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

Engineering bio-based polymers using alternative solvents and processes

The work presented in this thesis explores novel routes for the processing of bio-based polymers, developing a sustainable approach based on the use of alternative solvents such as supercritical carbon dioxide (scCO2), ionic liquids (ILs) and deep eutectic solvents (DES). The feasibility to produce polymeric foams via supercritical fluid (SCF) foaming, combined with these solvents was assessed, in order to replace conventional foaming techniques that use toxic and harmful solvents. A polymer processing methodology is presented, based on SCF foaming and using scCO2 as a foaming agent. The SCF foaming of different starch based polymeric blends was performed, namely starch/poly(lactic acid) (SPLA) and starch/poly(ε-caprolactone) (SPCL). The foaming process is based on the fact that CO2 molecules can dissolve in the polymer, changing their mechanical properties and after suitable depressurization, are able to create a foamed (porous) material. In these polymer blends, CO2 presents limited solubility and in order to enhance the foaming effect, two different imidazolium based ILs (IBILs) were combined with this process, by doping the blends with IL. The use of ILs proved useful and improved the foaming effect in these starch-based polymer blends. Infrared spectroscopy (FTIR-ATR) proved the existence of interactions between the polymer blend SPLA and ILs, which in turn diminish the forces that hold the polymeric structure. This is directly related with the ability of ILs to dissolve more CO2. This is also clear from the sorption experiments results, where the obtained apparent sorption coefficients in presence of IL are higher compared to the ones of the blend SPLA without IL. The doping of SPCL with ILs was also performed. The foaming of the blend was achieved and resulted in porous materials with conductivity values close to the ones of pure ILs. This can open doors to applications as self-supported conductive materials. A different type of solvents were also used in the previously presented processing method. If different applications of the bio-based polymers are envisaged, replacing ILs must be considered, especially due to the poor sustainability of some ILs and the fact that there is not a well-established toxicity profile. In this work natural DES – NADES – were the solvents of choice. They present some advantages relatively to ILs since they are easy to produce, cheaper, biodegradable and often biocompatible, mainly due to the fact that they are composed of primary metabolites such as sugars, carboxylic acids and amino-acids. NADES were prepared and their physicochemical properties were assessed, namely the thermal behavior, conductivity, density, viscosity and polarity. With this study, it became clear that these properties can vary with the composition of NADES, as well as with their initial water content. The use of NADES in the SCF foaming of SPCL, acting as foaming agent, was also performed and proved successful. The SPCL structure obtained after SCF foaming presented enhanced characteristics (such as porosity) when compared with the ones obtained using ILs as foaming enhancers. DES constituted by therapeutic compounds (THEDES) were also prepared. The combination of choline chloride-mandelic acid, and menthol-ibuprofen, resulted in THEDES with thermal behavior very distinct from the one of their components. The foaming of SPCL with THEDES was successful, and the impregnation of THEDES in SPCL matrices via SCF foaming was successful, and a controlled release system was obtained in the case of menthol-ibuprofen THEDES.

Vermiculite bio-barriers for Cu and Zn remediation: an eco-friendly approach for freshwater and sediments protection

The increase in heavy metal contamination in freshwater systems causes serious environmental problems in most industrialized countries, and the effort to find ecofriendly techniques for reducing water and sediment contamination is fundamental for environmental protection. Permeable barriers made of natural clays can be used as low-cost and eco-friendly materials for adsorbing heavy metals from water solution and thus reducing the sediment contamination. This study discusses the application of permeable barriers made of vermiculite clay for heavy metals remediation at the interface between water and sediments and investigates the possibility to increase their efficiency by loading the vermiculite surface with a microbial biofilm of Pseudomonas putida, which is well known to be a heavy metal accumulator. Some batch assays were performed to verify the uptake capacity of two systems and their adsorption kinetics, and the results indicated that the vermiculite bio-barrier system had a higher removal capacity than the vermiculite barrier (?34.4 and 22.8 % for Cu and Zn, respectively). Moreover, the presence of P. putida biofilm strongly contributed to fasten the kinetics of metals adsorption onto vermiculite sheets. In open-system conditions, the presence of a vermiculite barrier at the interface between water and sediment could reduce the sediment contamination up to 20 and 23 % for Cu and Zn, respectively, highlighting the efficiency of these eco-friendly materials for environmental applications. Nevertheless, the contribution of microbial biofilm in open-system setup should be optimized, and some important considerations about biofilm attachment in a continuous-flow system have been discussed.

Untersuchungen zur Nutzvolumenkapazität von stark sauren Kationenaustauschern

Ionenaustausch zieht sich durch viele Wissenschafts- und Wirtschaftsanwendungen. Diese Technologie wird allgemein zur Entfernung von gelösten Ionen aus einer wässrigen Phase genutzt. Erst in den 1950er Jahren entwickelt, ist sie heute voll ausgereift. Ihre Anwendung findet diese Technologie vor allem in der Wasseraufbereitung, Lebensmittel-, Chemie- und Pharmaindustrie. Die Demineralisierung von Wasser und die Wasserenthärtung sind vor allem in der Pharmaindustrie durch ihre hohen Wasserqualitätsansprüche von Bedeutung. Sogar für wertvolle Materialien, wie Uran und Plutonium, aus dem Abfall der nuklearen Industrie können Ionenaustauscher eingesetzt werden. Die elektrostatische Sorption in das Ionenaustauschermaterial ist entscheidend. Die entfernten Ionen aus dem Austauscher, werden durch die gleiche Ionenanzahl dergleichen Ladung in der Lösung ersetzt. Der Ionenaustausch wird durch verschiedene Parameter beeinflusst. Ein wichtiger Parameter ist die Kapazität und somit die Nutzzeit des Austauscherharzes im Betrieb. Somit spiegelt die Kapazität die Wirtschaftlichkeitdes Harzes wieder. Die Kapazität wird in Gesamtkapazität und nutzbare Kapazität unterschieden. Die Gesamtkapazität stellt die Gesamtzahl der austauschbaren Ionen dar. Die nutzbare Kapazität ist stets niedriger. Diese misst die Anzahl der Aktivgruppen,wo Ionenaustausch in der Sättigungsphase wirklich stattgefunden hat. Diese Arbeit soll einen Überblick über das große Thema der Ionenaustauscher geben. Dabei wird erläutert, was Ionenaustauscher sind und wie sie funktionieren. Im experimentellen Teil wird die nutzbare Kapazität eines stark sauren Kationenaustauschers bestimmt.

Preparació i caracterització de materials mesoporosos en sistemes tensioactius

Estudi elaborat a partir d’una estada a la Universitat Nacional de Yokohama des de maig fins a mitjans de juny del 2006. S'ha estudiat el comportament fàssic i la preparació de sílica mesoporosa pels nous tensioactius fluorats d'estructura C8F17SO2(C3H7)N(C2H4O)nH (abreujat C8F17(EO)n. El tensioactiu C8F17(EO)n forma micel•les allargades i cristalls líquids en aigua, i per tant pot ser adequat per a la preparació de materials mesoporosos. Sílica mesoestructurada es va preparar pel mètode de precipitació per autoagregació cooperativa. Un estudi sistemàtic es va realitzar, investigant la influència de les concentracions de tensioactiu i precursor (TEOS), l’efecte del pH i de la longitud de cadena de poliòxid d’etilè. Els materials es van caracteritzar per raigs X a angle petit (SAXS), sorció de nitrògen i TEM. Els materials obtinguts presenten diàmetres de por petits i parets de por gruixudes. A més, aquests materials posseeixen altes superfícies específiques, que s’han obtingut emprant concentracions de tensioactiu petites, produint parets de por robustes sense microporositat significativa. La superfície específica es manté durant el procés de calcinació, malgrat un petit encongiment degut a l’entrecreuament de la sílica. Els materials de sílica obtinguts han mostrat ser significativament més robustos que altres materials similars descrits a la bibliografia, com la sílica MCM-41.

Effect of biological surlie ageing on the sparkling wines’ quality and elaoration

Report for the scientific sojourn at the Université de Bourgogne, France, from July until October 2007..Surlie ageing after second fermentation is a fundamental operation in the production of quality sparkling wine like Cava and Champagne. Recently, the importance of the interaction between wine and lees cell surface has been reported. Cell surface properties depending on wall biochemical composition are major determinants in microbial interactions, having important repercussions in several technological aspects. Sorption and flocculation are especially important in sparkling wine production, and are governed by distinct cell surface properties. The aim of the present research carried out during the four months of the stage was to know the implication of lees surface modifications occurring during surlie ageing in sparkling wine quality and elaboration. The relationship between physico-chemical properties such as hydrophobicity, charge and electron-donor characteristics, and the yeast surface sorption capacities, we determined these factors in a model system. Then, real industrial lees samples were investigated. The surface properties of sparkling wine lees from the same strain of Saccharomyces cerevisiae were characterized according to the time of surlie ageing, and their possible influence on lees sorption and flocculation capacity was evaluated. Surlie ageing after second fermentation is a fundamental operation in the production of quality sparkling wine like Cava and Champagne. Recently, the importance of the interaction between wine and lees cell surface has been reported. Cell surface properties depending on wall biochemical composition are major determinants in microbial interactions, having important repercussions in several technological aspects. Sorption and flocculation are especially important in sparkling wine production, and are governed by distinct cell surface properties. The aim of the present research carried out during the four months of the stage was to know the implication of lees surface modifications occurring during surlie ageing in sparkling wine quality and elaboration. The relationship between physico-chemical properties such as hydrophobicity, charge and electron-donor characteristics, and the yeast surface sorption capacities, we determined these factors in a model system. Then, real industrial lees samples were investigated. The surface properties of sparkling wine lees from the same strain of Saccharomyces cerevisiae were characterized according to the time of surlie ageing, and their possible influence on lees sorption and flocculation capacity was evaluated.

Ecological characteristics of Triatoma patagonica at the Southern limit of its distribution (Chubut, Argentina)

This study aimed at identifying the ecological characteristics of Triatoma patagonica Del Ponte 1929 (Hemiptera: Reduviidae) and evaluating the epidemiological importance of this species at its southernmost distribution limit. We carried out two surveys in the Province of Chubut, in summer and in spring, 1998. In each survey, we interviewed local health care agents for triatomine recognition and reports of the bugs, followed by entomological searches in houses and peridomestic and silvatic biotopes. The presence of T. patagonica was confirmed in two of the five localities indicated by interview. In agreement with previous studies, all these positive localities were east of the 11°C isotherm, within the Monte phytogeographic province. Triatomine abundance and infestation levels (in peridomiciles and peridomestic biotopes) were higher in summer than in spring, possibly reflecting adverse environmental conditions such as flood and cold winter weather. In the silvatic environment, we found three adult bugs under rocks in summer. In peridomestic sites bugs were only found associated with chickens, which were also the only blood meal source identified. Infection by Trypanosoma cruzi was not detected. We conclude that T. patagonica at its southernmost distribution limit does not represent a risk to public health due to its low abundance, lack of association with humans, and absence of T. cruzi infection.

Remediation of a marine shore tailings deposit and the importance of water-rock interaction on element cycling in the coastal aquifer

We present the study of the geochemical processes associated with the first successful remediation of a marine shore tailings deposit in a coastal desert environment (Bahia de Ite, in the Atacama Desert of Peru). The remediation approach implemented a wetland on top of the oxidized tailings. The site is characterized by a high hydrauliz gradient produced by agricultural irrigation on upstream gravel terraces that pushed river water (similar to 500 mg/L SO(4)) toward the sea and through the tailings deposit. The geochemical and isotopic (delta(2)H(water) and delta(18)O(water), delta(34)S(sulfate) , delta(18)O(sulfate)) approach applied here revealed that evaporite horizons (anhydrite and halite) in the gravel terraces are the source of increased concentrations of SO(4), Cl, and Na up to similar to 1500 mg/L in the springs at the base of the gravel terraces. Deeper groundwater interacting with underlying marine sequences increased the concentrations of SO(4), Cl, and Na up to 6000 mg/L and increased the alkalinity up to 923 mg/L CaCO(3) eq. in the coastal aquifer. These waters infiltrated into the tailings deposit at the shelf-tailings interface. Nonremediated tailings had a low-pH oxidation zone (pH 1-4) with significant accumulations of efflorescent salts (10-20 cm thick) at the surface because of upward capillary transport of metal cations in the arid climate. Remediated tailings were characterized by neutral pH and reducing conditions (pH similar to 7, Eh similar to 100 mV). As a result, most bivalent metals such as Cu, Zn, and Ni had very low concentrations (around 0.01 mg/L or below detection limit) because of reduction and sorption processes. In contrast, these reducing conditions increased the mobility of iron from two sources in this system: (1) The originally Fe(III)-rich oxidation zone, where Fe(II) was reduced during the remediation process and formed an Fe(II) plume, and (2) reductive dissolution of Fe(III) oxides present in the original shelf lithology formed an Fe-Mn plume at 10-m depth. These two Fe-rich plumes were pushed toward the shoreline where more oxidizing and higher pH conditions triggered the precipitation of Fe(HI)hydroxide coatings on silicates. These coatings acted as a filter for the arsenic, which naturally infiltrated with the river water (similar to 500 mu g/L As natural background) into the tailings deposit.

A double layer model of the gas bubble/water interface

Zeta potential is a physico-chemical parameter of particular importance to describe sorption of contaminants at the surface of gas bubbles. Nevertheless, the interpretation of electrophoretic mobilities of gas bubbles is complex. This is due to the specific behavior of the gas at interface and to the excess of electrical charge at interface, which is responsible for surface conductivity. We developed a surface complexation model based on the presence of negative surface sites because the balance of accepting and donating hydrogen bonds is broken at interface. By considering protons adsorbed on these sites followed by a diffuse layer, the electrical potential at the head-end of the diffuse layer is computed and considered to be equal to the zeta potential. The predicted zeta potential values are in very good agreement with the experimental data of H-2 bubbles for a broad range of pH and NaCl concentrations. This implies that the shear plane is located at the head-end of the diffuse layer, contradicting the assumption of the presence of a stagnant diffuse layer at the gas/water interface. Our model also successfully predicts the surface tension of air bubbles in a KCl solution. (c) 2012 Elsevier Inc. All rights reserved.

Caution on the storage of waters and aqueous solutions in plastic containers for hydrogen and oxygen stable isotope analysis

RATIONALE The choice of containers for storage of aqueous samples between their collection, transport and water hydrogen (2H) and oxygen (18O) stable isotope analysis is a topic of concern for a wide range of fields in environmental, geological, biomedical, food, and forensic sciences. The transport and separation of water molecules during water vapor or liquid uptake by sorption or solution and the diffusive transport of water molecules through organic polymer material by permeation or pervaporation may entail an isotopic fractionation. An experiment was conducted to evaluate the extent of such fractionation. METHODS Sixteen bottle-like containers of eleven different organic polymers, including low and high density polyethylene (LDPE and HDPE), polypropylene (PP), polycarbonate (PC), polyethylene terephthalate (PET), and perfluoroalkoxy-Teflon (PFA), of different wall thickness and size were completely filled with the same mineral water and stored for 659?days under the same conditions of temperature and humidity. Particular care was exercised to keep the bottles tightly closed and prevent loss of water vapor through the seals. RESULTS Changes of up to +5 parts per thousand for d2H values and +2.0 parts per thousand for d18O values were measured for water after more than 1?year of storage within a plastic container, with the magnitude of change depending mainly on the type of organic polymer, wall thickness, and container size. The most important variations were measured for the PET and PC bottles. Waters stored in glass bottles with Polyseal (TM) cone-lined PP screw caps and thick-walled HDPE or PFA containers with linerless screw caps having an integrally molded inner sealing ring preserved their original d2H and d18O values. The carbon, hydrogen, and oxygen stable isotope compositions of the organic polymeric materials were also determined. CONCLUSIONS The results of this study clearly show that for precise and accurate measurements of the water stable isotope composition in aqueous solutions, rigorous sampling and storage procedures are needed both for laboratory standards and for unknown samples. Copyright (c) 2012 John Wiley & Sons, Ltd.

Geochemistry and stable isotope composition of fresh alkaline porphyry copper tailings: Implications on sources and mobility of elements during transport and early stages of deposition

Prevention of acid mine drainage (AMD) in sulfide-containing tailings requires the identification of the geochemical processes and element pathways in the early stages of tailing deposition. However, analyses of recently deposited tailings in active tailings impoundments are scarce because mineralogical changes occur near the detection limits of many assays. This study shows that a detailed geochemical study which includes stable isotopes of water (delta H-2, delta O-18), dissolved sulfates (delta S-34, delta O-18) and hydrochernical parameter (pH, Eh, DOC, major and trace elements) from tailings samples taken at different depths in rainy and dry seasons allows the understanding of weathering (oxidation, dissolution, sorption, and desorption), water and element pathways, and mixing processes in active tailings impoundments. Fresh alkaline tailings (pH 9.2-10.2) from the Cu-Mo porphyry deposit in El Teniente, Chile had low carbonate (0.8-1.1 Wt-% CaCO3 equivalent) and sulfide concentrations (0.8-1.3 wt.%, mainly as pyrite). In the alkaline tailings water, Mo and Cu (up to 3.9 mg/L Mo and 0.016 mg/L Cu) were mobile as MoO42- and Cu (OH)(2)(0). During the flotation, tailings water reached equilibrium with gypsum (up to 738 mg/L Ca and 1765 mg/ L SO4). The delta S-34 VS. delta O-18 covariations of dissolved sulfate (2.3 to 4.5% delta S-34 and 4.1 to 6.0 % delta O-18) revealed the sulfate sources: the dissolution of primary sulfates (12.0 to 13.2%. delta S-34, 7.4 to 10.9%.delta O-18) and oxidation of primary sulfides (-6.7 to 1.7%. delta S-34). Sedimented tailings in the tailings impoundment can be divided into three layers with different water sources, element pathways, and geochemical processes. The deeper sediments (> 1 m depth) were infiltrated by catchment water, which partly replaced the original tailings water, especially during the winter season. This may have resulted in the change from alkaline to near-neutral pH and towards lower concentrations of most dissolved elements. The neutral pH and high DOC (up to 99.4 mg/L C) of the catchment water mobilized Cu (up to 0.25 mg/L) due to formation of organic Cu complexes; and Zn (up to 130 mg/L) due to dissolution of Zn oxides and desorption). At I m depth, tailings pore water obtained during the winter season was chemically and isotopically similar to fresh tailings water (pH 9.8-10.6, 26.7-35.5 mg/L Cl, 2.3-6.0 mg/L Mo). During the summer, a vadose zone evolved locally and temporarily up to 1.2 m depth. resulting in a higher concentration of dissolved solids in the pore water due to evaporation. During periodical new deposition of fresh tailings, the geochemistry of the surface layer was geochemically similar to fresh tailings. In periods without deposition, sulfide oxidation was suggested by decreasing pH (7.7-9.5), enrichment of MoO42- and SO42-, and changes in the isotopic composition of dissolved sulfates. Further enrichment for Na, K, Cl, SO4, Mg, Cu, and Mo (up to 23.8 mg/L Mo) resulted from capillary transport towards the surface followed by evaporation and the precipitation of highly soluble efflorescent salts (e.g., mirabilite, syngenite) at the tailing surface during summer. (C) 2008 Elsevier B.V. All rights reserved.

Aspectos hidrológicos en el fondo marino peruano asociados a la Extensión Sur de la Corriente Cromwell (ESCC) entre 3° y 7°S

Para determinar la variabilidad estacional y espacial en el fondo marino del norte peruano, durante los últimos 30 años (1980-2009), se estudió la temperatura y el oxígeno disuelto entre las latitudes 3°-7°S. Se halló una mayor proyección latitudinal del oxígeno disuelto (OD), superior a 1,0 mL/L en la estación de otoño, delimitada por la isoterma de 15 °C al borde de la plataforma. Esta proyección estaría asociada a los flujos subsuperficiales hacia el sur, que constituyen la Extensión Sur de la Corriente de Cromwell (ESCC), a profundidades de 90-180 m. La oxigenación estaría influenciada por el incremento o repliegue de la ESCC presente en el área. La variación media de oxígeno registra valores de 0,7-1,3 mL/L en verano y 0,8-1,6 mL/L en otoño. Paita (5°S) presenta valores promedio de 1,0 mL/L en verano y de 1,4 mL/L en otoño. Los mayores valores de OD se asocian a latitudes menores en ambas estaciones; la estación de otoño presenta los mayores tenores de oxígeno, asociados a una mayor intensidad de la ESCC.