abstract: Nanoparticle suspensions, popularly termed “nanofluids,” have been extensively investigated for their thermal and radiative properties. Such work has generated great controversy, although it is arguably accepted today that the presence of nanoparticles rarely leads to useful enhancements in either thermal conductivity or convective heat transfer. On the other hand, there are still examples of unanticipated enhancements to some properties, such as the reported specific heat of molten salt-based nanofluids and the critical heat flux. Another largely overlooked example is the apparent effect of nanoparticles on the effective latent heat of vaporization (hfg) of aqueous nanofluids. A previous study focused on molecular dynamics (MD) modeling supplemented with limited experimental data to suggest that hfg increases with increasing nanoparticle concentration. Here, this research extends that exploratory work in an effort to determine if hfg of aqueous nanofluids can be manipulated, i.e., increased or decreased, by the addition of graphite or silver nanoparticles. Our results to date indicate that hfg can be substantially impacted, by up to ± 30% depending on the type of nanoparticle. Moreover, this dissertation reports further experiments with changing surface area based on volume fraction (0.005% to 2%) and various nanoparticle sizes to investigate the mechanisms for hfg modification in aqueous graphite and silver nanofluids. This research also investigates thermophysical properties, i.e., density and surface tension in aqueous nanofluids to support the experimental results of hfg based on the Clausius - Clapeyron equation. This theoretical investigation agrees well with the experimental results. Furthermore, this research investigates the hfg change of aqueous nanofluids with nanoscale studies in terms of melting of silver nanoparticles and hydrophobic interactions of graphite nanofluid. As a result, the entropy change due to those mechanisms could be a main cause of the changes of hfg in silver and graphite nanofluids. Finally, applying the latent heat results of graphite and silver nanofluids to an actual solar thermal system to identify enhanced performance with a Rankine cycle is suggested to show that the tunable latent heat of vaporization in nanofluilds could be beneficial for real-world solar thermal applications with improved efficiency. / Dissertation/Thesis / Doctoral Dissertation Mechanical Engineering 2015

abstract: Vapor intrusion (VI), can pose health risks to building occupants. Assessment and mitigation at VI impacted sites have been guided by a site conceptual model (SCM) in which vapors originate from subsurface sources, diffuse through soil matrix and enter into a building by gas flow across foundation cracks. Alternative VI pathways and groundwater table fluctuations are not often considered. Alternative VI pathways, involving vapor transport along sewer lines and other subsurface infrastructure, have recently been found to be significant contributors to VI impacts at some sites. This study evaluated approaches for identifying and characterizing the significance of alternative VI pathways and assessed the effectiveness of conventional mitigation at a site with an alternative VI pathway that can be manipulated to be on or off. The alternative pathway could not be identified using conventional pathway assessment procedures and can only be discovered under controlled pressure method (CPM) conditions. Measured emission rates were two orders of magnitude greater than screening model estimates and sub-foundation vertical soil gas profiles changed and were no longer consistent with the conventional VI conceptual model when the CPM test was conducted. The pipe flow VI pathway reduced the vacuum performance of the sub-slab depressurization (SSD) VI mitigation system, but the SSD system still provided sufficient protection to the house. The relationship between groundwater table fluctuations and subsurface vapor emissions and transport is examined using multi-year data from the field site, and is studied in the laboratory. In addition, a broader range of conditions is examined through use of modeling validated with the experimental data. The results indicate that fluctuating groundwater tables will lead to amplified volatile organic chemical (VOC) emissions from groundwater to soil surface relative to steady water table elevation, however, the magnitude of this amplification is less concerned when long-term water fluctuation present. No clear correlations were found between VOC emissions and water table changes at the study site where annual water table fluctuations of about 0.3 m existed. Significant VOC emission amplifications by water table fluctuation would be expected under shallow groundwater conditions according to model analysis results. / Dissertation/Thesis / Doctoral Dissertation Civil and Environmental Engineering 2015

abstract: Pyrite is a 0.95 eV bandgap semiconductor which is purported to have great potential in widespread, low–cost photovoltaic cells. A thorough material selection process was used in the design of a pyrite sequential vapor deposition chamber aimed at reducing and possibly eliminating contamination during thin film growth. The design process focused on identifying materials that do not produce volatile components when exposed to high temperatures and high sulfur pressures. Once the materials were identified and design was completed, the ultra–high vacuum growth system was constructed and tested. Pyrite thin films were deposited using the upgraded sequential vapor deposition chamber by varying the substrate temperature from 250°C to 420°C during deposition, keeping sulfur pressure constant at 1 Torr. Secondary Ion Mass Spectrometry (SIMS) results showed that all contaminants in the films were reduced in concentration by orders of magnitude from those grown with the previous system. Characterization techniques of Rutherford Back–scattering Spectrometry (RBS), X–Ray Diffraction (XRD), Raman Spectroscopy, Optical Profilometry and UV/Vis/Near–IR Spectroscopy were performed on the deposited thin films. The results indicate that stoichiometric ratio of S:Fe, structural–quality (epitaxy), optical roughness and percentage of pyrite in the deposited thin films improve with increase in deposition temperature. A Tauc plot of the optical measurements indicates that the pyrite thin films have a bandgap of 0.94 eV. / Dissertation/Thesis / Masters Thesis Materials Science and Engineering 2016

abstract: This dissertation describes fundamental studies of hollow carbon nanostructures, which may be used as electrodes for practical energy storage applications such as batteries or supercapacitors. Electron microscopy is heavily utilized for the nanoscale characterization. To control the morphology of hollow carbon nanostructures, ZnO nanowires serve as sacrificial templates. The first part of this dissertation focuses on the optimization of synthesis parameters and the scale-up production of ZnO nanowires by vapor transport method. Uniform ZnO nanowires with 40 nm width can be produced by using 1100 °C reaction temperature and 20 sccm oxygen flow rate, which are the two most important parameters. The use of ethanol as carbon source with or without water steam provides uniform carbonaceous deposition on ZnO nanowire templates. The amount of as-deposited carbonaceous material can be controlled by reaction temperature and reaction time. Due to the catalytic property of ZnO surface, the thicknesses of carbonaceous layers are typically in nanometers. Different methods to remove the ZnO templates are explored, of which hydrogen reduction at temperatures higher than 700 °C is most efficient. The ZnO templates can also be removed under ethanol environment, but the temperatures need to be higher than 850 °C for practical use. Characterizations of hollow carbon nanofibers show that the hollow carbon nanostructures have a high specific surface area (>1100 m2/g) with the presence of mesopores (~3.5 nm). The initial data on energy storage as electrodes of electrochemical double layer capacitors show that high specific capacitance (> 220 F/g) can be obtained, which is related to the high surface area and unique porous hollow structure with a thin wall. / Dissertation/Thesis / Doctoral Dissertation Physics 2016

abstract: A new class of layered materials called the transition metal trichalcogenides (TMTCs) exhibit strong anisotropic properties due to their quasi-1D nature. These 2D materials are composed of chain-like structures which are weakly bound to form planar sheets with highly directional properties. The vibrational properties of three materials from the TMTC family, specifically TiS3, ZrS3, and HfS3, are relatively unknown and studies performed in this work elucidates the origin of their Raman characteristics. The crystals were synthesized through chemical vapor transport prior to mechanical exfoliation onto Si/SiO¬2 substrates. XRD, AFM, and Raman spectroscopy were used to determine the crystallinity, thickness, and chemical signature of the exfoliated crystals. Vibrational modes and anisotropic polarization are investigated through density functional theory calculations and angle-resolved Raman spectroscopy. Particular Raman modes are explored in order to correlate select peaks to the b-axis crystalline direction. Mode III vibrations for TiS3, ZrS3, and HfS3 are shared between each material and serves as a unique identifier of the crystalline orientation in MX3 materials. Similar angle-resolved Raman studies were conducted on the novel Nb0.5Ti0.5S3 alloy material grown through chemical vapor transport. Results show that the anisotropy direction is more difficult to determine due to the randomization of quasi-1D chains caused by defects that are common in 2D alloys. This work provides a fundamental understanding of the vibrational properties of various TMTC materials which is needed to realize applications in direction dependent polarization and linear dichroism. / Dissertation/Thesis / Masters Thesis Materials Science and Engineering 2017

O hidrogênio é considerado uma das principais alternativas aos combustíveis fósseis. Dentre os processos para sua produção, a reforma a vapor do bio-óleo é uma das mais promissoras. Sendo o ácido acético um dos componentes majoritários do bio-óleo, ele vem sendo usado como molécula modelo na reforma a vapor. Porém, problemas como baixo desempenho catalítico e formação de coque ainda precisam ser contornados. Nesse sentido, o suporte utilizado tem um papel importante. No entanto, ainda não foi esclarecido quais propriedades do suporte contribuem mais para a eficiência catalítica. Neste trabalho, a reforma a vapor do ácido acético foi avaliada sobre catalisadores de níquel. Foram utilizados catalisadores constituídos de Ni0 ancorado em suportes com diferentes propriedades (MgO, ZrO2, TiO2 e Al2O3). A área superficial do suporte e a forte interação Ni-suporte foram fundamentais para a dispersão metálica dos catalisadores. A dispersão metálica e capacidade do suporte ativar a molécula de H2O foram as propriedades que aparentemente mais influenciaram no desempenho catalítico. Para as reações realizadas a 500 °C, a conversão do ácido acético, seletividade para H2 e formação de coque foram basicamente influenciadas pela dispersão metálica. Nas reações realizadas a 600 °C, a formação de coque foi menor para os catalisadores com maior dispersão metálica. A conversão do ácido acético e seletividade para H2 a 600 °C foram influenciadas pela dispersão metálica dos catalisadores, mas aparentemente a capacidade do suporte ativar a molécula de H2O foi o que mais contribui. O catalisador 10Ni/Al2O3 apresentou a maior dispersão metálica e em reações a 500 °C isso levou a uma alta conversão e alta seletividade para H2 com baixa formação de coque. O catalisador 10Ni/MgO apresentou desempenho regular em ambas as temperaturas. Já o catalisador 10Ni/TiO2 teve o pior desempenho independente da temperatura, devido à baixa dispersão metálica. Apesar da alta formação de coque devido à dispersão metálica relativamente baixa, o catalisador 10Ni/ZrO2 exibiu alta conversão e foi o mais seletivo para H2 a 600 °C, provavelmente pela capacidade do ZrO2 ativar a molécula de H2O. / Hydrogen (H2) is considered one of major alternatives to fossil fuels. Among the processes for H2 production, steam reforming of bio-oil is one of the most promising. As acetic acid is present in large amounts in bio-oil, it is used as model molecule in steam reforming reactions. However, problems such as low catalytic performance and coke formation yet need to be solved. In this sense, supports used display important role. However, it is not clear what support characteristics contribute more to catalytic properties. Here, acetic acid steam reforming was carried out over Ni catalysts. It were used catalysts consisting by Ni0 anchored in supports with different properties (MgO, ZrO2, TiO2 and Al2O3). Surface area of support and strong Ni-support interaction were key to metal dispersion of catalysts. Metal dispersion and the capacity of support to activate H2O molecule were apparently the properties that more influence the catalytic performance. For reactions carried out at 500 °C acetic acid conversion, H2 selectivity and coke formation were primarily influenced by metal dispersion. In reactions performed at 600 °C coke formation was lower for catalysts with higher metal dispersion. Acetic acid conversion and H2 selectivity at 600 °C were influenced by metal dispersion of catalysts, but apparently the ability of support to activate H2O molecule was the most important. 10Ni/Al2O3 showed higher metal dispersion and at 500 °C this led to a high conversion and high selectivity for H2 with low coke formation. 10Ni/MgO catalyst showed intermediate performance at both temperatures. Already 10Ni/TiO2 catalyst had the worst performance independent of temperature due to low metal dispersion. Despite the high coke formation, due to the relatively low metal dispersion, 10Ni/ZrO2 catalyst exhibited high conversion and was the most selective to H2 at 600 °C, probably due to the ability of ZrO2 to activate H2O molecules.

Lors d'un accident grave dans un réacteur à neutrons rapides refroidi au sodium, le combustible fondu peut entrer en contact avec le sodium environnant, conduisant alors à une interaction communément appelée Interaction Combustible-Réfrigérant. L'objectif de ce travail est d'améliorer la connaissance relative aux transferts thermiques en régime d'ébullition en film du sodium, essentielle pour étudier les risques liés à une éventuelle explosion de vapeur. Peu d'études, tant expérimentales que théoriques, ont été menées sur l'ébullition en film du sodium. Une unique expérience permet d'étudier l'ébullition en film du sodium en convection naturelle. Lors de l'analyse de ces essais, deux sous-régimes d'ébullition en film, non identifiés par l'auteur mais déjà observés pour l'eau, ont été mis en évidence : un régime de film qualifié de stable, sans contact liquide-solide, et un régime de film qualifié d'instable, avec contacts. D'un point de vue théorique, un seul modèle dédié à l'ébullition en film du sodium est proposé dans la littérature, dont l'analyse a révélé de nombreux défauts. Dans un premier temps, une analyse d'échelles du problème a été effectuée en convection naturelle et en convection forcée, en distinguant les cas d'un fort et d'un faible sous-refroidissement. Cette approche simplifiée, cohérente avec les résultats expérimentaux, a permis de définir les nombres adimensionnels pertinents pour l'établissement de corrélations. Un modèle a ensuite été développé pour traiter l'ébullition en film du sodium autour d'une sphère dans le cas le plus général - en convection naturelle ou forcée, pour un métal liquide saturé ou sous-refroidi. Ce modèle est basé sur l'approximation de double couche limite et met en œuvre une méthode intégrale en considérant les termes inertiels et convectifs, classiquement négligés, dans les équations de bilan de l'écoulement de vapeur. Par ailleurs, le rayonnement est pris en compte de manière couplée à l'interface liquide-vapeur et contribue directement à la production de vapeur. Ce modèle permet d'évaluer correctement le flux de chaleur perdu par un corps chaud en comparaison aux résultats des essais, en particulier lorsque ceux-ci sont corrigés des biais expérimentaux. La partition du flux de chaleur, entre chauffage et vaporisation, est également estimée : il s'agit d'une information indispensable à la description d'une explosion de vapeur et non accessible expérimentalement. En outre, l'influence de différents paramètres - sous-refroidissement du sodium, surchauffe et diamètre de la sphère, vitesse de l'écoulement externe, pression du système - dans les conditions pouvant être celles d'un accident grave a été étudiée. Enfin, un modèle simplifié a été utilisé pour étudier la transition entre les deux sous-régimes d'ébullition en film identifiés dans l'expérience. Les tendances obtenues par cette approche sont analogues à celles observées expérimentalement. / During a severe accident in a sodium-cooled fast reactor, molten fuel may come into contact with the surrounding liquid sodium, resulting in a so-called Fuel-Coolant Interaction. This work aims at providing a better understanding and knowledge of the associated heat transfer, likely to be in the film-boiling regime and required to study the risks related to a vapor explosion. Scarce literature has been found on sodium film boiling, both from an experimental and a theoretical point of view. Only one experiment has been conducted to investigate sodium pool film-boiling heat transfer. In our analysis of the experiment, two film-boiling regimes have been identified: a stable film boiling regime, without liquid-solid contact, and an unstable film-boiling regime, with contacts. Besides, the only theoretical model dedicated to sodium film boiling has shown some weaknesses. First, a scaling analysis of the problem has been proposed for free and forced convection, considering the two extreme cases of saturated and highly subcooled liquid. This simplified approach, which shows a good agreement with the experimental data, provides the dimensionless numbers which should be used to build correlations. A theoretical model has been developed to describe sodium film-boiling heat transfer from a hot sphere in free and forced convection, whatever the liquid subcooling. It is based on a two-phase laminar boundary layer integral method and includes the inertial and convective terms in the vapor momentum and energy equations, usually neglected. The radiation has been taken into account in the interfacial energy balance and contributes directly to produce vapor. This model enables to predict the heat lost from a hot body within an acceptable error compared to the tests results especially when the experimental uncertainties are considered. The heat partition between liquid heating and vaporization, essential to study the vapor explosion phenomenon, is also estimated. The influence of different parameters - sodium subcooling, sphere superheat and diameter, external flow velocity, system pressure - under accident conditions has been studied. Eventually, a simplified model has been used to investigate the transition between the two film boiling regimes identified in the experiment. The trends obtained with this approach are similar to those observed experimentally.

Orientador: João Francisco Galera Monico / Coorientador: Luis Fernando Sapucci / Banca: Rui Manuel da Silva Fernandes / Banca: Felipe Geremia Nievinski / Resumo: Um dos produtos meteorológicos advindos do processamento de alta precisão de dados GNSS é a estimativa do atraso zenital troposférico o qual pode ser utilizado para quantificar o vapor d'água integrado na coluna atmosférica, importante medida para as ciências atmosféricas. A combinação de séries temporais do atraso troposférico visa gerar uma solução única, mais confiável se comparada com as soluções individuais estimadas via processamento de dados GNSS. Esta dissertação propõe uma combinação em tempo quase real do atraso zenital troposférico baseada em múltiplas soluções para um tempo específico. Nessas circunstâncias, optou-se por uma combinação obtida por meio do método dos mínimos quadrados, com controle de qualidade realizado pelo processo detecção, identificação e adaptação. As estimativas do atraso zenital troposférico foram obtidas por meio dos softwares de processamento de dados GNSS, GAMIT e GIPSY-OASIS II (GOA-II), os quais utilizam diferentes métodos e estratégias de processamento... / Abstract: One of meteorological products obtained from the high-precision GNSS data processing is the zenithal tropospheric delay, which can be used to quantify the integrated water vapor, an important measurement for atmospheric sciences. Combination of tropospheric delay time series aims to generate a single solution, more reliable than each individual series. This dissertation proposes a combination in near real time of tropospheric delay parameters based on multiple solutions for a specific time. Under these circumstances, it was decided a combination derived by the least squares method and the quality control process based on detection, identification and adaptation. The zenithal tropospheric delay was derived by GIPSY-OASIS II and GAMIT GNSS data processing software systems, each one using different processing methods and strategies... / Mestre

In this work a procedure for arsenic speciation using criogenic trapping coupled to hydride generation atomic absorption spectrometry (HG-CT-AAS) was developed. Biological (chiken liver) and drug (N-methylglucamine antimonate)samples were investigated and the biological sample was introduced using slurry sampling to avoid the use of an extraction step. The material and the size of the cryogenic trapping tube ( U tube) were the parameters chosen to check the performance of the criogenic trapping step and arsenic species separation. The development of a new gas-liquid separator was also investigated. In addition, slurry concentration, foaming formed during the reaction with NaBH4, use of surfactant (Triton X-100) to achieve a homogenized particle distribution and the concentration of NaBH4 were studied. The results obtained using slurry sampling were compared with those using extraction with diluted phosphoric acid and tetramethylammonium hydroxide (TMAH) in different concentration. Water and biological tissue certified reference materials were used to evaluate the accuracy. The best separation efficiency of inorganic arsenic species, monomethylarsonic acid (MMA), dimethylarsinic acid (DMA) and trimethylarsine oxide (TMAO) was achieved using a quartz U tube (305 mm of length, 2.5 mm i.d. and 24 mm of broad). Using 1% (m/v) NaBH4, 1% (m/v) anti-foaming and sample injection of 0.5 ml (slurry in the concentration of 10%, m/v), prepared in 0.5% Triton, the recovery for arsenic (in inorganic form) was 71.6 ± 2.3%. With the addition of 5% (m/v) TMAH in the slurry, the recovery was 75.4 ± 1.9%. It is important to point out that the recoveries obtained for the other arsenic species were similar in comparison with arsenic in inorganic form. Limits of detection (LOD) were 0.09, 0.03, 0.04 and 0.06 mg g-1 for inorganic As, MMA, DMA and TMAO, respectively. Using the proposed procedure by HG-CT-AAS it was possible to analyze four arsenic species with the respective oxidation state. However, due to low recoveries obtained, the procedure was not used as an alternative for arsenic speciation in biological samples using slurry sampling. Therefore, additional studies could be performed in order to obtain better results. The procedure HG-CT-AAS was also used for arsenic speciation in Nmethylglucamine antimonate (meglumine antimonate) drug. Initially, suppression in the analytical signal was observed due to high concentration of Sb in the matrix sample. Therefore, the use of citric acid (1 to 10%) and hydrogen (15 to 33 ml min-1) and oxygen (32 to 70 ml min-1) flow rate were studied to avoid SbH3 formation and, consequently, enhance the resistance towards atomization interferences due to more uniform filling of the optical tube volume with H-radicals. The development of a valve, positioned before the atomizer, to release the SbH3 formed, was used to reduce the interference. Using hydrogen (21 ml min-1) and oxygen (45 ml min-1) and the valve, recoveries of 94.9 ± 3.3, 103.3 ± 8.3, 95.3 ± 4.7 and 100.8 ± 3.1% were obtained for inorganic arsenic species, MMA, DMA, TMAO, respectively. In spite of good recoveries were obtained for all arsenic species studied, only the inorganic arsenic determination was performed, since other species were not observed in the drug samples. The results obtained for inorganic As(III) and As(V) in five samples by HGCT- AAS were compared with those obtained for total arsenic concentration obtained by inductively coupled plasma mass spectrometry (ICP-MS). In addition, inorganic As(III) and As(V) determination was performed by liquid chromatography (LC) coupled to ICP-MS. No statistic difference (t-test with confidence level of 95%) was observed between the results obtained for total As and As(III) e As(V), determined by HG-CT-AAS with those obtained by ICP-MS and LC-ICP-MS. The LOD for As determination in inorganic form using the proposed procedure was 0.11 mg l-1. Therefore, it was possible to determine As(III) and As(V), in the inorganic form, in low concentrations in the meglumine antimonate drug, since the Sb interference was avoided by HG-CT-AAS. In addition, the proposed procedure presents a relatively, low coast in comparison with other techniques used for arsenic speciation, as LCICP-MS. / Neste trabalho é proposto um procedimento para a análise de especiação de arsênio empregando pré-concentração com aprisionamento criogênico e determinação por espectrometria de absorção atômica com geração de hidretos (HG-CT-AAS). O procedimento foi aplicado para a análise de especiação de As em amostra biológica (fígado de frango) e de medicamento (antimoniato de meglumina), sendo que a amostra biológica foi introduzida na forma de suspensão, evitando, assim, o uso de uma etapa de extração. As dimensões e o material utilizado na etapa de aprisionamento foram os critérios escolhidos para avaliar o desempenho de retenção e separação das espécies. O desenvolvimento de um separador gáslíquido (GLS) também foi avaliado. A concentração da suspensão de material biológico, formação de espuma durante a reação de redução com NaBH4, uso de tensoativo (Triton X-100) para uniformizar a distribuição das partículas na solução e a concentração da solução de NaBH4, foram estudados. Os resultados obtidos com o emprego da amostragem direta de suspensão foram comparados com o procedimento de extração empregando H3PO4 diluído e com o uso de hidróxido de tetrametilamônio (TMAH) em diferentes concentrações. Materiais de referência certificados de água e tecido biológico foram empregados para a avaliação da exatidão do procedimento. A melhor eficiência de separação entre as espécies de As na forma inorgânica, ácido monometilarsônico (MMA), ácido dimetilarsínico (DMA) e óxido de trimetilarsina (TMAO), foi obtida empregando um tubo em U de quartzo com 305 mm de comprimento, 2,5 mm d.i. e 24 mm de largura. Utilizando uma solução de NaBH4 1% (m/v), adição de anti-espumante (1%, m/v) e injeção de 0,5 ml de amostra (suspensão 10%), preparada em 0,5% (m/v) de Triton, a recuperação obtida foi de 71,6 ± 2,3% para a espécie de As na forma inorgânica. Com o emprego da adição de TMAH (5%, m/v) na suspensão 10% o valor da recuperação de As na forma inorgânica foi de 75,4 ± 1,9%. Cabe ressaltar que os valores das recuperações obtidas para as demais espécies foram da mesma ordem de magnitude em comparação com a espécie de As na forma inorgânica. Os limites de detecção (LOD) obtidos foram de 0,09, 0,03, 0,04 e 0,06 mg g-1 para as espécies de As na forma inorgânica, MMA, DMA e TMAO, respectivamente. O procedimento de HG-CT-AAS permitiu a análise de especiação de quatro espécies de As com a identificação dos respectivos estados de oxidação. Contudo, devido aos teores de recuperação obtidos não terem sido quantitativos, o procedimento não foi implementado como uma metodologia alternativa para a análise de especiação de As em material biológico com amostragem direta de suspensão. O procedimento de HG-CT-AAS foi, também, utilizado para a análise de especiação de As no medicamento antimoniato de N-metilglucamina (antimoniato de meglumina). Foi verificada a supressão do sinal analítico devido à elevada concentração de Sb na matriz do medicamento. Desta forma, o emprego de ácido cítrico (1 a 10%) e a vazão de hidrogênio (15 a 33 ml min-1) e oxigênio (32 a 70 ml min-1) foram estudados para reduzir a formação de SbH3 e promover maior tolerância à atomização de interferente, respectivamente. O desenvolvimento de uma válvula, previamente à etapa de atomização, para a liberação da estibina (SbH3) formada, também foi empregada para verificar a redução da ação do interferente. Para as vazões de hidrogênio (21 ml min-1) e oxigênio (45 ml min-1), juntamente como emprego da válvula, as recuperações obtidas foram de 94,9 ± 3,3, 103,3 ± 8,3, 95,3 ± 4,7 e 100,8 ± 3,3% para as espécies de As na forma inorgânica, MMA, DMA, TMAO, respectivamente. Embora recuperações quantitativas tenham sido obtidas para todas as espécies de As estudadas, apenas a determinação de As na forma inorgânica foi efetuada, visto que não foram identificadas outras espécies de As no medicamento. Os resultados obtidos para a determinação de As(III) e As(V) na forma inorgânica por HG-CT-AAS em cinco lotes do medicamento foram, posteriormente, comparados com os resultados obtidos para a determinação da concentração total de As empregando a espectrometria de massa com plasma indutivamente acoplado (ICP-MS). Adicionalmente, a determinação de As(III) e As(V) na forma inorgânica foi feita por cromatografia a líquido (LC) acoplada a ICPMS. Os resultados obtidos por ICP-MS e LC-ICP-MS foram comparados, individualmente, com os resultados obtidos empregando o procedimento por HG-CTAAS (teste-t com intervalo de confiança de 95%) e não apresentaram diferença estatística. O LOD para a determinação de As na forma inorgânica, para o procedimento proposto, foi de 0,11 mg l-1. Portanto, foi possível efetuar a determinação de As(III) e As(V), na forma inorgânica, no medicamento antimoniato de meglumina, visto que a interferência da matriz foi minimizada com o emprego da HG-CT-AAS. Adicionalmente, o procedimento proposto por HG-CT-AAS possui um custo de montagem e análise, relativamente, baixo quando comparado a outras técnicas como, por exemplo, LC-ICP-MS.

A esterilização a vapor em ciclo flash refere-se a qualquer processo de esterilização a vapor que processe itens para uso imediato, sem nenhum empacotamento e com tempo insuficiente para secagem. A Association for the Advancement of Medical Instrumentation e a Association of Perioperative Registered Nurses recomendam-na para situações de emergência e trazem critérios específicos para sua utilização. Essa pesquisa teve como hipótese a utilização pelos profissionais de enfermagem da esterilização a vapor em ciclo flash não restrita a situações emergenciais, contrariando as recomendações oficiais e da literatura. Portanto, o objetivo desse estudo foi de analisar as práticas relacionadas à esterilização em ciclo flash. Para o alcance deste propósito, foram coletadas informações, através de um questionário, de pessoas em evento de abrangência nacional realizado pela Sociedade Brasileira de Enfermeiros em Centro Cirúrgico, Central de Material e Esterilização e Recuperação Anestésica (SOBECC), a fim de obter dados de como esse processo de esterilização tem sido executado. Dos 560 questionários entregues, 113 (20,1%) foram devolvidos. Das características dos respondentes, 89,1% eram enfermeiros, apresentavam idade entre 25 e 50 anos, com tempo médio de formação de 12,7 anos, sendo a maioria da região Sudeste. Cerca de 46,0% trabalhavam no Centro Cirúrgico (CC) e 36,0% no Centro de Material (CME), com uma média de atuação no serviço de 8,1 anos. Das características da instituição, 40,0% eram de instituições públicas e 72,0% de caráter geral. Em relação à utilização do ciclo flash, 41,0% realizavam-na em autoclaves convencionais, sendo que 69,0% tinham seus esterilizadores no CME, local também em que 73,4% realizavam a limpeza do material. Para essa atividade, 61,4% tinham regras definidas, e 12,7% o faziam sem detergente sendo que dos profissionais envolvidos nesse processo, 81,2% eram da enfermagem. Para situações de emergência mais de 90,0% utilizavam o método de esterilização flash, mas um número razoável de respondentes (38,0%) o utilizavam como rotina, o que confirmou a hipótese da pesquisa, demonstrando o não cumprimento das recomendações das diretrizes internacionais e sim, a “adequação” de um arsenal de instrumentos para atender a demanda cirúrgica. Dos que embalam o material (62,2%), 84,0% o reesterilizavam caso não fosse usado. A esterilização de implantáveis em flash é realizada por apenas 8,0%. Dos respondentes, 78,0% monitoravam o processo de alguma maneira, inclusive com indicador químico e biológico 46,7%. Quanto à associação da freqüência de uso do ciclo flash com a presença das autoclaves de mesa infere-se que a inserção desse equipamento no mercado tem estimulado a utilização desse ciclo pelos profissionais. No estudo, percebeu-se que os índices de quem o faz de maneira inadequada, considerando todo o reprocessamento, não são substimáveis, mas preocupantes. Por esses índices, as recomendações das diretrizes internacionais não podem ser questionadas, mas entende-se que o empenho em reeducar o profissional da saúde e não simplesmente proibí-lo sem dar maiores justificativas seja o melhor caminho. A esterilização a vapor em ciclo flash só deve ser realizada se todos os passos fundamentais no reprocessamento de materiais forem cumpridos / The steam sterilization in flash cycle means any process of steam sterilization that processes items for immediate use, unwrapped and with insufficient time for drying. The Association for the Advancement of Medical Instrumentation and Association of Perioperative Registered Nurses recommend its for emergency situations and brings specific criteria for use. This research had as hypothesis that the use of steam sterilization in flash cycle by nursing professional is not restricted to emergency situations, opposing the official recommendations and literature. Therefore, the objective of this study was to analyze the practical ones related to the sterilization in flash cycle. For the reach of this intention, information had been collected, through a questionnaire, of people in a national event carried through by the Brazilian Society of Nurses in Surgical Center, Center of Material and Sterilization and Anesthesic Recuperation (SOBECC), in order to get given how this process of sterilization has been executed. Of the 560 questionnaires delivered, 113 (20.1%) had been returned. About the characteristics of the respondents, 89.1% were nurses, presented age between 25 and 50 years, with average time of formation of 12,7 years, being the majority of the Southeastern region, 46,0% worked in Surgical Center (CC) and 36.0% in the Center of Material (CME), with average of performance in the service of 8,1 years. About the characteristics of the institution, 40.0% were of public institutions and 72.0% of general character. In relation to the use of the flash cycle, 41.0% carry through in to the conventional sterilizers, being that 69.0% had its sterilizers in the CME, place where 73.4% carried through the cleanness of the material. For this activity, 61.4% had defined rules, and 12.7% made it without detergent being that of the involved professionals in this process, 81.2% were of nursing. For situations of emergency more than 90.0% used the flash sterilization method, but a reasonable number of respondents (38.0%) used it as routine, what it confirmed the hypothesis of the research, demonstrating not the fulfilment of the recommendations of the international lines of direction and yes, the “adequacy” of an armory of instruments to take care of the surgical demand. Of who packed the material (62.2%), 84.0% reprocessed it in case that he were not used. The flash sterilization of implanted is carried through by only 8.0%. Of the respondents, 78.0% monitored the process in some way, also with chemical and biological pointer 46.7%. How much to the association of the frequency of use of the flash cycle with the presence of the table sterilizers it is inferred that the insertion of this equipment in the market has stimulated the use of this cycle for the professionals. In the study, it was perceived that the indices of who make it in inadequate way, considering all the reprocessing, are preoccupying. By these indices, the recommendations of the international lines of direction cannot be questioned, but it understands that the persistence in reeducation the professional of health and not simply to forbid it without giving goods justifications is an optimum way. The steam sterilization in flash cycle must be carried through just if all basic steps in the reprocessing of materials will be fulfilled