single hydrogen bond through either its hydroxyl or carbonyl functionality. While the simulant work has allowed us to make predictions agent-surface interactions, actual experiments with the live agents need to be conducted to fully understand this chemistry. To this end, a new surface science instrument specifically designed for agent-surface experiments has been developed, constructed, and tested. The instrument, located at Edgewood Chemical Biological Center, now makes it possible to make direct comparisons between simulants and agents that will aid in choosing which simulants best model live agent chemistry for a given system. These fundamental studies will also contribute to the development of new agent detection and decontamination strategies. / Ph. D.

Indiana University-Purdue University Indianapolis (IUPUI) / In forensic chemistry, a quicker and more accurate analysis of a sample is always being pursued. Speedy analyses allow the analyst to provide quick turn-around times and potentially decrease back-logs that are known to be a problem in the field. Accurate analyses are paramount with the futures and lives of the accused potentially on the line. One of the most common methods of analysis in forensic chemistry laboratories is gas chromatography, chosen for the relative speed and efficiency afforded by this method. Two major routes were attempted to further improve on gas chromatography applications in forensic chemistry. The first route was to decrease separation times for analysis of ignitable liquid residues by using micro-bore wall coated open-tubular columns. Micro-bore columns are much shorter and have higher separation efficiencies than the standard columns used in forensic chemistry, allowing for faster analysis times while maintaining the expected peak separation. Typical separation times for fire debris samples are between thirty minutes and one hour, the micro-bore columns were able to achieve equivalent performance in three minutes. The reduction in analysis time was demonstrated by analysis of ignitable liquid residues from simulated fire debris exemplars. The second route looked at a relatively new detector for gas chromatography known as a vacuum ultraviolet (VUV) spectrophotometer. The VUV detector uses traditional UV and far-ultraviolet light to probe the pi and sigma bonds of the gas phase analytes as well as Rydberg traditions to produce spectra that are nearly unique to a compound. Thus far, the only spectra that were not discernable were from enantiomers, otherwise even diastereomers have been differentiated. The specificity attained with the VUV detector has achieved differentiation of compounds that mass spectrometry, the most common detection method for chromatography in forensic chemistry labs, has difficulty distinguishing. This specificity has been demonstrated herein by analyzing various classes of drugs of abuse and applicability to “real world” samples has been demonstrated by analysis of de-identified seized samples.

<p>Analysis of explosives (intact and post-blast) is of interest to the forensic science community to qualitatively identify the explosive(s) in an improvised explosive device (IED). This requires high sensitivity, selectivity, and specificity. Forensic science laboratories typically utilize visual/microscopic exams, spectroscopic analysis (e.g., Fourier Transform Infrared Spectroscopy (FTIR)) and gas chromatography/mass spectrometry (GC/MS) for explosive analysis/identification. However, GC/MS has limitations for explosive analysis due to difficulty differentiating between structural isomers (e.g., 2,4-dinitrotoluene, 2,5-dinitrotoluene and 2,6-dinitrotoluene) and thermally labile compounds (e.g., ethylene glycol dinitrate (EGDN), nitroglycerine (NG) and pentaerythritol tetranitrate (PETN)) due to mass spectra with very similar fragmentation patterns. </p><p>The development of a benchtop vacuum ultraviolet spectrometer coupled to a gas chromatography (GC/VUV) was developed in 2014 with a wavelength region of 120 nm to 430 nm. GC/VUV can overcome limitations in differentiating explosive compounds that produces similar mass spectra. This work encompasses analysis of explosive compounds via GC/VUV to establish the sensitivity, selectivity, and specificity for the potential application for forensic explosive analysis. Nitrate ester and nitramine explosive compounds thermally decompose in the VUV flow cell resulting in higher specificity due to fine structure in the VUV spectra. These fine structures originate as vibronic and Rydberg transitions in the small decomposition compounds (nitric oxide, carbon monoxide, formaldehyde, water, and oxygen) and were analyzed computationally. The thermal decomposition process was further investigated for the determination of decomposition temperatures for the nitrate ester and nitramine compounds which range between 244 ºC and 277 ºC. Nitrated compounds were extensively investigated to understand the absorption characteristics of the nitro functional group in the VUV region. The nitro absorption maximum appeared over a wide range (170 - 270 nm) with the wavelength and intensity being highly dependent upon the structure of the rest of the molecule. Finally, the GC/VUV system was optimized for post-blast debris analysis. Parameters optimized include the final temperature of a ramped multimode inlet program (200 ºC), GC carrier gas flow rate (1.9 mL/min), and VUV make-up gas pressure (0.00 psi). The transfer line/flow cell temperature was determined not to be statistically significant.</p><br>

京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第20656号 / 理博第4321号 / 新制||理||1621(附属図書館) / 京都大学大学院理学研究科物理学・宇宙物理学専攻 / (主査)教授 佐々木 節, 教授 田中 貴浩, 教授 川合 光 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DFAM

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第20702号 / 工博第4399号 / 新制||工||1683(附属図書館) / 京都大学大学院工学研究科材料工学専攻 / (主査)教授 杉村 博之, 教授 河合 潤, 教授 邑瀬 邦明 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

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The objective of this project was to design, construct and test a wall climbing vehicle which uses a novel vacuum tread system for both adhesion and locomotion. The design and manufacturing of this proof of concept vehicle is detailed with particular emphasis on the design decisions that proved most impactful to the performance of both the vehicle and the tread system. Adhesion performance was characterized by a series of tests that validate the concept, but also identify improvements and design recommendations for future embodiments of the adhesion/locomotion system.

The inductively coupled plasma - mass spectrometer (ICP-MS) is the analytical instrument of choice for trace element detection and quantification. Despite the popularity of ICP-MS, significant degradation in sensitivity and precision occurs as the result of matrix and instrument-induced effects. The sources of these effects are not well understood, characterized, or correlated to particular plasma operating condition settings or matrix compositions and involve both neutral and charged species. The purpose of this study is to characterize the behavior of metastable Ar (I) atom and Ca (II) ion through the measurement of Doppler velocities and fluorescence line width "temperatures." For the characterization of Ar (I), axial and radial velocity and temperature profiles were collected as a function of nebulizer rate, incident ICP power and matrix composition to establish a behavioral baseline for neutral species in the first vacuum stage expansion of an ICP-MS. Velocities were determined from the Doppler shift of laser-induced Ar (I) fluorescence compared to stationary population wavelength reference. Unambiguous evidence of a thick Mach disk forming 10-12 mm downstream and persisting through 17-18 mm downstream, under standard ICP conditions, conflicts with the widely held view of a thin Mach disk located between 15-17 mm downstream. Characterization of Ca (II) ion focused on the effect of changing ICP conditions and matrix composition on calcium ion Doppler velocity and temperature profiles in the first vacuum stage expansion. Evidence of the plasma potential acceleration of ions through the interface was found as a higher Ca (II) terminal velocity than that of Ar (I) under standard ICP conditions. Additionally, the effect of a lithium matrix on Ca (II) velocity and temperature profiles was generally opposite than on Ar (I) velocity and temperature profiles.