Towards the development of poly (phenylene sulphide) based nanocomposites with enhanced mechanical, electrical and tribological properties

Novel poly(phenylene sulphide) (PPS) nanocomposites reinforced with an aminated derivative (PPS-NH2) covalently attached to acid-treated single-walled carbon nanotubes (SWCNTs) were prepared via simple melt-blending technique. Their morphology, viscoelastic behaviour, electrical conductivity, mechanical and tribological properties were investigated. Scanning electron microscopy revealed that the grafting process was effective in uniformly dispersing the SWCNTs within the matrix. The storage and loss moduli as a function of frequency increased with the SWCNT content, tending to a plateau in the low-frequency regime. The electrical conductivity of the nanocomposites was considerably enhanced in the range 0.1?0.5 wt% SWCNTs; electrical and rheological percolation thresholds occurred at similar nanotube concentrations. Mechanical tests demonstrated that with only 1.0 wt% SWCNTs the Young's modulus and tensile strength of the matrix improved by 51 and 37%, respectively, without decrement in toughness, ascribed to a very efficient load transfer. A moderate decrease in the friction coefficient and a 75% reduction in wear rate were found for the abovementioned nanotube loading, indicating that PPS-NH2-g-SWCNTs are good tribological additives for thermoplastic polymers. Based on the promising results obtained in this work, it is expected that these nanofillers will be used to develop high-performance thermoplastic/CNT nanocomposites for structural applications.

Un método de diferencias finitas generalizadas para simular la actividad eléctrica de un tejido cardiaco

Una evolución del método de diferencias finitas ha sido el desarrollo del método de diferencias finitas generalizadas (MDFG) que se puede aplicar a mallas irregulares o nubes de puntos. En este método se emplea una expansión en serie de Taylor junto con una aproximación por mínimos cuadrados móviles (MCM). De ese modo, las fórmulas explícitas de diferencias para nubes irregulares de puntos se pueden obtener fácilmente usando el método de Cholesky. El MDFG-MCM es un método sin malla que emplea únicamente puntos. Una contribución de esta Tesis es la aplicación del MDFG-MCM al caso de la modelización de problemas anisótropos elípticos de conductividad eléctrica incluyendo el caso de tejidos reales cuando la dirección de las fibras no es fija, sino que varía a lo largo del tejido. En esta Tesis también se muestra la extensión del método de diferencias finitas generalizadas a la solución explícita de ecuaciones parabólicas anisótropas. El método explícito incluye la formulación de un límite de estabilidad para el caso de nubes irregulares de nodos que es fácilmente calculable. Además se presenta una nueva solución analítica para una ecuación parabólica anisótropa y el MDFG-MCM explícito se aplica al caso de problemas parabólicos anisótropos de conductividad eléctrica. La evidente dificultad de realizar mediciones directas en electrocardiología ha motivado un gran interés en la simulación numérica de modelos cardiacos. La contribución más importante de esta Tesis es la aplicación de un esquema explícito con el MDFG-MCM al caso de la modelización monodominio de problemas de conductividad eléctrica. En esta Tesis presentamos un algoritmo altamente eficiente, exacto y condicionalmente estable para resolver el modelo monodominio, que describe la actividad eléctrica del corazón. El modelo consiste en una ecuación en derivadas parciales parabólica anisótropa (EDP) que está acoplada con un sistema de ecuaciones diferenciales ordinarias (EDOs) que describen las reacciones electroquímicas en las células cardiacas. El sistema resultante es difícil de resolver numéricamente debido a su complejidad. Proponemos un método basado en una separación de operadores y un método sin malla para resolver la EDP junto a un método de Runge-Kutta para resolver el sistema de EDOs de la membrana y las corrientes iónicas. ABSTRACT An evolution of the method of finite differences has been the development of generalized finite difference (GFD) method that can be applied to irregular grids or clouds of points. In this method a Taylor series expansion is used together with a moving least squares (MLS) approximation. Then, the explicit difference formulae for irregular clouds of points can be easily obtained using a simple Cholesky method. The MLS-GFD is a mesh-free method using only points. A contribution of this Thesis is the application of the MLS-GFDM to the case of modelling elliptic anisotropic electrical conductivity problems including the case of real tissues when the fiber direction is not fixed, but varies throughout the tissue. In this Thesis the extension of the generalized finite difference method to the explicit solution of parabolic anisotropic equations is also given. The explicit method includes a stability limit formulated for the case of irregular clouds of nodes that can be easily calculated. Also a new analytical solution for homogeneous parabolic anisotropic equation has been presented and an explicit MLS- GFDM has been applied to the case of parabolic anisotropic electrical conductivity problems. The obvious difficulty of performing direct measurements in electrocardiology has motivated wide interest in the numerical simulation of cardiac models. The main contribution of this Thesis is the application of an explicit scheme based in the MLS-GFDM to the case of modelling monodomain electrical conductivity problems using operator splitting including the case of anisotropic real tissues. In this Thesis we present a highly efficient, accurate and conditionally stable algorithm to solve a monodomain model, which describes the electrical activity in the heart. The model consists of a parabolic anisotropic partial differential equation (PDE), which is coupled to systems of ordinary differential equations (ODEs) describing electrochemical reactions in the cardiac cells. The resulting system is challenging to solve numerically, because of its complexity. We propose a method based on operator splitting and a meshless method for solving the PDE together with a Runge-Kutta method for solving the system of ODE’s for the membrane and ionic currents.

Thermal, stress, and traps effects in AlGaN/GaN HEMTs

GaN y AlN son materiales semiconductores piezoeléctricos del grupo III-V. La heterounión AlGaN/GaN presenta una elevada carga de polarización tanto piezoeléctrica como espontánea en la intercara, lo que genera en su cercanía un 2DEG de grandes concentración y movilidad. Este 2DEG produce una muy alta potencia de salida, que a su vez genera una elevada temperatura de red. Las tensiones de puerta y drenador provocan un stress piezoeléctrico inverso, que puede afectar a la carga de polarización piezoeléctrica y así influir la densidad 2DEG y las características de salida. Por tanto, la física del dispositivo es relevante para todos sus aspectos eléctricos, térmicos y mecánicos. En esta tesis se utiliza el software comercial COMSOL, basado en el método de elementos finitos (FEM), para simular el comportamiento integral electro-térmico, electro-mecánico y electro-térmico-mecánico de los HEMTs de GaN. Las partes de acoplamiento incluyen el modelo de deriva y difusión para el transporte electrónico, la conducción térmica y el efecto piezoeléctrico. Mediante simulaciones y algunas caracterizaciones experimentales de los dispositivos, hemos analizado los efectos térmicos, de deformación y de trampas. Se ha estudiado el impacto de la geometría del dispositivo en su auto-calentamiento mediante simulaciones electro-térmicas y algunas caracterizaciones eléctricas. Entre los resultados más sobresalientes, encontramos que para la misma potencia de salida la distancia entre los contactos de puerta y drenador influye en generación de calor en el canal, y así en su temperatura. El diamante posee une elevada conductividad térmica. Integrando el diamante en el dispositivo se puede dispersar el calor producido y así reducir el auto-calentamiento, al respecto de lo cual se han realizado diversas simulaciones electro-térmicas. Si la integración del diamante es en la parte superior del transistor, los factores determinantes para la capacidad disipadora son el espesor de la capa de diamante, su conductividad térmica y su distancia a la fuente de calor. Este procedimiento de disipación superior también puede reducir el impacto de la barrera térmica de intercara entre la capa adaptadora (buffer) y el substrato. La muy reducida conductividad eléctrica del diamante permite que pueda contactar directamente el metal de puerta (muy cercano a la fuente de calor), lo que resulta muy conveniente para reducir el auto-calentamiento del dispositivo con polarización pulsada. Por otra parte se simuló el dispositivo con diamante depositado en surcos atacados sobre el sustrato como caminos de disipación de calor (disipador posterior). Aquí aparece una competencia de factores que influyen en la capacidad de disipación, a saber, el surco atacado contribuye a aumentar la temperatura del dispositivo debido al pequeño tamaño del disipador, mientras que el diamante disminuiría esa temperatura gracias a su elevada conductividad térmica. Por tanto, se precisan capas de diamante relativamente gruesas para reducer ele efecto de auto-calentamiento. Se comparó la simulación de la deformación local en el borde de la puerta del lado cercano al drenador con estructuras de puerta estándar y con field plate, que podrían ser muy relevantes respecto a fallos mecánicos del dispositivo. Otras simulaciones se enfocaron al efecto de la deformación intrínseca de la capa de diamante en el comportamiento eléctrico del dispositivo. Se han comparado los resultados de las simulaciones de la deformación y las características eléctricas de salida con datos experimentales obtenidos por espectroscopía micro-Raman y medidas eléctricas, respectivamente. Los resultados muestran el stress intrínseco en la capa producido por la distribución no uniforme del 2DEG en el canal y la región de acceso. Además de aumentar la potencia de salida del dispositivo, la deformación intrínseca en la capa de diamante podría mejorar la fiabilidad del dispositivo modulando la deformación local en el borde de la puerta del lado del drenador. Finalmente, también se han simulado en este trabajo los efectos de trampas localizados en la superficie, el buffer y la barrera. Las medidas pulsadas muestran que tanto las puertas largas como las grandes separaciones entre los contactos de puerta y drenador aumentan el cociente entre la corriente pulsada frente a la corriente continua (lag ratio), es decir, disminuir el colapse de corriente (current collapse). Este efecto ha sido explicado mediante las simulaciones de los efectos de trampa de superficie. Por su parte, las referidas a trampas en el buffer se enfocaron en los efectos de atrapamiento dinámico, y su impacto en el auto-calentamiento del dispositivo. Se presenta también un modelo que describe el atrapamiento y liberación de trampas en la barrera: mientras que el atrapamiento se debe a un túnel directo del electrón desde el metal de puerta, el desatrapamiento consiste en la emisión del electrón en la banda de conducción mediante túnel asistido por fonones. El modelo también simula la corriente de puerta, debida a la emisión electrónica dependiente de la temperatura y el campo eléctrico. Además, también se ilustra la corriente de drenador dependiente de la temperatura y el campo eléctrico. ABSTRACT GaN and AlN are group III-V piezoelectric semiconductor materials. The AlGaN/GaN heterojunction presents large piezoelectric and spontaneous polarization charge at the interface, leading to high 2DEG density close to the interface. A high power output would be obtained due to the high 2DEG density and mobility, which leads to elevated lattice temperature. The gate and drain biases induce converse piezoelectric stress that can influence the piezoelectric polarization charge and further influence the 2DEG density and output characteristics. Therefore, the device physics is relevant to all the electrical, thermal, and mechanical aspects. In this dissertation, by using the commercial finite-element-method (FEM) software COMSOL, we achieved the GaN HEMTs simulation with electro-thermal, electro-mechanical, and electro-thermo-mechanical full coupling. The coupling parts include the drift-diffusion model for the electron transport, the thermal conduction, and the piezoelectric effect. By simulations and some experimental characterizations, we have studied the device thermal, stress, and traps effects described in the following. The device geometry impact on the self-heating was studied by electro-thermal simulations and electrical characterizations. Among the obtained interesting results, we found that, for same power output, the distance between the gate and drain contact can influence distribution of the heat generation in the channel and thus influence the channel temperature. Diamond possesses high thermal conductivity. Integrated diamond with the device can spread the generated heat and thus potentially reduce the device self-heating effect. Electro-thermal simulations on this topic were performed. For the diamond integration on top of the device (top-side heat spreading), the determinant factors for the heat spreading ability are the diamond thickness, its thermal conductivity, and its distance to the heat source. The top-side heat spreading can also reduce the impact of thermal boundary resistance between the buffer and the substrate on the device thermal behavior. The very low electrical conductivity of diamond allows that it can directly contact the gate metal (which is very close to the heat source), being quite convenient to reduce the self-heating for the device under pulsed bias. Also, the diamond coated in vias etched in the substrate as heat spreading path (back-side heat spreading) was simulated. A competing mechanism influences the heat spreading ability, i.e., the etched vias would increase the device temperature due to the reduced heat sink while the coated diamond would decrease the device temperature due to its higher thermal conductivity. Therefore, relative thick coated diamond is needed in order to reduce the self-heating effect. The simulated local stress at the gate edge of the drain side for the device with standard and field plate gate structure were compared, which would be relevant to the device mechanical failure. Other stress simulations focused on the intrinsic stress in the diamond capping layer impact on the device electrical behaviors. The simulated stress and electrical output characteristics were compared to experimental data obtained by micro-Raman spectroscopy and electrical characterization, respectively. Results showed that the intrinsic stress in the capping layer caused the non-uniform distribution of 2DEG in the channel and the access region. Besides the enhancement of the device power output, intrinsic stress in the capping layer can potentially improve the device reliability by modulating the local stress at the gate edge of the drain side. Finally, the surface, buffer, and barrier traps effects were simulated in this work. Pulsed measurements showed that long gates and distances between gate and drain contact can increase the gate lag ratio (decrease the current collapse). This was explained by simulations on the surface traps effect. The simulations on buffer traps effects focused on illustrating the dynamic trapping/detrapping in the buffer and the self-heating impact on the device transient drain current. A model was presented to describe the trapping and detrapping in the barrier. The trapping was the electron direct tunneling from the gate metal while the detrapping was the electron emission into the conduction band described by phonon-assisted tunneling. The reverse gate current was simulated based on this model, whose mechanism can be attributed to the temperature and electric field dependent electron emission in the barrier. Furthermore, the mechanism of the device bias via the self-heating and electric field impact on the electron emission and the transient drain current were also illustrated.

Approach to the potential production of giant reed in surplus saline lands of Spain

Growing energy crops on marginal land has been promoted as a way of ensuring that biomass production involves an acceptable and sustainable use of land. Saline and saline-prone agricultural lands represent an opportunity for growing energy crops avoiding the displacement of food production and contributing to restoration of degraded land. Giant reed (Arundo donax L.) is a perennial grass that has been proposed as a promising energy crop for lignocellulosic biomass production while its tolerance to salinity has been proved. In this work, the identification of surplus saline lands that could be irrigated with saline waters for growing tolerant-energy crops (giant reed) in the mainland of Spain and the assessment of the agronomically attainable yield in these limiting growing conditions were undertaken. To this purpose, a GIS analysis was conducted using geodatabases related to saline areas, agro-climatic conditions, irrigation water requirements, agricultural land availability, restrictions regarding the range of electrical conductivity tolerated by the crop, competition with agro-food crops and irrigation water provisions. According to the approach developed, the irrigated and saline agricultural area available and suitable for biomass production from giant reed amounted up to 34 412 ha. The agronomically attainable yield in these limiting conditions was estimated at 12.7 – 22.2 t dm ha−1 yr−1 and the potential production of lignocellulosic biomass, 597 338 t dm yr−1. The methodology followed in this study can be applied to other target regions; it allows the identification of this type of marginal lands, where salinity-tolerant plant species could be grown for bioenergy purposes, avoiding competition with agro-food crops, and where soil restoration measurements should be undertaken.

Conductivity test in seeds of different passion flower species

The objective of this work was to evaluate the use of the conductivity test as a means of predicting seed viability in seven Passiflora species: P. alata, P. cincinnata, P. edulis f. edulis, P. edulis f. flavicarpa, P. morifolia, P. mucronata, and P. nitida. Conductivity of non?desiccated (control), desiccated, and non?desiccated cryopreserved seeds was determined and related to their germination percentage. The obtained results suggest that the electrical conductivity test has potential as a germination predictor for P. edulis f. flavicarpa seed lots, but not for the other tested species. Index terms: Passiflora, seed cryopreservation, seed desiccation, seed viability.