Optical properties of dye-doped zirconia films by spectroscopic ellipsometry

The optical properties of zirconia films doped with rhodamine 6G and oxazine 725 by the sol-gel process were investigated using spectroscopic ellipsometry (SE). Accurate refractive index n and the extinction coefficient k were determined using a three-oscillator classical Lorentz model in the wavelength range of 300-800 nm. The derived refractive index of dye-doped films exhibited anomalous dispersion in the absorption region. Wavelength tunable output lasing action yellow and near-infrared wavelength region was achieved by DFB configuration using zirconia films doped with R6G and oxazine 725. (c) 2006 Elsevier B.V. All rights reserved.

Kilka population dynamics in the south of the Caspian Sea

Populations of kilka in the Caspian Sea have important role in the food chain. This study was conducted to determine population parameters of three species of kilka in the south of the Caspian Sea, during 2006-2007. Mean length was 102.4±9.7 mm for common kilka, 117.8±6.9 mm for anchovy and 119.5±10.9 mm for bigeye. The relationship between length and weight indicated the negative allometric growth in the all three species. Mean age for common kilka, anchovy and bigeye were 3.6, 4.6 and 4.6 years, respectively. Sex ratio (M:F) were 0.52:1 for anchovy, 0.60:1 for common kilka and 1.60:1 for bigeye. The value of growth coefficient (K) was the highest (0.321) for the common kilka, (0.267) for the bigeye, and the lowest for the anchovy kilka (0.245). Total mortality estimated from the descending of the catch curve using the age structure, Z=1.280 yr-1 for common kilka, Z=1.067 yr-1 for anchovy, and Z=1.015 yr-1 for bigeye. Natural mortality (M) were estimated using Pauly formula as M=0.622, M=0.537 and M=0.503 per year for common kilka, bigeye and anchovy, respectively. Value of fishing mortality (F) were estimated from Z and M, as F=0.658 for common kilka, F=0.564 for anchovy and F=0.478 for bigeye. The exploitation rate (E) were estimated E=0.514 for common kilka, E=0.528 for anchovy and E= 0.471 for bigeye. The estimate of MCY (Maximum Constant Yield) was calculated using the more reliable time series of commercial catch data from 2001-2007, which resulted in an estimate of MCY for the kilka fishery of 14100 tonnes.

An assessment of the earth pressure coefficient in overconsolidated clays

The determination of the earth pressure coefficient K 0 in a natural clay deposit is a problem of considerable significance in geotechnical engineering. While the methods for evaluation of K 0 are reliable for normally consolidated soils, significant difficulties still exist in evaluating K 0 in overconsolidated clays, given that it is influenced by the stress history of the material, together with the age, structure, mineralogical composition and depositional environment. Indeed, some of these factors are responsible for the soil becoming anisotropic. The existing framework for prediction of K 0 in overconsolidated soils does not account for any influences caused by anisotropy. The work reported in this paper evaluates the validity of a revised relationship between K 0oc and OCR (overconsolidation ratio) using data obtained from laboratory investigations. The tests were performed on reconstituted and undisturbed samples of Belfast Upper Boulder Clay, London Clay and Gault Clay. Tests were also performed on reconstituted samples of kaolin. The values of K 0oc were determined using various approaches, including on-sample measurements. The results have confirmed that reliable predictions of K 0oc can be made using the proposed relationship.

Plasma Polymerised Organic Thin Films-A Study on the Structural, Electrical and Nonlinear Optical Properties for Possible Applications

This proposed thesis is entitled “Plasma Polymerised Organic Thin Films: A study on the Structural, Electrical, and Nonlinear Optical Properties for Possible Applications. Polymers and polymer based materials find enormous applications in the realm of electronics and optoelectronics. They are employed as both active and passive components in making various devices. Enormous research activities are going on in this area for the last three decades or so, and many useful contributions are made quite accidentally. Conducting polymers is such a discovery, and eversince the discovery of conducting polyacetylene, a new branch of science itself has emerged in the form of synthetic metals. Conducting polymers are useful materials for many applications like polymer displays, high density data storage, polymer FETs, polymer LEDs, photo voltaic devices and electrochemical cells. With the emergence of molecular electronics and its potential in finding useful applications, organic thin films are receiving an unusual attention by scientists and engineers alike. This is evident from the vast literature pertaining to this field appearing in various journals. Recently, computer aided design of organic molecules have added further impetus to the ongoing research activities in this area. Polymers, especially, conducting polymers can be prepared both in the bulk and in the thinfilm form. However, many applications necessitate that they are grown in the thin film form either as free standing or on appropriate substrates. As far as their bulk counterparts are concerned, they can be prepared by various polymerisation techniques such as chemical routes and electrochemical means. A survey of the literature reveals that polymers like polyaniline, polypyrrole, polythiophene, have been investigated with a view to studying their structural electrical and optical properties. Among the various alternate techniques employed for the preparation of polymer thin films, the method of plasma polymerisation needs special attention in this context. The technique of plasma polymerisation is an inexpensive method and often requires very less infra structure. This method includes the employment of ac, rf, dc, microwave and pulsed sources. They produce pinhole free homogeneous films on appropriate substrates under controlled conditions. In conventional plasma polymerisation set up, the monomer is fed into an evacuated chamber and an ac/rf/dc/ w/pulsed discharge is created which enables the monomer species to dissociate, leading to the formation of polymer thin films. However, it has been found that the structure and hence the properties exhibited by plasma polymerized thin films are quite different from that of their counterparts produced by other thin film preparation techniques such as electrochemical deposition or spin coating. The properties of these thin films can be tuned only if the interrelationship between the structure and other properties are understood from a fundamental point of view. So very often, a through evaluation of the various properties is a pre-requisite for tailoring the properties of the thin films for applications. It has been found that conjugation is a necessary condition for enhancing the conductivity of polymer thin films. RF technique of plasma polymerisation is an excellent tool to induce conjugation and this modifies the electrical properties too. Both oxidative and reductive doping can be employed to modify the electrical properties of the polymer thin films for various applications. This is where organic thin films based on polymers scored over inorganic thin films, where in large area devices can be fabricated with organic semiconductors which is difficult to achieve by inorganic materials. For such applications, a variety of polymers have been synthesized such as polyaniline, polythiophene, polypyrrole etc. There are newer polymers added to this family every now and then. There are many virgin areas where plasma polymers are yet to make a foray namely low-k dielectrics or as potential nonlinear optical materials such as optical limiters. There are also many materials which are not been prepared by the method of plasma polymerisation. Some of the materials which are not been dealt with are phenyl hydrazine and tea tree oil. The advantage of employing organic extracts like tea tree oil monomers as precursors for making plasma polymers is that there can be value addition to the already existing uses and possibility exists in converting them to electronic grade materials, especially semiconductors and optically active materials for photonic applications. One of the major motivations of this study is to synthesize plasma polymer thin films based on aniline, phenyl hydrazine, pyrrole, tea tree oil and eucalyptus oil by employing both rf and ac plasma polymerisation techniques. This will be carried out with the objective of growing thin films on various substrates such as glass, quartz and indium tin oxide (ITO) coated glass. There are various properties namely structural, electrical, dielectric permittivity, nonlinear optical properties which are to be evaluated to establish the relationship with the structure and the other properties. Special emphasis will be laid in evaluating the optical parameters like refractive index (n), extinction coefficient (k), the real and imaginary components of dielectric constant and the optical transition energies of the polymer thin films from the spectroscopic ellipsometric studies. Apart from evaluating these physical constants, it is also possible to predict whether a material exhibit nonlinear optical properties by ellipsometric investigations. So further studies using open aperture z-scan technique in order to evaluate the nonlinear optical properties of a few selected samples which are potential nonlinear optical materials is another objective of the present study. It will be another endeavour to offer an appropriate explanation for the nonlinear optical properties displayed by these films. Doping of plasma polymers is found to modify both the electrical conductivity and optical properties. Iodine is found to modify the properties of the polymer thin films. However insitu iodine doping is tricky and the film often looses its stability because of the escape of iodine. An appropriate insitu technique of doping will be developed to dope iodine in to the plasma polymerized thin films. Doping of polymer thin films with iodine results in improved and modified optical and electrical properties. However it requires tools like FTIR and UV-Vis-NIR spectroscopy to elucidate the structural and optical modifications imparted to the polymer films. This will be attempted here to establish the role of iodine in the modification of the properties exhibited by the films

Characterisation of nickel(II) extraction by 2-hydroxy-5-nonylacetophenone oxime (LIX 84) in a micellar phase

The properties of the nickel(II)/2-hydroxy-5-nonylacetophenone oxime (HNAPO), an active ingredient in LIX 84, extraction system were characterised in a micellar system. The extinction coefficient, λ_max of HNAPO (316 nm) and the Ni²⁺ complex (387 nm) in a neutral micellar system, poly dispersed octa-ethyleneglycol mono-n-dodecyl ether (G₁₂A₈) were determined as 3100 and 3500 M⁻¹ cm⁻¹, respectively. HNAPO was found to have a neutral micellar phase and bulk aqueous phase pK_a of 11.5 and 12.5, respectively. The extraction equilibrium constant, K_ex, was determined to be 10^−8.0, and the deviation from theory observed at high pH can be accounted for by consideration of the competition for nickel(II) ions by hydroxide ions and HNAPO. A micellar phase of octa-ethyleneglycol mono-n-dodecyl ether (C₁₂E₈) was determined to be an appropriate model of the free oil/water interface from the solubilised location of HNAPO. Utilising the interfacial probe, 4-heptadecyl-7-hydroxy coumarin (HHC) allowed the determination of the electrostatic surface potential of mixed micelles of G₁₂A₈ and sodium dodecyl sulphate (SDS) or dodecyl trimethyl ammonium chloride (DTAC). The electrostatic surface potential was a linear function of the number of additional surfactant monomers within the G₁₂A₈ micelle, for the concentration range studied. For G₁₂A₈/DTAC mixed micelles, the surface potential was given by +1.1 mV per DTAC molecule per micelle, and for G₁₂A₈/SDS mixed micelles the relationship was −1.4 mV per SDS molecule per micelle.

Doxorubicin biocompatible O/W microemulsion stabilized by mixed surfactant containing soya phosphatidylcholine

Microemulsions (ME) containing soya phosphatidylcholine (SPC/polyoxyethylenglycerol trihydroxystearate 40 (EU)/sodium oleate (SO) as surfactant cholesterol (CHO) as oil phase and aqueous buffer were studied. Pseudo-ternary phase diagrams of the investigated systems were obtained at constant SPC/EU/SO weight ratio 3.5:3.5:3.0 by titration, in order to characterize the proportions between the components to form clear systems. The dynamic light scattering results showed that the size of the oil droplets decreases significantly with the ratio of surfactant/oil phase added to system. Depending on the composition ME system could exhibit a thixotropic behavior. The apparent viscosity increased 25- and 13-folds with cholesterol concentration for drug-free and drug-load ME, respectively. It was also verified that the octanol/aqueous buffer partition coefficient (K-O/B) of doxorubicin (DOX) was pH dependent increasing abruptly above pH 6.0. It was possible to incorporate 2.24 mg/ml of DOX into ME. The incorporation of DOX in the ME systems increased the droplets size for all surfactant concentrations used in the system. The results suggest that DOX interacts with the microstructure of the ME at the studied pH increasing significantly the drug solubility. It was possible to conclude that the investigated ME can be a very promising vehicle as drug-carrier for administration of doxorubicin. (c) 2006 Elsevier B.V. All rights reserved.

Determination of a method for calculation of allometric condition factor of fish

There is no agreement among authors that study fish condition by the allometric method (K=W/Lb) with regard to the best procedure for b coefficient calculation. Some authors use a constant coefficient for all sub-samples (seasons of the year, for instance), whilst others calculate b value for each sub-sample. To demonstrate which of these methods fits better, this study verified that the use of one b value for each sub-sample leads to distortion of Condition Factor values. Comparing the two tested methods, it may be concluded that the method which calculates b coefficient from groupings of all individuals and uses b as a constant value for all sub-samples is the most convenient method to study fish condition.

Índice geométrico e perda de carga localizada em conexões de emissores "online"

The objective of this research is to present a study on a relationship between the local head loss in connection of emitters in pipes with different diameters used in drip irrigation, with the online geometry of the emitter connectors, that allows an easy quantification of such head loss regarding of the size of the connectors. The experiment was carried out according to the Reynolds Numbers at a turbulent flow interval, obtained by the variation of the pipe outflow at a constant temperature of water. The results indicated that the friction factor of the Darcy-Weisbach equation can be estimated by the Blasius equation with the coefficients b = 0.300 and m = 0.25, for the above mentioned pipes. The head losses produced by the connections of the emitters, in relation to the pipe without emitter, was of 62%. A relationship between the kinetic load coefficient (K) and the index of blockage (IO) provoked by the online connector is presented by an algebraic equation which shows a coefficient of adjustment of approximately 96%.

Parametric Analysis of Effective Material Properties of Thickness-Shear Piezoelectric Macro-Fibre Composites

A previous study on the characterization of effective material properties of a d(15) thickness-shear piezoelectric Macro-Fibre Composite (MFC) made of seven layers (Kapton, Acrylic, Electrode, Piezoceramic Fibre and Epoxy Composite, Electrode, Acrylic, Kapton) using a finite element homogenization method has shown that the packaging reduces significantly the shear stiffness of the piezoceramic material and, thus, leads to significantly smaller effective electromechanical coupling coefficient k(15) and piezoelectric stress constant e(15) when compared to the piezoceramic fibre properties. Therefore, the main objective of this work is to perform a parametric analysis in which the effect of the variations of fibre volume fraction, Epoxy elastic modulus, electrode thickness and active layer thickness on the MFC effective material properties is evaluated. Results indicate that an effective d(15) MFC should use relatively thick fibres having relatively high shear modulus and relatively stiff epoxy filler. On the other hand, the electrode thickness does not affect significantly the MFC performance.

Caracterización del hormigón en relación a la difusión de gases y su correlación con el radón

Radon gas (Rn) is a natural radioactive gas present in some soils and able to penetrate buildings through the building envelope in contact with the soil. Radon can accumulate within buildings and consequently be inhaled by their occupants. Because it is a radioactive gas, its disintegration process produces alpha particles that, in contact with the lung epithelia, can produce alterations potentially giving rise to cancer. Many international organizations related to health protection, such as WHO, confirm this causality. One way to avoid the accumulation of radon in buildings is to use the building envelope as a radon barrier. The extent to which concrete provides such a barrier is described by its radon diffusion coefficient (DRn), a parameter closely related to porosity (ɛ) and tortuosity factor (τ). The measurement of the radon diffusion coefficient presents challenges, due to the absence of standard procedures, the requirement to establish adequate airtightness in testing apparatus (referred to here as the diffusion cell), and due to the fact that measurement has to be carried out in an environment certified for use of radon calibrated sources. In addition to this calibrated radon sources are costly. The measurement of the diffusion coefficient for non-radioactive gas is less complex, but nevertheless retains a degree of difficulty due to the need to provide reliably airtight apparatus for all tests. Other parameters that can characterize and describe the process of gas transport through concrete include the permeability coefficient (K) and the electrical resistivity (ρe), both of which can be measured relatively easily with standardized procedure. The use of these parameters would simplify the characterization of concrete behaviour as a radon barrier. Although earlier studies exist, describing correlation among these parameters, there is, as has been observed in the literature, little common ground between the various research efforts. For precisely this reason, prior to any attempt to measure radon diffusion, it was deemed necessary to carry out further research in this area, as a foundation to the current work, to explore potential relationships among the following parameters: porosity-tortuosity, oxygen diffusion coefficient, permeability coefficient and resistivity. Permeability coefficient measurement (m2) presents a more straightforward challenge than diffusion coefficient measurement. Some authors identify a relationship between both coefficients, including Gaber (1988), who proposes: k= a•Dn Equation 1 Where: a=A/(8ΠD020), A = sample cross-section, D020 = diffusion coefficient in air (m2/s). Other studies (Klink et al. 1999, Gaber and Schlattner 1997, Gräf and Grube et al. 1986), experimentally relate both coefficients of different types of concrete confirming that this relationship exists, as represented by the simplified expression: k≈Dn Equation 2 In each particular study a different value for n was established, varying from 1.3 to 2.5, but this requires determination of a value for n in a more general way because these proposed models cannot estimate diffusion coefficient. If diffusion coefficient has to be measured to be able to establish n, these relationships are not interesting. The measurement of electric resistivity is easier than diffusion coefficient measurement. Correlation between the parameters can be established via Einstein´s law that relates movement of electrical charges to media conductivity according to the expression: D_e=k/ρ Equation 3 Where: De = diffusion coefficient (cm2/s), K = constant, ρ = electric resistivity (Ω•cm). The tortuosity factor is used to represent the uneven geometry of concrete pores, which are described as being not straight, but tortuous. This factor was first introduced in the literature to relate global porosity with fluid transport in a porous media, and can be formulated in a number of different ways. For example, it can take the form of equation 4 (Mason y Malinauskas), which combines molecular and Knudsen diffusion using the tortuosity factor: D=ε^τ (3/2r √(πM/8RT+1/D_0 ))^(-1) Equation 4 Where: r = medium radius obtained from MIP (µm), M = gas molecular mass, R = ideal gases constant, T = temperature (K), D0 = coefficient diffusion in the air (m2/s). Few studies provide any insight as to how to obtain the tortuosity factor. The work of Andrade (2012) is exceptional in this sense, as it outlines how the tortuosity factor can be deduced from pore size distribution (from MIP) from the equation: ∅_th=∅_0•ε^(-τ). Equation 5 Where: Øth = threshold diameter (µm), Ø0 = minimum diameter (µm), ɛ = global porosity, τ = tortuosity factor. Alternatively, the following equation may be used to obtain the tortuosity factor: DO2=D0*ɛτ Equation 6 Where: DO2 = oxygen diffusion coefficient obtained experimentally (m2/s), DO20 = oxygen diffusion coefficient in the air (m2/s). This equation has been inferred from Archie´s law ρ_e=〖a•ρ〗_0•ɛ^(-m) and from the Einstein law mentioned above, using the values of oxygen diffusion coefficient obtained experimentally. The principal objective of the current study was to establish correlations between the different parameters that characterize gas transport through concrete. The achievement of this goal will facilitate the assessment of the useful life of concrete, as well as open the door to the pro-active planning for the use of concrete as a radon barrier. Two further objectives were formulated within the current study: 1.- To develop a method for measurement of gas coefficient diffusion in concrete. 2.- To model an analytic estimation of radon diffusion coefficient from parameters related to concrete porosity and tortuosity factor. In order to assess the possible correlations, parameters have been measured using the standardized procedures or purpose-built in the laboratory for the study of equations 1, 2 y 3. To measure the gas diffusion coefficient, a diffusion cell was designed and manufactured, with the design evolving over several cycles of research, leading ultimately to a unit that is reliably air tight. The analytic estimation of the radon diffusion coefficient DRn in concrete is based on concrete global porosity (ɛ), whose values may be experimentally obtained from a mercury intrusion porosimetry test (MIP), and from its tortuosity factor (τ), derived using the relations expressed in equations 5 y 6. The conclusions of the study are: Several models based on regressions, for concrete with a relative humidity of 50%, have been proposed to obtain the diffusion coefficient following the equations K=Dn, K=a*Dn y D=n/ρe. The final of these three relations is the one with the determination coefficient closest to a value of 1: D=(19,997*LNɛ+59,354)/ρe Equation 7 The values of the obtained oxygen diffusion coefficient adjust quite well to those experimentally measured. The proposed method for the measurement of the gas coefficient diffusion is considered to be adequate. The values obtained for the oxygen diffusion coefficient are within the range of those proposed by the literature (10-7 a 10-8 m2/s), and are consistent with the other studied parameters. Tortuosity factors obtained using pore distribution and the expression Ø=Ø0*ɛ-τ are inferior to those from resistivity ρ=ρ0*ɛ-τ. The closest relationship to it is the one with porosity of pore diameter 1 µm (τ=2,07), being 7,21% inferior. Tortuosity factors obtained from the expression DO2=D0*ɛτ are similar to those from resistivity: for global tortuosity τ=2,26 and for the rest of porosities τ=0,7. Estimated radon diffusion coefficients are within the range of those consulted in literature (10-8 a 10-10 m2/s).ABSTRACT El gas radón (Rn) es un gas natural radioactivo presente en algunos terrenos que puede penetrar en los edificios a través de los cerramientos en contacto con el mismo. En los espacios interiores se puede acumular y ser inhalado por las personas. Al ser un gas radioactivo, en su proceso de desintegración emite partículas alfa que, al entrar en contacto con el epitelio pulmonar, pueden producir alteraciones del mismo causando cáncer. Muchos organismos internacionales relacionados con la protección de la salud, como es la OMS, confirman esta causalidad. Una de las formas de evitar que el radón penetre en los edificios es utilizando las propiedades de barrera frente al radón de su propia envolvente en contacto con el terreno. La principal característica del hormigón que confiere la propiedad de barrera frente al radón cuando conforma esta envolvente es su permeabilidad que se puede caracterizar mediante su coeficiente de difusión (DRn). El coeficiente de difusión de un gas en el hormigón es un parámetro que está muy relacionado con su porosidad (ɛ) y su tortuosidad (τ). La medida del coeficiente de difusión del radón resulta bastante complicada debido a que el procedimiento no está normalizado, a que es necesario asegurar una estanquidad a la celda de medida de la difusión y a que la medida tiene que ser realizada en un laboratorio cualificado para el uso de fuentes de radón calibradas, que además son muy caras. La medida del coeficiente de difusión de gases no radioactivos es menos compleja, pero sigue teniendo un alto grado de dificultad puesto que tampoco está normalizada, y se sigue teniendo el problema de lograr una estanqueidad adecuada de la celda de difusión. Otros parámetros que pueden caracterizar el proceso son el coeficiente de permeabilidad (K) y la resistividad eléctrica (ρe), que son más fáciles de determinar mediante ensayos que sí están normalizados. El uso de estos parámetros facilitaría la caracterización del hormigón como barrera frente al radón, pero aunque existen algunos estudios que proponen correlaciones entre estos parámetros, en general existe divergencias entre los investigadores, como se ha podido comprobar en la revisión bibliográfica realizada. Por ello, antes de tratar de medir la difusión del radón se ha considerado necesario realizar más estudios que puedan clarificar las posibles relaciones entre los parámetros: porosidad-tortuosidad, coeficiente de difusión del oxígeno, coeficiente de permeabilidad y resistividad. La medida del coeficiente de permeabilidad (m2) es más sencilla que el de difusión. Hay autores que relacionan el coeficiente de permeabilidad con el de difusión. Gaber (1988) propone la siguiente relación: k= a•Dn Ecuación 1 En donde: a=A/(8ΠD020), A = sección de la muestra, D020 = coeficiente de difusión en el aire (m2/s). Otros estudios (Klink et al. 1999, Gaber y Schlattner 1997, Gräf y Grube et al. 1986) relacionan de forma experimental los coeficientes de difusión de radón y de permeabilidad de distintos hormigones confirmando que existe una relación entre ambos parámetros, utilizando la expresión simplificada: k≈Dn Ecuación 2 En cada estudio concreto se han encontrado distintos valores para n que van desde 1,3 a 2,5 lo que lleva a la necesidad de determinar n porque no hay métodos que eviten la determinación del coeficiente de difusión. Si se mide la difusión ya deja de ser de interés la medida indirecta a través de la permeabilidad. La medida de la resistividad eléctrica es muchísimo más sencilla que la de la difusión. La relación entre ambos parámetros se puede establecer a través de una de las leyes de Einstein que relaciona el movimiento de cargas eléctricas con la conductividad del medio según la siguiente expresión: D_e=k/ρ_e Ecuación 3 En donde: De = coeficiente de difusión (cm2/s), K = constante, ρe = resistividad eléctrica (Ω•cm). El factor de tortuosidad es un factor de forma que representa la irregular geometría de los poros del hormigón, al no ser rectos sino tener una forma tortuosa. Este factor se introduce en la literatura para relacionar la porosidad total con el transporte de un fluido en un medio poroso y se puede formular de distintas formas. Por ejemplo se destaca la ecuación 4 (Mason y Malinauskas) que combina la difusión molecular y la de Knudsen utilizando el factor de tortuosidad: D=ε^τ (3/2r √(πM/8RT+1/D_0 ))^(-1) Ecuación 4 En donde: r = radio medio obtenido del MIP (µm), M = peso molecular del gas, R = constante de los gases ideales, T = temperatura (K), D0 = coeficiente de difusión de un gas en el aire (m2/s). No hay muchos estudios que proporcionen una forma de obtener este factor de tortuosidad. Destaca el estudio de Andrade (2012) en el que deduce el factor de tortuosidad de la distribución del tamaño de poros (curva de porosidad por intrusión de mercurio) a partir de la ecuación: ∅_th=∅_0•ε^(-τ) Ecuación 5 En donde: Øth = diámetro umbral (µm), Ø0 = diámetro mínimo (µm), ɛ = porosidad global, τ = factor de tortuosidad. Por otro lado, se podría utilizar también para obtener el factor de tortuosidad la relación: DO2=D0*-τ Ecuación 6 En donde: DO2 = coeficiente de difusión del oxígeno experimental (m2/s), DO20 = coeficiente de difusión del oxígeno en el aire (m2/s). Esta ecuación está inferida de la ley de Archie ρ_e=〖a•ρ〗_0•ɛ^(-m) y la de Einstein mencionada anteriormente, utilizando valores del coeficiente de difusión del oxígeno DO2 obtenidos experimentalmente. El objetivo fundamental de la tesis es encontrar correlaciones entre los distintos parámetros que caracterizan el transporte de gases a través del hormigón. La consecución de este objetivo facilitará la evaluación de la vida útil del hormigón así como otras posibilidades, como la evaluación del hormigón como elemento que pueda ser utilizado en la construcción de nuevos edificios como barrera frente al gas radón presente en el terreno. Se plantean también los siguientes objetivos parciales en la tesis: 1.- Elaborar una metodología para la medida del coeficiente de difusión de los gases en el hormigón. 2.- Plantear una estimación analítica del coeficiente de difusión del radón a partir de parámetros relacionados con su porosidad y su factor de tortuosidad. Para el estudio de las correlaciones posibles, se han medido los parámetros con los procedimientos normalizados o puestos a punto en el propio Instituto, y se han estudiado las reflejadas en las ecuaciones 1, 2 y 3. Para la medida del coeficiente de difusión de gases se ha fabricado una celda que ha exigido una gran variedad de detalles experimentales con el fin de hacerla estanca. Para la estimación analítica del coeficiente de difusión del radón DRn en el hormigón se ha partido de su porosidad global (ɛ), que se obtiene experimentalmente del ensayo de porosimetría por intrusión de mercurio (MIP), y de su factor de tortuosidad (τ), que se ha obtenido a partir de las relaciones reflejadas en las ecuaciones 5 y 6. Las principales conclusiones obtenidas son las siguientes: Se proponen modelos basados en regresiones, para un acondicionamiento con humedad relativa de 50%, para obtener el coeficiente de difusión del oxígeno según las relaciones: K=Dn, K=a*Dn y D=n/ρe. La propuesta para esta última relación es la que tiene un mejor ajuste con R2=0,999: D=(19,997*LNɛ+59,354)/ρe Ecuación 7 Los valores del coeficiente de difusión del oxígeno así estimados se ajustan a los obtenidos experimentalmente. Se considera adecuado el método propuesto de medida del coeficiente de difusión para gases. Los resultados obtenidos para el coeficiente de difusión del oxígeno se encuentran dentro del rango de los consultados en la literatura (10-7 a 10-8 m2/s) y son coherentes con el resto de parámetros estudiados. Los resultados de los factores de tortuosidad obtenidos de la relación Ø=Ø0*ɛ-τ son inferiores a la de la resistividad (ρ=ρ0*ɛ-τ). La relación que más se ajusta a ésta, siendo un 7,21% inferior, es la de la porosidad correspondiente al diámetro 1 µm con τ=2,07. Los resultados de los factores de tortuosidad obtenidos de la relación DO2=D0*ɛτ son similares a la de la resistividad: para la porosidad global τ=2,26 y para el resto de porosidades τ=0,7. Los coeficientes de difusión de radón estimados mediante estos factores de tortuosidad están dentro del rango de los consultados en la literatura (10-8 a 10-10 m2/s).

Accessing chain length dependent termination rate coefficients of methyl methacrylate (MMA) via the reversible addition fragmentation chain transfer (RAFT) process

The RAFT-CLD-T methodology is demonstrated to be not only applicable to 1-substituted monomers such as styrene and acrylates, but also to 1,1-disubstituted monomers such as MMA. The chain length of the terminating macromolecules is controlled by CPDB in MMA bulk free radical polymerization at 80 degrees C. The evolution of the chain length dependent termination rate coefficient, k(t)(i,i), was constructed in a step-wise fashion, since the MMA/CPDB system displays hybrid behavior (between conventional and living free radical polymerization) resulting in initial high molecular weight polymers formed at low RAFT agent concentrations. The obtained CLD of k(t) in MMA polymerizations is compatible with the composite model for chain length dependent termination. For the initial chain-length regime, up to a degree of polymerization of 100, k(t) decreases with alpha (in the expression k(t)(i,i) = k(t)(0) . i(-alpha)) being close to 0.65 at 80 degrees C. At chain lengths exceeding 100, the decrease is less pronounced (affording an alpha of 0.15 at 80 degrees C). However, the data are best represented by a continuously decreasing nonlinear functionality implying a chain length dependent alpha.

Electrografting of poly (carbazole-co-acrylamide) onto highly oriented pyroltic graphite. A cyclovoltammetric, atomic force microscopic and ellipsometric study

The electrocopolymerization of carbazole and acrylamide on highly oriented pyrolytic graphite (HOPG) from ACN solutions via cyclovoltammetry (CV) was studied in order to evaluate the possibility to deposit uniform and thin but pinhole-free and still reactive coatings onto graphite-like substrates. The morphology of the coatings was investigated using atomic force microscopy and the coating thicknesses and optical parameters were measured using ellipsometry. It was found that under the chosen conditions thin (coating thickness hf>180 nm) and relatively smooth (root mean square surface roughness RMS<150 nm) P(Cz-co-AAm)-coatings exhibiting a uniform globuoidal morphology can be deposited onto graphite. From a certain coating thickness (hf>50 nm) no pinholes could be detected. It was found that the thickness of the deposited coatings increases almost linearly with increasing number of CV-cycles while keeping all other experimental parameters (scan rate and comonomer concentration ratio) constant. No influence of the comonomer concentration ratio on the film thickness and coating appearance could be observed, however, at quite low initial concentrations. However, the CV-scanning rate has quite a significant influence on the thickness of the deposited coatings. Higher scan rates (100 mV/s) result in thin (hf≈22 nm) coatings whereas at lower scan rates (<50 mV/s) coatings with thicknesses of approximately 50 nm were obtained. The optical coating parameters (the refractive index n and extinction coefficient k) seem to be independent of the deposition parameters and therefore averaged values of n̄=1.54±0.03 and k̄=0.08±0.03 were obtained.

Assembly of a high-dielectric constant thin TiOX layer directly on H-terminated semiconductor diamond

A high-dielectric constant (high-k) TiOx thin layer was fabricated on hydrogen-terminated diamond (H-diamond) surface by low temperature oxidation of a thin titanium layer in ambient air. The metallic titanium layer was deposited by sputter deposition. The dielectric constant of the resultant TiOx was calculated to be around 12. The capacitance density of the metal-oxide-semiconductor (MOS) based on the TiOx/H-diamond was as high as 0.75 µF/cm2 contributed from the high-k value and the very thin thickness of the TiOx layer. The leakage current was lower than 10-13 A at reverse biases and 10-7A at the forward bias of -2 V. The MOS field-effect transistor based on the high-k TiOx/H-diamond was demonstrated. The utilization of the high-k TiOx with a very thin thickness brought forward the features of an ideally low subthreshold swing slope of 65 mV per decade and improved drain current at low gate voltages. The advantages of the utilization high-k dielectric for diamond MOSFETs are anticipated.

Ajustes de coeficientes integrantes de processos físicos e bioquímicos na autedepuração em curso de água de médio porte

The mathematical modeling in the simulation of self-purification capacity in lotic environment is an important tool in the planning and management of hydric resources in hydrographic basin scale. It satisfactorily deals with the self-purification process when the coefficients of physical and biochemical processes are calibrated from monitorated water quality data, which was the main focus of this study. The present study was conducted to simulate the behavior of the parameters OD, BOD5, total phosphorus, E. coli, ammonia, nitrite, nitrate and the total metals cadmium, chromium, copper, lead and zinc in the Uberabinha’s lower course (with an approximate annual growth flow between 4-35 m3/s), in a stretch of 19 km downstream of the treated effluent release by the WWTP of the city. The modelings, on the present study, show the importance of constant water quality parameters monitoration over the water course, based on the comparison of the simulations from calibrated coefficients and coefficients obtained in the literature for the period of June until November 2015. After coefficients calibration, there were good adjustments between simulated and measured data for the parameters OD, BOD, Ptotal, ammonia and nitrate and unsatisfactory adjust for the parameters nitrite and E. coli. About the total metals, the adjustments were not satisfactory on the reservoir’s vicinity of the Small Hydropower Plant Martins, due the considerable increase of the bottom sediment in lentic region. The greatest scientific contribution of this study was to calibrate the decay coefficient K and the quantification of the release by the fund S of total metals in watercourse midsize WWTP pollutant load receptor, justified by the lack of studies in the literature about the subject. For the metals cadmium, chromium, copper, lead and zinc, the borderline for K and S calibrated were: 0.0 to 13.0 day-1 and 0.0 to 1.7 g/m3.day; 0.0 to 0.9 day-1 and 0.0 to 7.3 g/m3.day; 0.0 to 25.0 day-1 and 0.0 to 1.8 g/m3.day; 0.0 to 7.0 day-1 and 0.0 to 40.3 g/m3.day; 0.0 to 30.0 day-1 and 0.0 to 70.1 g/m3.day.

Investigation of electrically active defects at the interface of high-k dielectrics and compound semiconductors

As silicon based devices in integrated circuits reach the fundamental limits of dimensional scaling there is growing research interest in the use of high electron mobility channel materials, such as indium gallium arsenide (InGaAs), in conjunction with high dielectric constant (high-k) gate oxides, for Metal-Oxide-Semiconductor Field Effect Transistor (MOSFET) based devices. The motivation for employing high mobility channel materials is to reduce power dissipation in integrated circuits while also providing improved performance. One of the primary challenges to date in the field of III-V semiconductors has been the observation of high levels of defect densities at the high-k/III-V interface, which prevents surface inversion of the semiconductor. The work presented in this PhD thesis details the characterization of MOS devices incorporating high-k dielectrics on III-V semiconductors. The analysis examines the effect of modifying the semiconductor bandgap in MOS structures incorporating InxGa1-xAs (x: 0, 0.15. 0.3, 0.53) layers, the optimization of device passivation procedures designed to reduce interface defect densities, and analysis of such electrically active interface defect states for the high-k/InGaAs system. Devices are characterized primarily through capacitance-voltage (CV) and conductance-voltage (GV) measurements of MOS structures both as a function of frequency and temperature. In particular, the density of electrically active interface states was reduced to the level which allowed the observation of true surface inversion behavior in the In0.53Ga0.47As MOS system. This was achieved by developing an optimized (NH4)2S passivation, minimized air exposure, and atomic layer deposition of an Al2O3 gate oxide. An extraction of activation energies allows discrimination of the mechanisms responsible for the inversion response. Finally a new approach is described to determine the minority carrier generation lifetime and the oxide capacitance in MOS structures. The method is demonstrated for an In0.53Ga0.47As system, but is generally applicable to any MOS structure exhibiting a minority carrier response in inversion.