Preparation of gas-filled porous microparticles (GPPs) and microbubbles (MBs) by PGSS method

Dissertation to obtain the Master Degree in Biotechnology

Gas gap heat switch for CryoFree project

Cryogen-free superconducting magnet systems have become popular during the last two decades for the simple reason that with the use of liquid helium is rather cumbersome and is a scarce resource. Some available CFMS uses a mechanical cryocooler as cold source of the superconductor magnet. However, the cooling of the sample holder is still made through an open circuit of helium. A thermal management of a completely cryogen-free system is possible to be implemented by using a controlled gas gap heat switch (GGHS) between the cryocooler and the variable temperature insert (VTI). This way it would eliminate the helium open circuit. Heat switches are devices that allow to toggle between two distinct thermal states (ON and OFF state). Several cryogenic applications need good thermal contact and a good thermal insulation at different stages of operation. A versatile GGHS was designed and built with a 100 mm gap and tested with helium as exchange gas. An analytic thermal model was developed and a good agreement with the experimental data was obtained. The device was tested on a crycooler at 4 to 80 K ranges. A 285 mW/K thermal conductance was measured at ON state and 0.09 mW/K at OFF. 3000 ON/OFF thermal conductance ratio was obtained at 4 K with helium.

Molecular simulation of gas adsorption equilibria in nanoporous materials

This work is divided into two distinct parts. The first part consists of the study of the metal organic framework UiO-66Zr, where the aim was to determine the force field that best describes the adsorption equilibrium properties of two different gases, methane and carbon dioxide. The other part of the work focuses on the study of the single wall carbon nanotube topology for ethane adsorption; the aim was to simplify as much as possible the solid-fluid force field model to increase the computational efficiency of the Monte Carlo simulations. The choice of both adsorbents relies on their potential use in adsorption processes, such as the capture and storage of carbon dioxide, natural gas storage, separation of components of biogas, and olefin/paraffin separations. The adsorption studies on the two porous materials were performed by molecular simulation using the grand canonical Monte Carlo (μ,V,T) method, over the temperature range of 298-343 K and pressure range 0.06-70 bar. The calibration curves of pressure and density as a function of chemical potential and temperature for the three adsorbates under study, were obtained Monte Carlo simulation in the canonical ensemble (N,V,T); polynomial fit and interpolation of the obtained data allowed to determine the pressure and gas density at any chemical potential. The adsorption equilibria of methane and carbon dioxide in UiO-66Zr were simulated and compared with the experimental data obtained by Jasmina H. Cavka et al. The results show that the best force field for both gases is a chargeless united-atom force field based on the TraPPE model. Using this validated force field it was possible to estimate the isosteric heats of adsorption and the Henry constants. In the Grand-Canonical Monte Carlo simulations of carbon nanotubes, we conclude that the fastest type of run is obtained with a force field that approximates the nanotube as a smooth cylinder; this approximation gives execution times that are 1.6 times faster than the typical atomistic runs.

Gas tungsten arc welding of NiTi shape memory alloy

Shape memory alloys are characterized by the ability of recovering their initial shape after being deformed and by superelasticity. Since the discovery of these alloys, a new field of interest emerged not only for the scientific community but also to many industries. However, these alloys present poor machinability which constitute a constrain in the design of complex components for new applications. Thus, the demand for joining techniques able to join these alloys without compromising their properties became of great importance to enlarge the complexity of existing applications. Literature shows that these alloys are joined mainly using laser welding. In the present study, similar NiTi butt joints, were produced using TIG welding. The welds were performed in 1.5 mm thick plates across the rolling direction. A special fixture and gas assist device was designed and manufactured. Also a robot arm was adapted to accommodate the welding torch to assure the repeatability of the welding parameters. Welds were successfully achieved without macroscopic defects, such as pores and distortions. Very superficial oxidation was seen on the top surface due to insufficient shielding gas flow on the weld face. The welded joints were mechanically tested and structurally characterized. Testing methods were used to evaluate macro and microstructure, as well as the phase transformation temperatures, the mechanical single and cyclic behaviour and the shape recovery ability. Differential Scanning Calorimetry (DSC), Scanning Electron Microscopy (SEM), Energy Dispersive Spectroscopy (EDS), microhardness measurements were techniques also used to evaluate the welded joints. A depletion in Ni in the fusion zone was seen, as well as a shift in Ms temperature. For strain values of 4% the accumulated irrecoverable strain was of about 30% and increased with the strain imposed during cycling. Nevertheless, a complete recovery of initial shape was observed when testing the shape memory effect on a dedicated device that introduces a deformation of 6.7%. That is, the welding procedure does not remove the ability of the specimens to recover their initial shape.

Building a thinner gap in a gas-gap heat switch

25th International Cryogenic Engineering Conference and the International Cryogenic Materials Conference in 2014, ICEC 25–ICMC 2014

Untersuchung des Flüssigkeitseintrages auf die Temperaturverteilung in Gas-/Feststoff-Wirbelschichten

Liquid separation efficiency, liquid penetration, modeling, arrays of temperature, distribution, fluidized bed, two-phase-nozzle

Estudi de la reductibilitat de catalitzadors basats en cobalt i el seu comportament en la reacció de desplaçament de gas d'aigua de CO

Projecte de recerca elaborat a partir d’una estada a la universitat d'Udine, Itàlia, entre setembre i desembre del 2006.S'han caracteritzat mitjançant la reducció a temperatura programada i tests catalítics catalitzadors en pols basats en cobalt i supostats en òxid de zinc i monòlits ceràmics funcionaliltzats també amb cobalt i òxid de zinc. L'addició de promotors (manganès, crom i ferro ) als catalitzadors en pols, preparats per impregnació i precipitació, no afecta significativament ni la temperatura a la qual té lloc la reducció ni al percentatge global de reducció. En els cicles de reducció-oxidació sí que s'observen diferències entre el primer perfil de reducció i els següents, especialment en el cas de la mostra que té ferro com a promotor, on les diferències s'accentuen en cicles successius (fins al quart). S'ha evaluat l'activitat d'aquests catalitzadors en la reacció de desplaçament de gas d'aigua, obtenint uns resultats satisfactoris. Finalment s'han realitzat reduccions a temperatura programada i tests catalítics en la reacció de desplaçament de gas d'aigua amb monòlits funcionalitzats amb cobalt i òxid de zinc (en cap d'ells s'ha introduït promotors). El nivell de conversió assolit és menor que en el cas de catalitzadors en pols, fet que s'associa a la geometria d'aquests sistemes catalítics, però la relació CH4/CO2 és més favorable que en els catalitzadors en pols, el que els converteix en sistemes molt selectius.

Accuracy profile validation of a new method for carbon monoxide measurement in the human blood using headspace-gas chromatography-mass spectrometry (HS-GC-MS).

The aim of our study was to provide an innovative headspace-gas chromatography-mass spectrometry (HS-GC-MS) method applicable for the routine determination of blood CO concentration in forensic toxicology laboratories. The main drawback of the GC/MS methods discussed in literature for CO measurement is the absence of a specific CO internal standard necessary for performing quantification. Even if stable isotope of CO is commercially available in the gaseous state, it is essential to develop a safer method to limit the manipulation of gaseous CO and to precisely control the injected amount of CO for spiking and calibration. To avoid the manipulation of a stable isotope-labeled gas, we have chosen to generate in a vial in situ, an internal labeled standard gas ((13)CO) formed by the reaction of labeled formic acid formic acid (H(13)COOH) with sulfuric acid. As sulfuric acid can also be employed to liberate the CO reagent from whole blood, the procedure allows for the liberation of CO simultaneously with the generation of (13)CO. This method allows for precise measurement of blood CO concentrations from a small amount of blood (10 μL). Finally, this method was applied to measure the CO concentration of intoxicated human blood samples from autopsies.

Simultaneous determination of plasma levels of fluvoxamine and of the enantiomers of fluoxetine and norfluoxetine by gas chromatography-mass spectrometry.

A gas chromatographic-mass spectrometric method is presented which allows the simultaneous determination of the plasma concentrations of fluvoxamine and of the enantiomers of fluoxetine and norfluoxetine after derivatization with the chiral reagent, (S)-(-)-N-trifluoroacetylprolyl chloride. No interference was observed from endogenous compounds following the extraction of plasma samples from six different human subjects. The standard curves were linear over a working range of 10 to 750 ng/ml for racemic fluoxetine and norfluoxetine and of 50 to 500 ng/ml for fluvoxamine. Recoveries ranged from 50 to 66% for the three compounds. Intra- and inter-day coefficients of variation ranged from 4 to 10% for fluvoxamine and from 4 to 13% for fluoxetine and norfluoxetine. The limits of quantitation of the method were found to be 2 ng/ml for fluvoxamine and 1 ng/ml for the (R)- and (S)-enantiomers of fluoxetine and norfluoxetine, hence allowing its use for single dose pharmacokinetics. Finally, by using a steeper gradient of temperature, much shorter analysis times are obtained if one is interested in the concentrations of fluvoxamine alone.

A pilot assessment of alpha-stat vs pH-stat arterial blood gas analysis after cardiac arrest.

PURPOSE: Resuscitated cardiac arrest (CA) patients typically receive therapeutic hypothermia, but arterial blood gases (ABGs) are often assessed after adjustment to 37°C (alpha-stat) instead of actual body temperature (pH-stat). We sought to compare alpha-stat and pH-stat assessment of Pao2 and Paco2 in such patients. MATERIALS AND METHODS: Using ABG data obtained during the first 24 hours of intensive care unit admission, we determined the impact of measured alpha vs calculated pH-stat on Pao2 and Paco2 on patient classification and outcomes for CA patients. RESULTS: We assessed 1013 ABGs from 120 CA patients with a median age of patients 66 years (interquartile range, 50-76). Median alpha-stat Pao2 changed from 122 (95-156) to 107 (82-143) mm Hg with pH-stat and median Paco2 from 39 (34-46) to 35 (30-41) mm Hg (both P < .001). Using the categories of hyperoxemia, normoxemia, and hypoxemia, pH-stat estimation of Pao2 reclassified approximately 20% of patients. Using the categories of hypercapnia, normocapnia, and hypocapnia, pH stat estimation of Paco2 reclassified approximately 40% of patients. The mortality of patients in different Pao2 and Paco2 categories was similar for pH-stat and alpha-stat. CONCLUSIONS: Using the pH-stat method, fewer resuscitated CA patients admitted to intensive care unit were classified as hyperoxemic or hypercapnic compared with alpha-stat. These findings suggest an impact of ABG assessment methodology on Pao2, Paco2, and patient classification but not on associated outcomes.

Nanosized Nb-TiO2 gas sensors derived from alkoxides hydrolization

Nanocrystalline TiO2 modified with Nb has been produced through the sol-gel technique. Nanopowders have been obtained by means of the hydrolysis of pure alkoxides with deionized water and peptization of the resulting hydrolysate with diluted acid nitric at 100 C. The addition of Nb stabilizes the anatase phase to higher temperatures. XRD spectra of the undoped and the Nb-doped samples show that the undoped sample has been almost totally converted to rutile at 600 C, meanwhile the doped samples present still a low percentage of rutile phase. Nanocrystalline powders stabilized at 600 C with grain sizes of about 17 nm have successfully been synthesized by the addition of Nb with a concentration of 2% at., which appears to be an adequate additive concentration to improve the gas sensor performances, such as it is suggested by the catalytic conversion efficiency experiments performed from FTIR measurements. FTIR absorbance spectra show that catalytic conversion of CO occurs at lower temperatures when niobium is introduced. The electrical response of the films to different concentrations of CO and ethanol has been monitored in dry and wet environments in order to test the influence of humidity in the sensor response. The addition of Nb decreases the working temperature and increases the stability of the layers. Also, large enhancement of the response time is obtained even with lower working temperatures. Moreover, humidity effects on the gas sensor response toward CO and ethanol are less important in Nb-doped samples than in the undoped ones.

Gas collisions and pressure quenching of the photoluminescence of silicon nanopowder grown by plasma-enhanced chemical vapor deposition

The quenching of the photoluminescence of Si nanopowder grown by plasma-enhanced chemical vapor deposition due to pressure was measured for various gases ( H2, O2, N2, He, Ne, Ar, and Kr) and at different temperatures. The characteristic pressure, P0, of the general dependence I(P) = I0¿exp(¿P/P0) is gas and temperature dependent. However, when the number of gas collisions is taken as the variable instead of pressure, then the quenching is the same within a gas family (mono- or diatomic) and it is temperature independent. So it is concluded that the effect depends on the number of gas collisions irrespective of the nature of the gas or its temperature.

Structural and gas-sensing properties of WO3 nanocrystalline powders obtained by a sol-gel method from tungstic acid

WO3 nanocrystalline powders were obtained from tungstic acid following a sol-gel process. Evolution of structural properties with annealing temperature was studied by X-ray diffraction and Raman spectroscopy. These structural properties were compared with those of WO3 nanopowders obtained by the most common process of pyrolysis of ammonium paratungstate, usually used in gas sensors applications. Sol-gel WO3 showed a high sensor response to NO2 and low response to CO and CH4. The response of these sensor devices was compared with that of WO3 obtained from pyrolysis, showing the latter a worse sensor response to NO2. Influence of operating temperature, humidity, and film thickness on NO2 detection was studied in order to improve the sensing conditions to this gas.

Nanosized Nb-TiO2 gas sensors derived from alkoxides hydrolization

Nanocrystalline TiO2 modified with Nb has been produced through the sol-gel technique. Nanopowders have been obtained by means of the hydrolysis of pure alkoxides with deionized water and peptization of the resulting hydrolysate with diluted acid nitric at 100 C. The addition of Nb stabilizes the anatase phase to higher temperatures. XRD spectra of the undoped and the Nb-doped samples show that the undoped sample has been almost totally converted to rutile at 600 C, meanwhile the doped samples present still a low percentage of rutile phase. Nanocrystalline powders stabilized at 600 C with grain sizes of about 17 nm have successfully been synthesized by the addition of Nb with a concentration of 2% at., which appears to be an adequate additive concentration to improve the gas sensor performances, such as it is suggested by the catalytic conversion efficiency experiments performed from FTIR measurements. FTIR absorbance spectra show that catalytic conversion of CO occurs at lower temperatures when niobium is introduced. The electrical response of the films to different concentrations of CO and ethanol has been monitored in dry and wet environments in order to test the influence of humidity in the sensor response. The addition of Nb decreases the working temperature and increases the stability of the layers. Also, large enhancement of the response time is obtained even with lower working temperatures. Moreover, humidity effects on the gas sensor response toward CO and ethanol are less important in Nb-doped samples than in the undoped ones.

Gas-sensing properties of sprayed films of (CdO)x(ZnO)1-x mixed oxide

A novel NO2 sensor based on (CdO)x(ZnO)1-x mixed-oxide thin films deposited by the spray pyrolysis technique is developed. The sensor response to 3-ppm NO2 is studied in the range 50°C-350°C for three different film compositions. The device is also tested for other harmful gases, such as CO (300 ppm) and CH4 (3000 ppm). The sensor response to these reducing gases is different at different temperatures varying from the response typical for the p-type semiconductor to that typical for the n-type semiconductor. Satisfactory response to NO2 and dynamic behavior at 230°C, as well as low resistivity, are observed for the mixed-oxide film with 30% Cd. The response to interfering gas is poor at working temperature (230°C). On the basis of this study, a possible sensing mechanism is proposed.