Evaluación de tenacidad a la fractura e integridad estructural de tubos de generadores de vapor nucleares.

Dado el impacto negativo asociado a la ocurrencia de fallas en tubos de generadores de vapor (TGVs) en centrales nucleares, el estudio de la integridad estructural de éstos ha comenzado a recibir mayor atención recientemente. Diversas metodologías basadas en análisis de carga límite han sido propuestas para asegurar la integridad estructural de los tubos, según los requerimientos establecidos por las autoridades regulatorias. Éstas han conducido, sin embargo, a la definición de criterios de reparación o taponado de TGVs excesivamente conservativos. Por lo tanto, con el objetivo de reducir la cantidad de tubos innecesariamente removidos de servicio, nuevos criterios de evaluación de integridad han sido propuestos recientemente en la literatura. En este contexto, la mecánica de fractura elastoplástica se presenta como una alternativa para la evaluación de la integridad de TGVs, requiriéndose dos elementos para su aplicación: la estimación de la fuerza impulsora en términos del parámetro elastoplástico (por ejemplo, la integral J) y la medición experimental de la tenacidad a la fractura del material de los tubos (por ejemplo, a través de la curva de resistencia J-R). Este trabajo presenta el desarrollo de técnicas experimentales no normalizadas para la determinación de curvas J-R para TGVs con fisuras pasantes circunferenciales y longitudinales. Debido a las dimensiones reducidas de los TGVs, diferentes probetas no normalizadas fueron propuestas. Además, en los ensayos se utilizaron condiciones de carga de tracción y flexión con el objetivo de modelar más adecuadamente los estados tensionales y las condiciones de constraint reales en TGVs. Los valores de la integral J fueron estimados utilizando el método del factor η. La aptitud del método fue evaluada a partir de simulaciones numéricas de los ensayos propuestos mediante análisis elastoplásticos con la técnica de elementos finitos. Se encontró que condiciones de mayor constraint asociadas con fisuras profundas y cargas de flexión favorecen la validez del método del factor η, mientras que configuraciones de menor constraint dan como resultado factores η que exhiben una mayor dependencia con el nivel de carga aplicada. También se observó que los factores η basados en la apertura de la boca de la fisura (Crack Mouth Opening Displacement o CMOD) presentan una dependencia mucho menor con el nivel de carga respecto a los factores η definidos a partir del desplazamiento del punto de aplicación de la carga (Load Line Displacement o LLD). Se presentan los valores del factor η para las probetas estudiadas con fisuras profundas (a/W ≥ 0,40). Se realizaron ensayos de fractura a temperatura ambiente y 300 °C con probetas obtenidas de TGVs nucleares fabricados a partir de las aleaciones 690 (Ni: 61; Cr: 29; Fe: 8,95, % en peso) y 800 (Ni: 33; Cr: 21,6; Fe: 42,2, % en peso). Durante los ensayos de fractura a temperatura ambiente, la extensión estable de fisura fue medida mediante una técnica óptica utilizando un microscopio digital. Para estos ensayos también se aplicó el método de normalización que propone la norma ASTM E1820-15 en el Anexo 15, encontrándose una buena coincidencia entre las longitudes estimadas por éste y las medidas ópticamente. De esta manera, el método de normalización fue utilizado para los ensayos a alta temperatura. Los resultados experimentales mostraron que ambos materiales tienen elevadas tenacidades a la fractura, siendo la aleación 800 la que presentó curvas J-R más elevadas que la aleación 690 tanto para fisuras circunferenciales como longitudinales. Las curvas J-R para ambas aleaciones mostraron un efecto marcado con la orientación de la fisura, es decir que existe una importante anisotropía en las propiedades de fractura: las fisuras circunferenciales presentaron curvas J-R más elevadas que las fisuras longitudinales. El nivel de constraint desarrollado en los ensayos, dado por las condiciones de carga de tracción y flexión, evidenció poco efecto sobre las curvas J-R para probetas con fisuras profundas (a/W ~ 0,50). A su vez, la temperatura de ensayo (temperatura ambiente y 300 °C) presentó un efecto prácticamente nulo para ambas aleaciones. Usando las propiedades de fractura obtenidas en este trabajo, la metodología FAD (Failure Assessment Diagram) fue propuesta y utilizada para la predicción de las condiciones de falla de TGVs fisurados para diferentes geometrías de fisura y condiciones de carga. La comparación entre análisis teóricos y datos experimentales muestra la potencialidad del FAD como una metodología capaz de predecir adecuadamente las fallas de estos componentes.

Diseño de una turbina experimental de vapor de baja potencia.

Este trabajo se enfoca en el diseño de una turbina de vapor de carácter experimental para simular, en un laboratorio de transferencia térmica, la dinámica propia de una turbina de mayor tamaño en el circuito secundario de un ciclo de potencia. La máquina diseñada produciría 185 kW de potencia en el eje a 9.000 RPM con un rendimiento interno del 88 %, tomando en la entrada 0,4 kg/s de vapor saturado a 40 bar y descargando a una presión de 1,5 bar. Se desarrolló la teoría de turbomáquinas necesaria para realizar los cálculos fuidodinámicos y se propuso un método de diseño apropiado para el alcance del trabajo. Se decidió que la turbina sería de tres etapas, dos Curtis y una de impulso, y se realizaron los cálculos correspondientes. Una vez que el diseño fluidodinámico estaba definido, se procedió a dimensionar los distintos elementos mecánicos, con el alcance correspondiente a ingeniería conceptual y básica. Se realizaron detalladamente los cálculos propios del dimensionado del rotor (eje y discos), rodamientos, carcasa, válvula de seguridad de presión y asociados. Además se presentó el diseño conceptual de los elementos restantes, sistema de control y otros auxiliares. Finalmente, se realizaron los modelos en software 3D de todas las piezas y se produjeron los planos correspondientes.

Evaluación de la integridad estructural de tubos de generadores de vapor con defectos volumétricos debidos al fretting.

Los Generadores de vapor (GVs) en una central nuclear están conformados por un manojo de tubos que actúan como una barrera entre el sistema primario contaminado y el secundario. A través de los tubos de GVs (TGVs) se desarrolla el intercambio de calor que produce el vapor que después accionará las turbinas de la central. Estos componentes están sometidos a unas condiciones térmicas, químicas y mecánicas bastante severas, que pueden provocar la aparición de defectos geométricos y volumétricos comprometiendo su integridad estructural. Es por esta razón que el mantenimiento de los GVs es importante para la operación económica y segura de las centrales nucleares. Uno de los principales mecanismos de desgaste de los tubos de GVs es el fenómeno conocido como fretting. El mismo provoca el adelgazamiento de las paredes de los TGVs debido a pequeños movimientos relativos entre superficies en contacto. Dado el caso particular de los GVs del reactor CAREM-25 en los que el circuito primario se encuentra del lado externo de los tubos que lo constituyen, la ocurrencia de este mecanismo de daño podría comprometer la integridad de los mismos haciéndolos más susceptibles al daño por colapso. El presente trabajo constituye una continuación del Proyecto integrador finalizado en el 2015 por Pablo Lazo en el que se evaluó la influencia de efectos de ovalización en el colapso de los tubos de los GVs. Se evalúa ahora la influencia de defectos volumétricos debido a fretting. Esto se realizó a través de modelos numéricos que estiman la presión de colapso en los tubos con y sin defecto. Los resultados de los modelos se compararon con resultados de expresiones analíticas obtenidas por otros autores, valores experimentales propios y otros valores de referencia. A partir del análisis de los resultados se derivaron algunas conclusiones que ayudan a entender el comportamiento de los tubos de GVs con defectos debido a mecanismo de daño por fretting. Además se desarrollaron expresiones matemáticas que ayudan a definir las dimensiones de los defectos que comprometen la integridad estructural de los TGVs en el caso del reactor CAREM-25.

Evaluation of mechanical properties and water vapor permeability in Chitosan biofilms using Sorbitol and Glycerol

Chitosan biofilms were prepared with and without plasticizer (glycerol and sorbitol). The physical and mechanical properties of chitosan biofilms with and without plasticizer were evaluated. Chitosan was obtained from shrimp wastes and characterized. The film forming solution (FFS) was obtained through chitosan dissolution and drying. The solution had its pH adjusted to 6.0 and oven dried (40 8C, 24 h) with forced air circulation. Chitosan biofilms without plasticizer showed a tensile strength about 36% higher than biofilms produced with plasticizer. On the other hand, biofilms with plasticizer presented superior values of elongation. The permeability of the water vapor and color presented significant difference (p<0.05) between all biofilms. Chitosan/plasticizer biofilms showed higher values of water vapor permeability in relation to chitosan biofilms without plasticizer.

Growth and characterization of III-V compound semiconductor nanostructures by metalorganic chemical vapor deposition

Planar <110> GaAs nanowires and quantum dots grown by atmospheric MOCVD have been introduced to non-standard growth conditions such as incorporating Zn and growing them on free-standing suspended films and on 10° off-cut substrates. Zn doped nanowires exhibited periodic notching along the axis of the wire that is dependent on Zn/Ga gas phase molar ratios. Planar nanowires grown on suspended thin films give insight into the mobility of the seed particle and change in growth direction. Nanowires that were grown on the off-cut sample exhibit anti-parallel growth direction changes. Quantum dots are grown on suspended thin films and show preferential growth at certain temperatures. Envisioned nanowire applications include twin-plane superlattices, axial pn-junctions, nanowire lasers, and the modulation of nanowire growth direction against an impeding barrier and varying substrate conditions.

Improving the stability of an oxime based electrochemical microsensor for organo-phosphate vapor detection

A micro gas sensor has been developed by our group for the detection of organo-phosphate vapors using an aqueous oxime solution. The analyte diffuses from the high flow rate gas stream through a porous membrane to the low flow rate aqueous phase. It reacts with the oxime PBO (1-Phenyl-1,2,3,-butanetrione 2-oxime) to produce cyanide ions, which are then detected electrochemically from the change in solution potential. Previous work on this oxime based electrochemistry indicated that the optimal buffer pH for the aqueous solution was approximately 10. A basic environment is needed for the oxime anion to form and the detection reaction to take place. At this specific pH, the potential response of the sensor to an analyte (such as acetic anhydride) is maximized. However, sensor response slowly decreases as the aqueous oxime solution ages, by as much as 80% in first 24 hours. The decrease in sensor response is due to cyanide which is produced during the oxime degradation process, as evidenced by the cyanide selective electrode. Solid phase micro-extraction carried out on the oxime solution found several other possible degradation products, including acetic acid, N-hydroxy benzamide, benzoic acid, benzoyl cyanide, 1-Phenyl 1,3-butadione, 2-isonitrosoacetophenone and an imine derived from the oxime. It was concluded that degradation occurred through nucleophilic attack by a hydroxide or oxime anion to produce cyanide, as well as a nitrogen atom rearrangement similar to Beckmann rearrangement. The stability of the oxime in organic solvents is most likely due to the lack of water, and specifically hydroxide ions. The reaction between oxime and organo-phosphate to produce cyanide ions requires hydroxide ions, and therefore pure organic solvents are not compatible with the current micro-sensor electrochemistry. By combining a concentrated organic oxime solution with the basic aqueous buffer just prior to being used in the detection process, oxime degradation can be avoided while preserving the original electrochemical detection scheme. Based on beaker cell experiments with selective cyanide sensitive electrodes, ethanol was chosen as the best organic solvent due to its stabilizing effect on the oxime, minimal interference with the aqueous electrochemistry, and compatibility with the current microsensor material (PMMA). Further studies showed that ethanol had a small effect on micro-sensor performance by reducing the rate of cyanide production and decreasing the overall response time. To avoid incomplete mixing of the aqueous and organic solutions, they were pre-mixed externally at a 10:1 ratio, respectively. To adapt the microsensor design to allow for mixing to take place within the device, a small serpentine channel component was fabricated with the same dimensions and material as the original sensor. This allowed for seamless integration of the microsensor with the serpentine mixing channel. Mixing in the serpentine microchannel takes place via diffusion. Both detector potential response and diffusional mixing improve with increased liquid residence time, and thus decreased liquid flowrate. Micromixer performance was studies at a 10:1 aqueous buffer to organic solution flow rate ratio, for a total rate of 5.5 μL/min. It was found that the sensor response utilizing the integrated micromixer was nearly identical to the response when the solutions were premixed and fed at the same rate.

Seleção e divergência genética de pessegueiros e nectarineiras e susceptibilidade a danos causados pelo frio na Estación Experimental de Aula Dei (CSIC)

The peaches and nectarines are highly appreciated by consumer, but it is climacteric fruits, with availability in the market in small time. It is necessary to invest to obtain genotypes with fruit quality and small perishability or that it presente less physiological disorders after storage. The aims of this work were i) to evaluate the genetic divergence among 40 peach and nectarine trees genotypes based on postharvest quality and select posible parents; ii) to evaluate the susceptibility to chilling injury in peaches and nectarines after cold storage; iii) to evaluate divergence of peaches and nectarines on the basis in the susceptibility for chiling injury and select superior genotypes; iv) evaluate the correlations between quality and susceptibility to chilling injury of peaches and nectarines v) select parents with the combination of lower susceptibility to chilling injury and higher quality fruit. The study was carried out in EEAD-CSIC, Zaragoza - Spain, during the production cycle 2013/2014. A total of 40 peaches and nectarines genotypes from germplasm collection were evaluated. The quality characteristics as flesh firmness, total soluble solids, titratable acidity, pH, rippining index and flesh color parameters were evaluated. The fruits were submitted to cold storage at 0 °C and 5 °C, with 95% average relative humidity. The evaluations were after 14 and 28 days, it being observed the presence of symptoms, such as wooliness through mealiness, flesh grainy, leatheriness and flesh color changes, through browning, bleeding and off flavor. As a selection parameter was adopted 20% of genotypes that had a higher frequency of superiority for quality characteristics, susceptibility to chilling injury and the combining of both. For quality characteristic presented greater divergence the ‘Queen Giant’, ‘Sudanel Blanco’ and ‘Borracho de Jarque’. Based on the quality the eight genotypes were selected, ‘Andross’, ‘San Jaime’, ‘San Lorenzo’, ‘Borracho de Jarque’, ‘Sudanell 1’, ‘Carson’, ‘Baby Gold 6’ and ‘Stanford’. All genotypes studied exhibited susceptibility to one or more symptoms caused by cold storage during 28 days, independent of temperature. For 14 days, the ‘Baby Gold 6’, ‘Flavortop’ and ‘Queen Giant’ genotypes did not show any physiological disorder caused by cold. In general, the temperature of 0 °C favored fruit postharvest conservation, it have a lower incidence and severity of symptoms caused by cold storage. The storage for 14 days contributed for the lower incidence of damage in the genotypes fruits studied. For 14 days, with both temperatures, it was observed divergence for ‘Queen Giant’, ‘Sudanell Blanco’, ‘Baby Gold 6’ ‘GF3’, ‘Baby Gold 8’, ‘Campiel’ and ‘Campiel Rojo’ genotypes. For 28 days, in the 5 °C condition, ‘Queen Giant’, ‘Big Top’, ‘Flavortop’ and ‘Redhaven’ genotypes were divergents. Based on susceptibility to chilling injury at 0 °C, the eight genotypes were selected, it being these, ‘Queen Giant’, ‘Keimoes’, ‘Flavortop’, ‘Big Top’, 'Redhaven', 'Sudanell 3', 'Bonet I' and ‘Carson’. The quality parameters as rippining index, soluble solids, firmness and titratable acidity presented correlation among them. These, also it had correlation with woolines and bowning, what it indicate that fruits with more ripening can have this symptoms more easily. The browning, mealiness, flesh grainy and off flavor variables were correlationed with the time period and temperartures, what it confirm that these symptoms are the main disorders caused by cold storage. The quality characteristics together susceptibility to chilling injury allowed selected ‘Baby Gold 6’, ‘Sarell’, ‘Keimoes’, ‘GF3’ ‘San Jaime’, ‘Big Top’, ‘Sudanell 1’, ‘Carson’, ‘Baby Gold 8’, and ‘San Lorenzo’ genotypes.

Synthesis, characterization and chemical vapor deposition of transition metal di(tert-butyl)amido compounds

Although the transition metal chemistry of many dialkylamido ligands has been well studied, the chemistry of the bulky di(tert-butyl)amido ligand has been largely overlooked. The di(tert-butyl)amido ligand is well suited for synthesizing transition metal compounds with low coordination numbers; such compounds may exhibit interesting structural, physical, and chemical properties. Di(tert-butyl)amido complexes of transition metals are expected to exhibit high volatilities and low decomposition temperatures, thus making them well suited for the chemical vapor deposition of metals and metal nitrides. Treatment of MnBr₂(THF)₂, FeI₂, CoBr₂(DME), or NiBr₂(DME) with two equivalents of LiN(t-Bu)2 in benzene affords the two-coordinate complex M[N(t-Bu)₂]₂, where M is Mn, Fe, Co, or Ni. Crystallographic studies show that the M-N distances decrease across the series: 1.9365 (Mn), 1.8790 (Fe), 1.845 (Co), 1.798 Å (Ni). The N-M- N angles are very close to linear for Mn and Fe (179.30 and 179.45°, respectively), but bent for Co and Ni (159.2 and 160.90°, respectively). As expected, the d⁵ Mn complex has a magnetic moment of 5.53 μΒ that is very close to the spin only value. The EPR spectrum is nearly axial with a low E/D ratio of 0.014. The d⁶ Fe compound has a room temperature magnetic moment of 5.55 μΒ indicative of a large orbital angular momentum contribution. It does not exhibit a Jahn-Teller distortion despite the expected doubly degenerate ground state. Applied field Mössbauer spectroscopy shows that the effective internal hyperfine field is unusually large, Hint = 105 T. The magnetic moments of Co[N(t-Bu)₂]₂ and Ni[N(t-Bu)₂]₂ are 5.24 and 3.02 μΒ respectively. Both are EPR silent at 4.2 K. Treatment of TiCl₄ with three equivalents of LiN(t-Bu)2 in pentane affords the briding imido compound Ti₂[μ-N(t-Bu)]₂Cl₂[N(t-Bu)₂]₂ via a dealkylation reaction. Rotation around the bis(tert-butyl)amido groups is hindered, with activation parameters of ΔH‡ = 12.8 ± 0.6 kcal mol-1 and ΔS‡ = -8 ± 2 cal K-1 ·mol-1, as evidenced by variable temperature 1H NMR spectroscopy. Treatment of TiCl₄ with two equivalents of HN(t-Bu)₂ affords Ti₂Cl₆[N(t-Bu)₂]₂. This complex shows a close-contact of 2.634(3) Å between Ti and the carbon atom of one of the CH₃ substituents on the tert-butyl groups. Theoretical considerations and detailed structural comparisons suggest this interaction is not agostic in nature, but rather is a consequence of interligand repulsions. Treatment of NiI₂(PPh3)₂ and PdCl₂(PPh₃)₂ with LiN(t-Bu)₂in benzene affords Ni[N(t-Bu)₂](PPh₃)I and Pd₃(μ₂-NBut₂)2(μ₂-PPh₂)Ph(PPh₃) respectively. The compound Ni[N(t-Bu)₂](PPh₃)I has distorted T-shape in geometry, whereas Pd₃(μ₂-NBut₂)₂(μ₂-PPh₂)Ph(PPh₃) contains a triangular palladium core. Manganese nitride films were grown from Mn[N(t-Bu)₂]₂ in the presence of anhydrous ammonia. The growth rate was several nanometers per minute even at the remarkably low temperature of 80⁰C. As grown, the films are carbon- and oxygen-free, and have a columnar morphology. The spacings between the columns become smaller and the films become smoother as the growth temperature is increased. The composition of the films is consistent with a stoichiometry of Mn₅N₂.

BATTERY POWERED PORTABLE VAPOR COMPRESSION CYCLE SYSTEM WITH PCM CONDENSER

A battery powered air-conditioning device was developed to provide an improved thermal comfort level for individuals in inadequately cooled environments. This device is a battery powered air-conditioning system with the phase change material (PCM) for heat storage. The condenser heat is stored in the PCM during the cooling operation and is discharged while the battery is charged by using the vapor compression cycle as a thermosiphon loop. The main focus of the current research was on the development of the cooling system. The cooling capacity of the vapor compression cycle measured was 165.6 W with system COP at 2.85. It was able to provide 2 hours cooling without discharging heat to the ambient. The PCM was recharged in nearly 8 hours under thermosiphon mode.