Temperature measurements, gas chemistry, and gas hydrates of the Dvurechenskii mud volcano

The sediment temperature distribution at mud volcanoes provides insights into their activity and into the occurrence of gas hydrates. If ambient pressure and temperature conditions are close to the limits of the gas hydrate stability field, the sediment temperature distribution not only limits the occurrence of gas hydrates, but is itself influenced by heat production and consumption related to the formation and dissociation of gas hydrates. Located in the Sorokin Trough in the northern Black Sea, the Dvurechenskii mud volcano (DMV) was in the focus of detailed investigations during the M72/2 and M73/3a cruises of the German R/V Meteor and the ROV Quest 4000 m in February and March 2007. A large number of in-situ sediment temperature measurements were conducted from the ROV and with a sensor-equipped gravity corer. Gas hydrates were sampled in pressurized cores using a dynamic autoclave piston corer (DAPC). The thermal structure of the DMV suggests a regime of fluid flow at rates decreasing from the summit towards the edges of the mud volcano, accompanied by intermittent mud expulsion at the summit. Modeled gas hydrate dissociation temperatures reveal that the gas hydrates at the DMV are very close to the stability limits. Changes in heat flow due to variable seepage rates probably do not result in changes in sediment temperature but are compensated by gas hydrate dissociation and formation.

Design and Experimental Investigation of a Hydroxyl Ammonium Nitrate Based Workhorse Microthruster

Thesis (Master's)--University of Washington, 2016-08

Wysokociśnieniowe przemiany strukturalne kryształów węglowodanów

Wydział Chemii

Study of ammonia borane and its derivatives: Influence of nanoconfinements and pressures

Recently, ammonia borane has increasingly attracted researchers’ attention because of its merging applications, such as organic synthesis, boron nitride compounds synthesis, and hydrogen storage. This dissertation presents the results from several studies related to ammonia borane. ^ The pressure-induced tetragonal to orthorhombic phase transition in ammonia borane was studied in a diamond anvil cell using in situ Raman spectroscopy. We found a positive Clapeyron-slope for this phase transformation in the experiment, which implies that the phase transition from tetragonal to orthorhombic is exothermic. The result of this study indicates that the rehydrogenation of the high pressure orthorhombic phase is expected to be easier than that of the ambient pressure tetragonal phase due to its lower enthalpy. ^ The high pressure behavior of ammonia borane after thermal decomposition was studied by in situ Raman spectroscopy at high pressures up to 10 GPa. The sample of ammonia borane was first decomposed at ∼140 degree Celcius and ∼0.7 GPa and then compessed step wise in an isolated sample chamber of a diamond anvil cell for Raman spectroscopy measurement. We did not observe the characteristic shift of Raman mode under high pressure due to dihydrogen bonding, indicating that the dihydrogen bonding disappears in the decomposed ammonia borane. Although no chemical rehydrogenation was detected in this study, the decomposed ammonia borane could store extra hydrogen by physical absorption. ^ The effect of nanoconfinement on ammonia borane at high pressures and different temperatures was studied. Ammonia borane was mixed with a type of mesoporous silica, SBA-15, and restricted within a small space of nanometer scale. The nano-scale ammonia borane was decomposed at ∼125 degree Celcius in a diamond anvil cell and rehydrogenated after applying high pressures up to ∼13 GPa at room temperature. The successful rehydrogenation of decomposed nano-scale ammonia borane gives guidance to further investigations on hydrogen storage. ^ In addition, the high pressure behavior of lithium amidoborane, one derivative of ammonia borane, was studied at different temperatures. Lithium amidoborane (LAB) was decomposed and recompressed in a diamond anvil cell. After applying high pressures on the decomposed lithium amidoborane, its recovery peaks were discovered by Raman spectroscopy. This result suggests that the decomposition of LAB is reversible at high pressures.^

Effects of solid poly (ethylene glycols) addition to the solutions of aniline or N,N-dimethylaniline with water:experimental measurements and modelling

In this work, the liquid-liquid and solid-liquid phase behaviour of ten aqueous pseudo-binary and three binary systems containing polyethylene glycol (PEG) 2050, polyethylene glycol 35000, aniline, N,N-dimethylaniline and water, in the temperature range 298.15-350.15 K and at ambient pressure of 0.1 MPa, was studied. The obtained temperature-composition phase diagrams showed that the only functional co-solvent was PEG2050 for aniline in water, while PEG35000 even showed a clear anti-solvent effect in the N,N-dimethylaniline aqueous system. The experimental solid-liquid equilibria (SLE) data have been correlated by the non-random two-liquid (NRTL) model, and the correlation results are in accordance with the experimental results.

Freeze-drying of ovalbumin loaded mesoporous silica nanoparticle vaccine formulation increases antigen stability under ambient conditions

Amino functionalised mesoporous silica nanoparticles (AM-41) have been identified as a promising vaccine delivery material. The capacity of AM-41 to stabilise vaccine components at ambient temperature (23–27 °C) was determined by adsorbing the model antigen ovalbumin (OVA) to AM-41 particles (OVA-41). The OVA-41 was successfully freeze-dried using the excipients 5% trehalose and 1% PEG8000. Both the immunological activity of OVA and the nanoparticle structure were maintained following two months storage at ambient temperature. The results of immunisation studies in mice with reconstituted OVA-41 demonstrated the induction of humoral and cell-meditated immune responses. The capacity of AM-41 particles to facilitate ambient storage of vaccine components without loss of immunological potency will underpin the further development of this promising vaccine delivery platform.

A molecular dynamics study of ambient and high pressure phases of silica: Structure and enthalpy variation with molar volume

Extensive molecular dynamics studies of 13 different silica polymorphs are reported in the isothermal-isobaric ensemble with the Parrinello-Rahman variable shape simulation cell. The van Beest-Kramer-van Santen (BKS) potential is shown to predict lattice parameters for most phases within 2%-3% accuracy, as well as the relative stabilities of different polymorphs in agreement with experiment. Enthalpies of high-density polymorphs - CaCl2-type, alpha-PbO2-type, and pyrite-type for which no experimental data are available as yet, are predicted here. Further, the calculated enthalpies exhibit two distinct regimes as a function of molar volume-for low and medium-density polymorphs, it is almost independent of volume, while for high-pressure phases a steep dependence is seen. A detailed analysis indicates that the increased short-range contributions to enthalpy in the high-density phases arise not only from an increased coordination number of silicon but also shorter Si-O bond lengths. Our results indicate that amorphous phases of silica exhibit better optimization of short-range interactions than crystalline phases at the same density while the magnitude of Coulombic contributions is lower in the amorphous phase. (C) 2014 AIP Publishing LLC.

Ambient Temperature Hydrocarbon Selective Catalytic Reduction of NOx Using Atmospheric Pressure Nonthermal Plasma Activation of a Ag/Al2O3 Catalyst

Atmospheric pressure nonthermal-plasma-activated catalysis for the removal of NOx using hydrocarbon selective catalytic reduction has been studied utilizing toluene and n-octane as the hydrocarbon reductant. When the plasma was combined with a Ag/Al2O3 catalyst, a strong enhancement in activity was observed when compared with conventional thermal activation with high conversions of both. NOx and hydrocarbons obtained at temperature at temperature ≤250 °C, where the silver catalyst is normally inactive. Importantly, even in the absence of an external heat source, significant activity was obtained. This low temperature activity provides the basis for applying nonthermal plasmas to activate emission control catalysts during cold start conditions, which remains an important issue for mobile and stationary applications.

Impact of long-term storage at ambient temperatures on the total quality and stability of high-pressure processed tomato juice

High-pressure processing (HPP) can produce tomato juice of high quality and safety with a short shelf life under refrigeration temperatures. Long-term higher temperature storage studies are rare and temperature tolerant products are challenging to develop. The effect of high-pressure processing (HPP) on the total quality (colour, microbial counts, phytochemical levels, antioxidant and enzymatic activities) and stability (retention over time) of tomato juice during long-term storage was investigated. Thermal processing (TP) was used as a control treatment, and overall, two different ambient conditions (20 °C and 28 °C) were tested. Immediately after processing, HPP products proved superior to TP ones (enhanced redness, total carotenoids and lycopene, stable total phenols and inactivation of pectin methyl esterase). During initial storage (30 d) most quality attributes of HPP juice remained stable. Prolonged storage, however, led to losses of most quality attributes, although HPP (20 °C) showed lower quality degradation rate constants comparison to TP and HPP (28 °C). Industrial Relevance: There is a demand for ambient stable tomato products, especially in some parts of the world, and current industrial practices (canning, pasteurisation) either compromise in product quality or require refrigeration conditions. High-pressure processing has been investigated as milder technology, with a potential to deliver superior quality. The drawback is that is also requires chill storage. The results of this study show how quality parameters behave in a high-pressured tomato product and pave the way for further development that could optimise this technology. This could be of economic importance for the tomato juice industry to develop new products stable in ambient temperatures and perhaps beneficial for cutting down the refrigeration costs under specific conditions.

Effects of drying methods and conditions on antimicrobial activity of edible chitosan films enriched with galangal extract

The aim of this work was to study the effects of drying methods and conditions (i.e., ambient drying, hot air drying at 40 degrees C, vacuum drying and low-pressure superheated steam drying within the temperature range of 70-90 degrees C at an absolute pressure of 10 kPa) as well as the concentration of galangal extract on the antimicrobial activity of edible chitosan films against Staphylococcus aureus. Galangal extract was added to the film forming solution as a natural antimicrobial agent in the concentration range of 0.3-0.9 g/100 g. Fourier transform infrared (FTIR) spectra and swelling of the films were also evaluated to investigate interaction between chitosan and the galangal extract. The antimicrobial activity of the films was evaluated by the disc diffusion and viable cell count method, while the morphology of bacteria treated with the antimicrobial films was observed via transmission electron microscopy (TEM). The antimicrobial activity, swelling and functional group interaction of the antimicrobial films were found to be affected by the drying methods and conditions as well as the concentration of the galangal extract. The electron microscopic observations revealed that cell wall and cell membrane of S. aureus treated by the antimicrobial films were significantly damaged. (C) 2009 Elsevier Ltd. All rights reserved.

Effect of apparent viscosity on the pressure drop during fluidized bed drying of soursop pulp

Pressure drop and minimum fluidization velocity were experimentally studied in a vibro-fluidized bed of inert particles subjected to different vibration intensities during drying of soursop pulp. Maltodextrin was added to the pulp in order to prevent stickiness between particles and the consequent bed collapse. Pulps were initially concentrated, resulting in pastes with different soluble solids content, and a constant fraction of maltodextrin was guaranteed in the final pulp samples. The pulp theological behavior as affected by temperature and total soluble solids content, including maltodextrin, was evaluated and the effect of pulp apparent viscosity on pressure drop and minimum vibro-fluidization velocity were investigated. Two types of inert particles -3.6 mm glass beads and 3 mm Teflon cylinders (length and diameter) - were tested and, due to lower pressure drop presented by Teflon cylinders during operation of the dry vibro-fluidized bed, these particles were adopted for pulp drying process. Increasing pulp apparent viscosity caused a considerable increase in the vibro-fluidized bed pressure drop during pulp drying and, as a consequence resulted in a larger value of minimum vibro-fluidization velocity. on the other hand, the negative effect of increasing apparent viscosity could be attenuated by increasing the fluidized bed vibration intensity, which could prevent stickiness between particles. (c) 2006 Elsevier B.V. All rights reserved.

Development, characterization, and application of flowing atmospheric-pressure afterglow ionization for mass spectrometric analysis of ambient organic aerosols

Addressing current limitations of state-of-the-art instrumentation in aerosol research, the aim of this work was to explore and assess the applicability of a novel soft ionization technique, namely flowing atmospheric-pressure afterglow (FAPA), for the mass spectrometric analysis of airborne particulate organic matter. Among other soft ionization methods, the FAPA ionization technique was developed in the last decade during the advent of ambient desorption/ionization mass spectrometry (ADI–MS). Based on a helium glow discharge plasma at atmospheric-pressure, excited helium species and primary reagent ions are generated which exit the discharge region through a capillary electrode, forming the so-called afterglow region where desorption and ionization of the analytes occurs. Commonly, fragmentation of the analytes during ionization is reported to occur only to a minimum extent, predominantly resulting in the formation of quasimolecular ions, i.e. [M+H]+ and [M–H]– in the positive and the negative ion mode, respectively. Thus, identification and detection of signals and their corresponding compounds is facilitated in the acquired mass spectra. The focus of the first part of this study lies on the application, characterization and assessment of FAPA–MS in the offline mode, i.e. desorption and ionization of the analytes from surfaces. Experiments in both positive and negative ion mode revealed ionization patterns for a variety of compound classes comprising alkanes, alcohols, aldehydes, ketones, carboxylic acids, organic peroxides, and alkaloids. Besides the always emphasized detection of quasimolecular ions, a broad range of signals for adducts and losses was found. Additionally, the capabilities and limitations of the technique were studied in three proof-of-principle applications. In general, the method showed to be best suited for polar analytes with high volatilities and low molecular weights, ideally containing nitrogen- and/or oxygen functionalities. However, for compounds with low vapor pressures, containing long carbon chains and/or high molecular weights, desorption and ionization is in direct competition with oxidation of the analytes, leading to the formation of adducts and oxidation products which impede a clear signal assignment in the acquired mass spectra. Nonetheless, FAPA–MS showed to be capable of detecting and identifying common limonene oxidation products in secondary OA (SOA) particles on a filter sample and, thus, is considered a suitable method for offline analysis of OA particles. In the second as well as the subsequent parts, FAPA–MS was applied online, i.e. for real time analysis of OA particles suspended in air. Therefore, the acronym AeroFAPA–MS (i.e. Aerosol FAPA–MS) was chosen to refer to this method. After optimization and characterization, the method was used to measure a range of model compounds and to evaluate typical ionization patterns in the positive and the negative ion mode. In addition, results from laboratory studies as well as from a field campaign in Central Europe (F–BEACh 2014) are presented and discussed. During the F–BEACh campaign AeroFAPA–MS was used in combination with complementary MS techniques, giving a comprehensive characterization of the sampled OA particles. For example, several common SOA marker compounds were identified in real time by MSn experiments, indicating that photochemically aged SOA particles were present during the campaign period. Moreover, AeroFAPA–MS was capable of detecting highly oxidized sulfur-containing compounds in the particle phase, presenting the first real-time measurements of this compound class. Further comparisons with data from other aerosol and gas-phase measurements suggest that both particulate sulfate as well as highly oxidized peroxyradicals in the gas phase might play a role during formation of these species. Besides applying AeroFAPA–MS for the analysis of aerosol particles, desorption processes of particles in the afterglow region were investigated in order to gain a more detailed understanding of the method. While during the previous measurements aerosol particles were pre-evaporated prior to AeroFAPA–MS analysis, in this part no external heat source was applied. Particle size distribution measurements before and after the AeroFAPA source revealed that only an interfacial layer of OA particles is desorbed and, thus, chemically characterized. For particles with initial diameters of 112 nm, desorption radii of 2.5–36.6 nm were found at discharge currents of 15–55 mA from these measurements. In addition, the method was applied for the analysis of laboratory-generated core-shell particles in a proof-of-principle study. As expected, predominantly compounds residing in the shell of the particles were desorbed and ionized with increasing probing depths, suggesting that AeroFAPA–MS might represent a promising technique for depth profiling of OA particles in future studies.

Retrofit of heat exchanger networks with pressure recovery of process streams at sub-ambient conditions

This paper presents a new mathematical programming model for the retrofit of heat exchanger networks (HENs), wherein the pressure recovery of process streams is conducted to enhance heat integration. Particularly applied to cryogenic processes, HENs retrofit with combined heat and work integration is mainly aimed at reducing the use of expensive cold services. The proposed multi-stage superstructure allows the increment of the existing heat transfer area, as well as the use of new equipment for both heat exchange and pressure manipulation. The pressure recovery of streams is carried out simultaneously with the HEN design, such that the process conditions (streams pressure and temperature) are variables of optimization. The mathematical model is formulated using generalized disjunctive programming (GDP) and is optimized via mixed-integer nonlinear programming (MINLP), through the minimization of the retrofit total annualized cost, considering the turbine and compressor coupling with a helper motor. Three case studies are performed to assess the accuracy of the developed approach, including a real industrial example related to liquefied natural gas (LNG) production. The results show that the pressure recovery of streams is efficient for energy savings and, consequently, for decreasing the HEN retrofit total cost especially in sub-ambient processes.

Experimental and modeling studies of forced convection storage and drying systems for sweet potatoes

Sweet potato is an important strategic agricultural crop grown in many countries around the world. The roots and aerial vine components of the crop are used for both human consumption and, to some extent as a cheap source of animal feed. In spite of its economic value and growing contribution to health and nutrition, harvested sweet potato roots and aerial vine components has limited shelf-life and is easily susceptible to post-harvest losses. Although post-harvest losses of both sweet potato roots and aerial vine components is significant, there is no information available that will support the design and development of appropriate storage and preservation systems. In this context, the present study was initiated to improve scientific knowledge about sweet potato post-harvest handling. Additionally, the study also seeks to develop a PV ventilated mud storehouse for storage of sweet potato roots under tropical conditions. In study one, airflow resistance of sweet potato aerial vine components was investigated. The influence of different operating parameters such as airflow rate, moisture content and bulk depth at different levels on airflow resistance was analyzed. All the operating parameters were observed to have significant (P < 0.01) effect on airflow resistance. Prediction models were developed and were found to adequately describe the experimental pressure drop data. In study two, the resistance of airflow through unwashed and clean sweet potato roots was investigated. The effect of sweet potato roots shape factor, surface roughness, orientation to airflow, and presence of soil fraction on airflow resistance was also assessed. The pressure drop through unwashed and clean sweet potato roots was observed to increase with higher airflow, bed depth, root grade composition, and presence of soil fraction. The physical properties of the roots were incorporated into a modified Ergun model and compared with a modified Shedd’s model. The modified Ergun model provided the best fit to the experimental data when compared with the modified Shedd’s model. In study three, the effect of sweet potato root size (medium and large), different air velocity and temperature on the cooling/or heating rate and time of individual sweet potato roots were investigated. Also, a simulation model which is based on the fundamental solution of the transient equations was proposed for estimating the cooling and heating time at the centre of sweet potato roots. The results showed that increasing air velocity during cooling and heating significantly (P < 0.05) affects the cooling and heating times. Furthermore, the cooling and heating times were significantly different (P < 0.05) among medium and large size sweet potato roots. Comparison of the simulation results with experimental data confirmed that the transient simulation model can be used to accurately estimate the cooling and heating times of whole sweet potato roots under forced convection conditions. In study four, the performance of charcoal evaporative cooling pad configurations for integration into sweet potato roots storage systems was investigated. The experiments were carried out at different levels of air velocity, water flow rates, and three pad configurations: single layer pad (SLP), double layers pad (DLP) and triple layers pad (TLP) made out of small and large size charcoal particles. The results showed that higher air velocity has tremendous effect on pressure drop. Increasing the water flow rate above the range tested had no practical benefits in terms of cooling. It was observed that DLP and TLD configurations with larger wet surface area for both types of pads provided high cooling efficiencies. In study five, CFD technique in the ANSYS Fluent software was used to simulate airflow distribution in a low-cost mud storehouse. By theoretically investigating different geometries of air inlet, plenum chamber, and outlet as well as its placement using ANSYS Fluent software, an acceptable geometry with uniform air distribution was selected and constructed. Experimental measurements validated the selected design. In study six, the performance of the developed PV ventilated system was investigated. Field measurements showed satisfactory results of the directly coupled PV ventilated system. Furthermore, the option of integrating a low-cost evaporative cooling system into the mud storage structure was also investigated. The results showed a reduction of ambient temperature inside the mud storehouse while relative humidity was enhanced. The ability of the developed storage system to provide and maintain airflow, temperature and relative humidity which are the key parameters for shelf-life extension of sweet potato roots highlight its ability to reduce post-harvest losses at the farmer level, particularly under tropical climate conditions.