The overall objective of this thesis is to evaluate the fundamentals of current low concentration CO2 separation technologies and to provide an alternate method using adsorption technology with existing as well as new adsorbents. Two different applications for the adsorption of CO2 are explored; Direct Air Capture (DAC) and excimer gas purification. The investigation of aerogels as possible adsorbent for these applications was also explored. The first application, DAC of CO2 using adsorbents, addresses climate change by reducing the amount of atmospheric CO2 levels that are directly correlated to global warming. Because of DAC being carbon negative, this field has gained significant attention in the literature. DAC as a CO2 reduction strategy was approached in two ways: 1. Chapter 2 investigates capturing and concentrating CO2 from 0.04% in the air to 95% to be able to sequester it into the ground. This research began by doing an adsorbent selection using pure gas gravimetric measurements on seven different commercially available type X zeolites that were determined to have potential for this separation. Breakthrough experiments were then carried out with the most promising zeolite by perturbing the bed with compressed ambient air. In the process studied, a basic four step temperature vacuum swing adsorption (TVSA) cycle was investigated comprising the following steps: pressurization, adsorption, blowdown, and desorption. Four different regeneration temperatures were tested along with four different gas space velocities. With this cycle configuration, CO2 was concentrated to 95% from 0.04% with total capture fractions as high as 81%. This study highlighted methods to reduce the energy consumption per ton of CO2 captured in the system as well as the potential of using low Si/Al ratio faujasite structured zeolites in DAC of CO2 for greenhouse gas reduction. 2. Chapter 3 expands on the research of Chapter 2 by capturing CO2 from 0.04% in the air and concentrating it to high purity CO2 levels where the cost for operating the process will be reimbursed through the value of the produced CO2. The goal of this research was to increase the CO2 to as high as possible because the purer the CO2, the more valuable it is. This research started by conducting an in-depth investigation into the pure gas adsorption of CO2, N2, O2, and Ar on the most promising zeolite from Chapter 2. The data was then fitted to the TD-Toth model which allowed for the evaluation of the TVSA cycle and showed the potential of reducing the pressure and/or elevating the temperature during the blowdown step in order to produce high purity CO2. To confirm this, the TVSA cycle was run on a fixed bed breakthrough experiment where high purity CO2 was produced between a concentration of 99.5% and 99.96% by lowering the blowdown pressure. By controlling the blowdown temperature, the concentration of the product was increased from 99.8% to 99.95%, however with a significant loss of CO2. This effect of N2, O2, and Ar desorbing during the blowdown step with CO2 desorbing during the evacuation step is shown graphically by measuring the concentration and flow rate of the exiting gas species. The results from this study show the potential for producing a valuable product of high purity CO2 from atmospheric concentrations. The second application in this thesis that is explored in Chapter 4 is the purification of trace impurities of CO2, CF4, COF2, and O2 from F2, Kr, and Ne for applications in excimer lasers. Due to the incompatibility of many adsorbents to F2 and HF, aluminas and polymeric adsorbents were selected as potentially compatible materials. To increase the compatibility of these adsorbents, the use of a cryo-cooler was determined to be feasible to precool the feed stream before separation, which increases the adsorption capacity and compatibility of the material to F2 and HF. To determine the adsorption potential in the low concentration of these adsorbents, the concentration pulse chromatographic technique was chosen to determine the Henry’s Law constants of CO2, CF4, and O2. This data was then plotted on the van’t Hoff plot and extrapolated to colder temperatures to determine the benefit of using a cryo-cooler. From this study, it was determined that HayeSep Q was the best polymeric adsorbent with significant adsorption of CO2 at temperatures below -50˚C while being the best performing CF4 adsorbent. AA-300 was the best performing alumina in this study while having significant adsorption of CF4 at temperatures below -135˚C. However, from a compatibility standpoint, both of these materials need to be tested to determine their robustness in the presence of F2 and HF at room and reduced temperatures. Chapters 5 & 6 in this thesis explore the fundamentals of adsorption on aerogels as a prelude to using aerogels as possible adsorbents for DAC of CO2. This investigation into aerogels looks at silica aerogels and carbon aerogels, which are both industrially produced and explores their adsorption with relation to like materials such as silica gel and activated carbons. Both of these Chapters utilize experimentally determined adsorption isotherms of CO2, N2, O2, and Ar as well as characterization to determine adsorption trends in the materials. Some major conclusions for silica aerogels were that common surface modifications to make the material more resilient against water adsorption impacts the adsorption of CO2 significantly with roughly 4 fold difference in adsorption capacity. For carbon aerogels some major conclusions were that the adsorption was increasingly dominated by the heterogeneous nature of the surface at lower pressures and increasingly dominated by the pore size at the higher pressures. Both chapters discuss the adsorption of air along with ideas such as the influence of gas thermal conductivity in the pores with respects to adsorption. L'objectif général de cette thèse est d'évaluer les principes fondamentaux des technologies actuelles de séparation du CO2 à faible concentration et de fournir une méthode alternative utilisant la technologie d’adsorption avec des adsorbants actuels ainsi que d'en découvrir de nouveaux. Deux applications différentes pour l'adsorption du CO2 ont été explorées; la capture directe dans l’air ambient (CAD) et la purification des gaz excimères, ainsi que la recherche d'aérogels comme adsorbant possible pour ces applications. La première application, le CAD du CO2 utilisant des adsorbants, pourrait répondre aux changements climatiques puisque les niveaux de CO2 atmosphérique sont directement corrélés au réchauffement climatique. Dernièrement, le CAD a fait l'objet d'une attention particulière en tant que stratégie de réduction du CO2, par conséquent, deux voies différentes ont été explorées dans cette thèse: 1. Le chapitre 2 étudie la capture et la concentration du CO2 de 0,04% dans l'air à 95% afin de pouvoir l’enfermer dans la terre. Pour ce faire, une sélection d'adsorbant a été effectué en utilisant des mesures gravimétriques à gaz pur sur sept zéolithes de type X disponibles dans le commerce qui ont été déterminés comme ayant un potentiel pour cette séparation. Des expériences révolutionnaires ont ensuite été réalisées avec la zéolite la plus prometteuse en perturbant le lit avec de l'air ambiant comprimé. Dans le processus étudié, un cycle basique à quatre étapes d’adsorption modulée en température et pression (AMTP) a été étudié, comprenant les étapes suivantes: pressurisation, adsorption, purge et désorption. Quatre températures de régénération différentes ont été testées ainsi que quatre vitesses spatiales de gaz différents. Avec cette configuration de cycle, le CO2 était concentré à 95% de 0,04% avec des fractions de capture totales aussi élevées que 81%. Cette étude a mis en évidence des méthodes pour réduire la consommation d'énergie par tonne de CO2 captée dans le système ainsi que le potentiel d'utilisation de zéolithes structurées à base de faujasite à faible rapport Si/Al dans le CAD du CO2 pour la réduction des gaz à effet de serre. 2. Le chapitre 3 approfondit les recherches du chapitre 2 en capturant le CO2 de 0,04% dans l'air et en le concentrant à des niveaux de très haute pureté où le processus sera remboursé par la valeur du CO2 produit. L'objectif de cette partie était d'augmenter la pureté du CO2 le plus possible car plus le CO2 est pur, plus il est précieux. Une enquête approfondie sur l'adsorption de gaz pur de CO2, N2, O2 et Ar sur la zéolite la plus prometteuse du chapitre 2. Les données ont ensuite été ajustées au modèle TD-Toth qui a permis d'évaluer le cycle AMTP et a montré le potentiel de réduire la pression et/ou d'élever la température pendant l'étape de purge afin de produire du CO2 de haute pureté. Pour confirmer cela, le cycle AMTP a été fait par le biais d’une expérience dans un lit fixe où du CO2 de haute pureté a été produit entre une concentration de 99,5% et 99,96% en abaissant la pression de purge. En contrôlant la température de purge, la concentration du produit est passée de 99,8% à 99,95%, mais avec une perte importante de CO2. Cet effet de la désorption de N2, O2 et Ar pendant l'étape de purge avec la désorption du CO2 pendant l'étape d'évacuation est illustré graphiquement en mesurant la concentration et le débit des espèces de gaz sortant. Les résultats de cette étude montrent le potentiel de production d'un produit précieux de CO2 de haute pureté à partir des concentrations atmosphériques. La deuxième application de cette thèse qui est explorée au Chapitre 4 est la purification des traces d'impuretés de CO2, CF4, COF2 et O2 de F2, Kr et Ne pour des applications dans les lasers à excimère. En raison de l'incompatibilité de nombreux adsorbants avec le F2 et le HF, les alumines et les adsorbants polymères ont été sélectionnés comme matériaux potentiellement compatibles. Pour augmenter la compatibilité de ces adsorbants, l'utilisation d'un cryoréfrigérant a été jugée possible pour pré-refroidir le flux d'alimentation avant la séparation, ce qui augmente la capacité d'adsorption et la compatibilité du matériau en F2 et HF. Pour déterminer le potentiel d'adsorption dans la faible concentration de ces adsorbants, la technique de chromatographie pulsée de concentration a été choisie pour déterminer les constantes de la loi de Henry de CO2, CF4 et O2. Ces données ont ensuite été tracées sur le graphique van’t Hoff et extrapolées à des températures plus froides pour déterminer les avantages de l’utilisation d’un cryoréfrigérant. À partir de cette étude, il a été déterminé que HayeSep Q était le meilleur adsorbant polymère avec une adsorption significative de CO2 à des températures inférieures à -50 ° C tout en étant l'adsorbant CF4 le plus performant. L'AA-300 était l'alumine la plus performante de cette étude tout en ayant une adsorption significative de CF4 à des températures inférieures à -135 °C. Cependant, du point de vue de la compatibilité, ces deux matériaux doivent être testés pour déterminer leur robustesse en présence de F2 et de HF à température ambiante et réduite. Les chapitres 5 et 6 explorent les principes fondamentaux de l'adsorption sur les aérogels en prélude à l'utilisation d'aérogels comme adsorbants possibles pour le CAD du CO2. Cette enquête sur les aérogels examine les aérogels de silice et les aérogels de carbone, qui sont tous les deux fabriqués industriellement et explore leur adsorption par rapport à des matériaux similaires tels que le gel de silice et les charbons actifs. Ces deux chapitres utilisent des isothermes d'adsorption déterminés expérimentalement de CO2, N2, O2 et Ar ainsi que la caractérisation pour déterminer les tendances d'adsorption dans les matériaux. Certaines conclusions majeures pour les aérogels de silice étaient que les modifications de surface courantes pour rendre le matériau plus résistant à l'adsorption d'eau ont un impact significatif sur l'adsorption de CO2 avec une différence d'environ 4 fois dans la capacité d'adsorption. Pour les aérogels de carbone, certaines conclusions majeures étaient que l'adsorption était de plus en plus dominée par la nature hétérogène de la surface à des pressions plus faibles et de plus en plus dominée par la taille des pores aux pressions plus élevées. Les deux chapitres discutent de l'adsorption d'air ainsi que des idées telles que l'influence de la conductivité thermique du gaz dans les pores en ce qui concerne l'adsorption.

Indiana University-Purdue University Indianapolis (IUPUI) / With bombings in the United States on the rise for the first time since 2016, the detection and identification of explosives remains of pertinent interest to law enforcement agencies. This work presents two soon-to-be published research articles that focus on the detection and identification of explosives by both chemical instrumentation and canines. The first article, Quantitative Analysis of Smokeless Powder Particles in Post-Blast Debris via Gas Chromatography/Vacuum Ultraviolet Spectroscopy (GC/VUV), utilizes gas chromatography/vacuum ultraviolet spectroscopy (GC/VUV) to determine the difference in chemical composition of two smokeless powders in both pre- and post-blast conditions. The compounds of interest in this study were nitroglycerin, 2,4- dinitrotoluene, diphenylamine, ethyl centralite, and di-n-butyl phthalate. Concentration changes between pre- and post-blast smokeless powder particles were determined as well as microscopic differences between pre- and post-blast debris for both smokeless powders in all devices. To our knowledge, this is the first use of GC/VUV for the quantification of explosives. The second article, An Odor-Permeable Membrane Device for the Storage of Canine Training Aids, proposes the use of an odor-permeable membrane device (OPMD) as a standardized storage method for canine training aids. It is hypothesized that the OPMD would minimize cross-contamination between training aids, and that the OPMD could be used for canine training as well as storage. The goal of this research is to use flux and evaporation rate to quantify the explosive odor that escapes from the OPMD compared to unconfined explosives. Preliminary data suggests that there is an exponential relationship between relative boiling point and evaporation rate. It has been determined that compounds with higher boiling points have lower evaporation rates than compounds that have lower boiling points. The materials studied thus far are known odor compounds produced by explosive formulations. These include nitromethane, nitroethane, 1- nitropropane, r-limonene, and toluene.

The diagnostic technique, polarization and depolarization current (PDC) is useful for insulation testing. It requires applying a DC step voltage to the test sample and measuring the current. To measure fast PDC phenomena a fast step is needed. One way of applying a fast high voltage step is to use power electronic switches. Series connection can be used to increase the voltage limit, but this result in unequal voltage sharing unless equipped with voltage balancing. In this work a high voltage vacuum reed switch is investigated as a simple and low-cost alternative to power electronic switches, handling up to 10 kV with a single device. The switch turn on and off behavior was studied. It was found that the initial turn-on is good, in the range of nanoseconds, but there is a problem with the vacuum recovering its insulating properties at low currents before the contacts fully close. The required output voltage level is therefore obtained only after a further settling time that increases with increased input voltage and is much longer than the initial breakdown, e.g. 20 µs for the case of 4.5 kV input voltage. Other limitations of the fast high voltage PDC were also studied. The output voltage was measured across the test sample without adding an intentional resistor in the circuit. There were large oscillations for 1 µs but these oscillations are damped due to inherent resistance of the connecting leads, series resistance of the capacitors and resistance of the reed switch. A comparison is made between the measured and the simulated results using MATLAB to see the effect of parasitic inductance. A damping resistor was added in the circuit and the output results were again compared. With the addition of the damping resistor, the number of oscillations were reduced and their time scale was limited to 0.1 µs . An analysis is made at the end which describes the limitation occurring in determining the high frequency component of PDC. The current during the step is many orders of magnitude higher than the polarization current even at 1 µs , so measurement of the current and protection of the apparatus is not trivial.

Indiana University-Purdue University Indianapolis (IUPUI) / In the area of forensic chemistry, improved or new analysis methods are continually being investigated. One common and powerful technique used in forensic chemistry is wall-coated open-tubular column (WCOT) gas chromatography with electron ionization single quadrupole mass spectrometry (GC-MS). Improvements to and effectiveness of alternatives to this instrumental platform were explored in an array of parallel inquiries. The areas studied included the column for the chromatographic separation, the universal detection method employed, and the fragmentation method used to enhance molecular identification. Superfine-micropacked capillary (SFµPC) columns may provide an alternative to commercial packed GC columns and WCOT GC columns that combines the benefits of the larger sample capacity of packed columns and the benefits of the excellent separation capabilities and mass spectrometry (MS) flow rate compatibility of WCOT columns. SFµPC columns suffer from high inlet pressure requirements and prior reported work has required specialized instrumentation for their use. Fabrication of and chromatography with SFµPC GC columns was successfully achieved with typical GC-MS instrumentation and within the flow rate limit of a MS. Additionally, the use of higher viscosity carrier gasses was demonstrated to reduce the required inlet pressure for SFµPC GC columns. Recently, a new vacuum ultraviolet spectrometer (VUV) universal detector has been commercialized for GC. The ability of VUV detectors to acquire absorbance spectra from 125 nm to 430 nm poses a potential alternative to MS. As such, GC-VUV provides an exciting potential alternative approach to achieving excellent quantitative and qualitative analysis across a wide range of analytes. The performance of VUV and MS detectors for forensic analysis in terms of quantitative and qualitative analysis was compared. Analysis of alkylbenzenes in ignitable liquids was explored, which can be important evidence from suspected arson fires and are difficult to differentiate with MS. The VUV detector was found to have superior specificity and comparable sensitivity to the MS detector in scan mode. Addition of thermolysis (Th) as an orthogonal fragmentation pathway provides the opportunity to increase the differences between MS fragmentation patterns. Fragmentation has been widely established to aid in identification of molecules with MS by providing characteristic fragments at characteristic relative abundances. However, molecules with very similar structures do not result in sizable spectral differences in all cases with typical MS fragmentation techniques. A series of Th units were fabricated and integrated into GC-Th-MS instruments. Th-MS was conducted with the thermally labile nitrate esters across a range of instrumentation and thermal conditions.

Haemolysis and other biochemical evaluations of vacuum-assisted venous drainage in cardiac surgery Aims of the study: Vacuum-assisted venous drainage (VAVD) improves the quality of venous return in procedures using extracorporeal circulation systems (ECC). Nevertheless, there is not an evidence that such high negative pressure applied to ECC in combination with selective bicaval cannulation due to open heart surgery cause a trauma to blood elements and deteriorates organ function. A prospective randomised study was designed to demonstrate that negative pressure of -20 mm Hg to -80 mm Hg does not cause a significant haemolysis and organ deterioration in such procedures. Materials and methods: 85 consecutive patients undergoing combined cardiac surgery procedure with two separate venous cannulas were randomised in three groups A, B and C. VAVD with negative pressure of -20 to -45 mm Hg was applied to 28 patients in group A and negative pressure of -45 mm Hg to -80 mmHg was applied to 28 patients in group B. There was zero negative pressure applied to 29 patients in group C. Six blood samples were taken from each patient and examinated for haemolysis and other indicators of organ deterioration such as hemoblobin, platelet count, free hemoglobin, aptoglobin, lactate-dehydrogenase, aspartate-amino-transferase,...

The optimisation of the specular reflectance of solar collectors is a key parameter to increase the global yield of concentrated solar power (CSP) plants. In this work, the influence of filtered cathodic vacuum arc deposition parameters, particularly working pressure and deposition time, on the specular and diffuse reflectance of aluminium thin films, was studied. Changes in specular reflectance, measured by ultraviolet–visible and near-infrared spectroscopy (UV-vis-NIR) spectrophotometry, were directly correlated with thin film elemental concentration depth profiles, obtained by Rutherford backscattering spectrometry (RBS), and surface and cross-sectional morphologies as measured by scanning electron microscopy (SEM) and profilometry. Finally, atomic force microscopy (AFM) provided information on the roughness and growth mechanism of the films. The two contributions to the total reflectance of the films, namely diffuse and specular reflectance, were found to be deeply influenced by deposition conditions. It was proven that working pressure and deposition time directly determine the predominant factor. Specular reflectance varied from 12 to 99.8% of the total reflectance for films grown at the same working pressure of 0.1 Pa and with different deposition times. This transformation could not be attributed to an oxidation of the films as stated by RBS, but was correlated with a progressive modification of the roughness, surface, and bulk morphology of the samples over the deposition time. Hence, the evolution in the final optical properties of the films is driven by different growth mechanisms and the resulting microstructures. In addition to the originally addressed CSP applications the potential of the developed aluminium films for other application rather than CSP, such as, for example, reference material for spectroscopic diffuse reflectance measurements, is also discussed.

The purpose of this study was to examine the clinical outcomes of negative pressure wound therapy (NPWT) using reticulated open-cell foam (ROCF) in the adjunctive management of abdominal wounds with exposed and known infected synthetic mesh. A non randomised, retrospective review of medical records for 21 consecutive patients with infected abdominal wounds treated with NPWT was conducted. All abdominal wounds contained exposed synthetic mesh [composite, polypropylene (PP), or knitted polyglactin 910 (PG) mesh]. Demographic and bacteriological data, wound history, pre-NPWT and comparative post-NPWT, operative procedures and complications, hospital length of stay (LOS) and wound healing outcomes were all analysed. Primary endpoints measured were (1) hospital LOS prior to initiation of NPWT, (2) total time on NPWT, (3) hospital LOS from NPWT initiation to discharge and (4) wound closure status at discharge. A total of 21 patients with abdominal wounds with exposed, infected mesh were treated with NPWT. Aetiology of the wounds was ventral hernia repair (n = 11) and acute abdominal wall defect (n = 10). Prior to NPWT initiation, the mean hospital LOS for the composite, PP and PG meshes were 76 days (range: 21-171 days), 51 days (range: 32-62 days) and 19 days (range: 12-39 days), respectively. The mean hospital LOS following initiation of NPWT for wounds with exposed composite, PP and PG mesh were 28, 31 and 32 days, respectively. Eighteen of the 21 wounds (86%) reached full closure after a mean time of 26 days of NPWT and a mean hospital LOS of 30 days postinitiation of NPWT. Three wounds, all with composite mesh left in situ, did not reach full closure, although all exhibited decreased wound dimensions, granulating beds and decreased surface area exposure of mesh. During NPWT/ROCF, one hypoalbuminemic patient with exposed PP mesh developed an enterocutaneous fistula over a prior enterotomy site. This patient subsequently underwent total mesh extraction, takedown of the fistula and PP mesh replacement followed by reinstitution of NPWT and flap closure. In addition to appropriate systemic antibiotics and nutritional optimisation, the adjunctive use of NPWT resulted in successful closure of 86% of infected abdominal wounds with exposed prosthetic mesh. Patient hospital LOS (except those with PG mesh), operative procedures and readmissions were decreased during NPWT compared with treatment prior to NPWT. Future multi-site prospective, controlled studies would provide a strong evidence base from which treatment decisions could be made in the management of these challenging and costly cases.

Gabriel A, Shores J, Bernstein B, de Leon J, Kamepalli R, Wolvos T, Baharestani MM, Gupta S. A Clinical Review of Infected Wound Treatment with Vacuum Assisted Closure ® (V.A.C. ®) Therapy: Experience and Case Series. ABSTRACT Over the last decade Vacuum Assisted Closure ® (KCI Licensing, Inc., San Antonio, TX) has been established as an effective wound care modality for managing complex acute and chronic wounds. The therapy has been widely adopted by many institutions to treat a variety of wound types. Increasingly, the therapy is being used to manage infected and critically colonized, difficult-to-treat wounds. This growing interest coupled with practitioner uncertainty in using the therapy in the presence of infection prompted the convening of an interprofessional expert advisory panel to determine appropriate use of the different modalities of negative pressure wound therapy (NPWT) as delivered by V.A.C. ® Therapy and V.A.C. Instill ® with either GranuFoam ™ or GranuFoam Silver ™ Dressings. The panel reviewed infected wound treatment methods within the context of evidence-based medicine coupled with experiential insight using V.A.C. ® Therapy Systems to manage a variety of infected wounds. The primary objectives of the panel were 1) to exchange state-of-practice evidence, 2) to review and evaluate the strength of existing data, and 3) to develop practice recommendations based on published evidence and clinical experience regarding use of the V.A.C. ® Therapy Systems in infected wounds. These recommendations are meant to identify which infected wounds will benefit from the most appropriate V.A.C. ® Therapy System modality and provide an infected wound treatment algorithm that may lead to a better understanding of optimal treatment strategies.

The need to minimize carbon dioxide (CO2) emissions is becoming increasingly important with the total number of vehicles throughout the world exceeding one billion. Carbon dioxide emissions can be reduced by improving vehicle fuel efficiency. While electric transportation is gaining popularity, most passenger vehicles are still powered by gasoline or diesel engines. The main objective of this work was to provide opportunities for studying and improving the fuel efficiency of internal combustion engines (ICE). This was achieved by 1) Designing, building and testing auxiliary systems necessary to run a Cummins 2.8 L engine in a an engine test cell; 2) Creating educational labs for the ICE class; and 3) Measuring the parasitic losses of the vacuum pump and water pump on the installed Cummins 2.8 L diesel engine. All auxiliary systems were completed at a hardware cost of $8100 and are rated to support an engine with the power output capacity of 233 kW (312 hp). The educational laboratories enable future engineers to measure and assess the efficiency of internal combustions engines. The parasitic losses of the vacuum pump and water pump were found to impact the relative brake fuel conversion efficiency by 1.3% and 1.5% respectively over the Federal Test Procedure (FTP) cycle.

This classic grounded theory study reflects companies work with corporate philanthropy (CP), and has a specific focus on companies with Swedish roots who are operating in South Africa. The theory illustrates how the companies perceive themselves to be forced to engage in CP, and their main solution to this problem is trying to optimise their CP work so it benefits both themselves and their beneficiaries. The companies are operating in a structural vacuum with regards to their CP work, and consequently, they make use of impressionistic tools in their attempt to optimise the work. There is arguably a need for companies to adopt a more strategic approach. The empirical data is collected from semi structured interviews with companies during 2012.