Influencia de la adición de nanosílice y microsílice en el comportamiento mecánico, microestructural y durable de un hormigón autocompactante

Desde mediados de la década de los 80 se está investigando sobre el hormigón autocompactante. Cada día, su uso en el mundo de la construcción es más común debido a sus numerosas ventajas como su excelente fluidez ya que puede fluir bajo su propio peso y llenar encofrados con formas complicadas y muy armados sin necesidad de compactaciones internas o externas. Por otra parte, la búsqueda de materiales más resistentes y duraderos, ha dado lugar a la incorporación de adiciones en materiales a base de cemento. En las últimas dos décadas, los ensayos con los nanomateriales, ha experimentado un gran aumento. Los resultados hasta ahora obtenidos pueden asumir no sólo un aumento en la resistencia de estos materiales, pero un cambio es su funcionalidad. Estas nanopartículas, concretamente la nanosílice, no sólo mejoran sus propiedades mecánicas y especialmente sus propiedades durables, sino que pueden implicar un cambio sustancial en las condiciones de uso y en su ciclo de vida. Este trabajo tiene como principal objetivo el estudio de las propiedades mecánicas, características microestructurales y durables de un hormigón autocompactante cuando se le agrega como adición nanosílice, microsílice y mezcla binarias de ambas, como adición al cemento. Para ello se han realizado 10 mezclas de hormigón. Se utilizó como referencia un hormigón autocompactante obtenido con cemento, caliza, árido, aditivo modificador de viscosidad Se han fabricado tres hormigones con la misma dosificación pero con diferentes contenidos de nanosílice. 2,5%, 5% y 7,5% Tres dosificaciones con adición de microsílice 2,5%, 5% y 7,5% y las tres restantes con mezclas binarias de nanosílice y microsílice con respectivamente2,5%-2,5%, 5%-2,5% y 2,5%-5%, sobre el peso del cemento. El contenido de superplastificante se modificó para conseguir las características de autocompactabilidad. Para observar los efectos de las adiciones añadidas al hormigón, se realiza una extensa campaña experimental. En ella se evaluaron en primer lugar, las características de autocompactabilidad del material en estado fresco, mediante los ensayos prescritos en la Instrucción Española del hormigón estructural EHE 08. Las propiedades mecánicas fueron evaluadas con ensayos de resistencia a compresión, resistencia a tracción indirecta y módulo de elasticidad. Las características microestructurales fueron analizadas mediante porosimetría por intrusión de mercurio, el análisis termogravimétrico y la microscopía electrónica de barrido. Para el estudio de la capacidad durable de las mezclas se realizaron ensayos de resistividad eléctrica, migración de cloruros, difusión de cloruros, carbonatación acelerada, absorción capilar y resistencia al hielo-deshielo. Los resultados ponen de manifiesto que la acción de las adiciones genera mejoras en las propiedades resistentes del material. Así, la adición de nanosílice proporciona mayores resistencias a compresión que la microsílice, sin embargo las mezclas binarias con bajas proporciones de adición producen mayores resistencias. Por otra parte, se observó mediante la determinación de las relaciones de gel/portlandita, que las mezclas que contienen nanosílice tienen una mayor actividad puzolánica que las que contienen microsílice. En las mezclas binarias se obtuvo como resultado que mientras mayor es el contenido de nanosílice en la mezcla mayor es la actividad puzolánica. Unido a lo anteriormente expuesto, el estudio de la porosidad da como resultado que la adición de nanosílice genera un refinamiento del tamaño de los poros mientras que la adición de microsílice disminuye la cantidad de los mismos sin variar el tamaño de poro medio. Por su parte, en las micrografías, se visualizó la formación de cristales procedentes de la hidratación del cemento. En ellas, se pudo observar, que al adicionar nanosílice, la velocidad de hidratación aumenta al aumentar la formación de monosulfoaluminatos con escasa presencia de etringita. Mientras que en las mezclas con adición de microsílice se observan mayor cantidad de cristales de etringita, lo que confirma que la velocidad de hidratación en estos últimos fue menor. Mediante el estudio de los resultados de las pruebas de durabilidad, se observó que no hay diferencias significativas entre el coeficiente de migración de cloruros y el coeficiente de difusión de cloruros en hormigones con adición de nano o microsílice. Aunque este coeficiente es ligeramente menor en mezclas con adición de microsílice. Sin embargo, en las mezclas binarias de ambas adiciones se obtuvo valores de los coeficientes de difusión o migración de cloruros inferiores a los obtenidos en mezclas con una única adición. Esto se evidencia en los resultados de las pruebas de resistividad eléctrica, de difusión de cloruros y de migración de cloruros. Esto puede ser debido a la suma de los efectos que producen el nano y micro adiciones en la porosidad. El resultado mostró que nanosílice tiene un papel importante en la reducción de los poros y la microsílice disminuye el volumen total de ellos. Esto permite definir la vida útil de estos hormigones a valores muy superiores a los exigidos por la EHE-08, por lo que es posible reducir, de forma notable, el recubrimiento exigido en ambiente de alta agresividad asegurando un buen comportamiento en servicio. Por otra parte, la pérdida de masa debido a los ciclos de congelación-descongelación es significativamente menor en los hormigones que contienen nanosílice que los que contienen microsílice. Este resultado está de acuerdo con el ensayo de absorción capilar. De manera general, se puede concluir que son las mezclas binarias y más concretamente la mezcla con un 5% de nanosílice y 2,5% de microsílice la que presenta los mejores resultados tanto en su comportamiento resistente con en su comportamiento durable. Esto puede ser debido a que en estas mezclas la nanosílice se comporta como un núcleo de activación de las reacciones puzolánicas rodeado de partículas de mayor tamaño. Además, el extraordinario comportamiento durable puede deberse también a la continuidad en la curva granulométrica por la existencia de la microsílice, el filler calizo, el cemento, la arena y la gravilla con tamaños de partículas que garantice mezclas muy compactas que presentan elevadas prestaciones. Since the middle of the decade of the 80 is being investigated about self-consolidating concrete. Every day, its use in the world of construction is more common due to their numerous advantages as its excellent fluidity such that it can flow under its own weight and fill formworks with complicated shapes and congested reinforcement without need for internal or external compactions. Moreover, the search for more resistant and durable materials, has led to the incorporation of additions to cement-based materials. In the last two decades, trials with nanomaterials, has experienced a large increase. The results so far obtained can assume not only an increase in the resistance of these materials but a change is its functionality. These nano particles, particularly the nano silica, not only improve their mechanical properties and especially its durable properties, but that may imply a substantial change in the conditions of use and in their life cycle. This work has as its main objective the study of the mechanical properties, the microstructural characteristics and durability capacity in one self-compacting concrete, when added as addition to cement: nano silica, micro silica o binary mixtures of both. To this effect, 10 concrete mixes have been made. As reference one with a certain amount of cement, limestone filler, viscosity modifying additive and water/binder relation. Furthermore they were manufactured with the same dosage three mix with addition of 2.5%, 5% and 7.5% of nano silica by weight of cement. Other three with 2.5%, 5% and 7.5% of micro silica and the remaining three with binary mixtures of 2.5%-2.5%, 5%-2.5% and 2.5%-5% of silica nano-micro silica respectively, b weight of cement, varying only the amount of superplasticizer to obtain concrete with characteristics of self-compactability. To observe the effects of the additions added to the concrete, an extensive experimental campaign was performed. It assessed, first, the characteristics of self-compactability of fresh material through the tests prescribed in the Spanish Structural Instruction Concrete EHE 08. The mechanical properties were evaluated by compression strength tests, indirect tensile strength and modulus of elasticity. The microstructural properties were analyzed by mercury intrusion porosimetry, thermogravimetric analysis and scanning electron microscopy. To study the durability, were performed electrical resistivity tests, migration and diffusion of chlorides, accelerated carbonation, capillary suction and resistance to freeze-thaw cycles. The results show that the action of the additions generates improvements in the strength properties of the material. Specifically, the addition of nano silica provides greater resistance to compression that the mix with micro silica, however binary mixtures with low addition rates generate higher strengths. Moreover, it was observed by determining relationships gel/portlandite, that the pozzolanic activity in the mixtures with nano silica was higher than in the mixtures with micro silica. In binary mixtures it was found that the highest content of nano silica in the mix is the one with the highest pozzolanic activity. Together with the foregoing, the study of the porosity results in the mixture with addition of nano silica generates a refinement of pore size while adding micro silica decreases the amount thereof without changing the average pore size. On the other hand, in the micrographs, the formation of crystals of cement hydration was visualized. In them, it was observed that by adding nano silica, the speed of hydration increases with increasing formation monosulfoaluminatos with scarce presence of ettringite. While in mixtures with addition of micro silica, ettringite crystals are observed, confirming that the hydration speed was lower in these mixtures. By studying the results of durability testing, it observed that no significant differences between the coefficient of migration of chlorides and coefficient of diffusion of chlorides in concretes with addition of nano or micro silica. Although this coefficient is slightly lower in mixtures with addition of micro silica. However, in binary mixtures of both additions was obtained values of coefficients of difusion o migration of chlorides lower than those obtained in mixtures with one of the additions. This is evidenced by the results of the tests electrical resistivity, diffusion of chlorides and migration of chlorides. This may be due to the sum of the effects that produced the nano and micro additions in the porosity. The result showed that nano silica has an important role in the pores refining and the micro silica decreases the total volume of them. This allows defining the life of these concretes in values to far exceed those required by the EHE-08, making it possible to reduce, significantly, the coating required in highly aggressive environment and to guarantee good behavior in service. Moreover, the mass loss due to freeze-thaw cycles is significantly lower in concretes containing nano silica than those containing micro silica. This result agrees with the capillary absorption test. In general, one can conclude that the binary mixture and more specifically the mixture with 5% of nano silica and 2.5% silica fume is which presents the best results in its durable behavior. This may be because in these mixtures, the nano silica behaves as cores activation of pozzolanic reactions. In addition, the durable extraordinary behavior may also be due to the continuity of the grading curve due to existence of micro silica, limestone filler, cement, sand and gravel with particle sizes that guarantees very compact mixtures which have high performance.

Soot measurements in steady and pulsed ethylene/air diffusion flames using Laser-Induced Incandescence

Combustion-generated carbon black nano particles, or soot, have both positive and negative effects depending on the application. From a positive point of view, it is used as a reinforcing agent in tires, black pigment in inks, and surface coatings. From a negative point of view, it affects performance and durability of many combustion systems, it is a major contributor of global warming, and it is linked to respiratory illness and cancer. Laser-Induced Incandescence (LII) was used in this study to measure soot volume fractions in four steady and twenty-eight pulsed ethylene diffusion flames burning at atmospheric pressure. A laminar coflow diffusion burner combined with a very-high-speed solenoid valve and control circuit provided unsteady flows by forcing the fuel flow with frequencies between 10 Hz and 200 Hz. Periodic flame oscillations were captured by two-dimensional phase-locked LII images and broadband luminosity images for eight phases (0° – 360°) covering each period. A comparison between the steady and pulsed flames and the effect of the pulsation frequency on soot volume fraction in the flame region and the post flame region are presented. The most significant effect of pulsing frequency was observed at 10 Hz. At this frequency, the flame with the lowest mean flow rate had 1.77 times enhancement in peak soot volume fraction and 1.2 times enhancement in total soot volume fraction; whereas the flame with the highest mean flow rate had no significant change in the peak soot volume fraction and 1.4 times reduction in the total soot volume fraction. A correlation (fvRe-1 = a + b·Str) for the total soot volume fraction in the flame region for the unsteady laminar ethylene flames was obtained for the pulsation frequency between 10 Hz and 200 Hz, and the Reynolds number between 37 and 55. The soot primary particle size in steady and unsteady flames was measured using the Time-Resolved Laser-Induced Incandescence (TIRE-LII) and the double-exponential fit method. At maximum frequency (200 Hz), the soot particles were smaller in size by 15% compared to the steady case in the flame with the highest mean flow rate.

The investigation of photocatalysts and iron based materials in the oxidation and adsorption of toxic organic and chromium materials

The presences of heavy metals, organic contaminants and natural toxins in natural water bodies pose a serious threat to the environment and the health of living organisms. Therefore, there is a critical need to identify sustainable and environmentally friendly water treatment processes. In this dissertation, I focus on the fundamental studies of advanced oxidation processes and magnetic nano-materials as promising new technologies for water treatments. Advanced oxidation processes employ reactive oxygen species (ROS) which can lead to the mineralization of a number of pollutants and toxins. The rates of formation, steady-state concentrations, and kinetic parameters of hydroxyl radical and singlet oxygen produced by various TiO2 photocatalysts under UV or visible irradiations were measured using selective chemical probes. Hydroxyl radical is the dominant ROS, and its generation is dependent on experimental conditions. The optimal condition for generation of hydroxyl radical by of TiO2 coated glass microspheres is studied by response surface methodology, and the optimal conditions are applied for the degradation of dimethyl phthalate. Singlet oxygen (1O2) also plays an important role for advanced processes, so the degradation of microcystin-LR by rose bengal, an 1O2 sensitizer was studied. The measured bimolecular reaction rate constant between MC-LR and 1O2 is ∼ 106 M-1 s-1 based on competition kinetics with furfuryl alcohol. The typical adsorbent needs separation after the treatment, while magnetic iron oxides can be easily removed by a magnetic field. Maghemite and humic acid coated magnetite (HA-Fe3O4) were synthesized, characterized and applied for chromium(VI) removal. The adsorption of chromium(VI) by maghemite and HA-Fe3O4 follow a pseudo-second-order kinetic process. The adsorption of chromium(VI) by maghemite is accurately modeled using adsorption isotherms, and solution pH and presence of humic acid influence adsorption. Humic acid coated magnetite can adsorb and reduce chromium(VI) to non-toxic chromium (III), and the reaction is not highly dependent on solution pH. The functional groups associated with humic acid act as ligands lead to the Cr(III) complex via a coupled reduction-complexation mechanism. Extended X-ray absorption fine structure spectroscopy demonstrates the Cr(III) in the Cr-loaded HA-Fe 3O4 materials has six neighboring oxygen atoms in an octahedral geometry with average bond lengths of 1.98 Å.

Soot Measurements in Steady and Pulsed Ethylene/Air Diffusion Flames Using Laser-Induced Incandescence

Combustion-generated carbon black nano particles, or soot, have both positive and negative effects depending on the application. From a positive point of view, it is used as a reinforcing agent in tires, black pigment in inks, and surface coatings. From a negative point of view, it affects performance and durability of many combustion systems, it is a major contributor of global warming, and it is linked to respiratory illness and cancer. Laser-Induced Incandescence (LII) was used in this study to measure soot volume fractions in four steady and twenty-eight pulsed ethylene diffusion flames burning at atmospheric pressure. A laminar coflow diffusion burner combined with a very-high-speed solenoid valve and control circuit provided unsteady flows by forcing the fuel flow with frequencies between 10 Hz and 200 Hz. Periodic flame oscillations were captured by two-dimensional phase-locked LII images and broadband luminosity images for eight phases (0°- 360°) covering each period. A comparison between the steady and pulsed flames and the effect of the pulsation frequency on soot volume fraction in the flame region and the post flame region are presented. The most significant effect of pulsing frequency was observed at 10 Hz. At this frequency, the flame with the lowest mean flow rate had 1.77 times enhancement in peak soot volume fraction and 1.2 times enhancement in total soot volume fraction; whereas the flame with the highest mean flow rate had no significant change in the peak soot volume fraction and 1.4 times reduction in the total soot volume fraction. A correlation (ƒv Reˉ1 = a+b· Str) for the total soot volume fraction in the flame region for the unsteady laminar ethylene flames was obtained for the pulsation frequency between 10 Hz and 200 Hz, and the Reynolds number between 37 and 55. The soot primary particle size in steady and unsteady flames was measured using the Time-Resolved Laser-Induced Incandescence (TIRE-LII) and the double-exponential fit method. At maximum frequency (200 Hz), the soot particles were smaller in size by 15% compared to the steady case in the flame with the highest mean flow rate.

Investigations on selected chalcogenide glasses towards the realization of photonic devices

Among various optical sensing schemes, infrared spectroscopy is a powerful tool for detecting and determining the composition of complex organic samples since vibrational finger prints of all biomolecules and organic species are located in this window. This spectroscopic technique is simple, reliable, fast, non-destructive, cost-effective while having low sensitivity. Use of metallic nanoparticles in association with a good IR transparent sensing substrate, is one of the promising solutions to enhance the sensitivity. Chalcogenide glasses are promising substrate material because of their extended optical transmission window starting from the visible to the far infrared range up to 20 μm, high refractive index usually between 2 and 3 and high optical nonlinearity, which make them good candidates as IR sensors and optical ultrafast nonlinear devices. These glasses are favorable sensor materials for the infrared spectral range because of their high IR transparency to allow for low optical loss at wavelengths corresponding to the characteristic optical absorption bands of organic molecules, high refractive index for tight confinement of optical energy within the resonator structure, processibility into thin film form, chemical compatibility for adhesion of silver nano particles and thin films and resistance to the chemical environment to be sensed. Molecules adsorbed to silver island structures shows enhanced IR absorption spectra and the extent of enhancement is determined by many factors such as the size, density and morphology of silver structures, optical and dielectric properties of the substrate material etc.

Fabrication, Optical Analysis and Photonic Applications of Certain Metallic Nanostructure-Integrated Dye Doped Polymer Optical Fibers” submitted by Ms. Suneetha Sebastian

Polymer Optical Fibers have occupied historically a place for large core flexible fibers operating in short distances. In addition to their practical passive application in short-haul communication they constitute a potential research field as active devices with organic dopants. Organic dyes are preferred as dopants over organic semiconductors due to their higher optical cross section. Thus organic dyes as gain media in a polymer fiber is used to develop efficient and narrow laser sources with a tunability throughout the visible region or optical amplifier with high gain. Dyes incorporated in fiber form has added advantage over other solid state forms such as films since the pump power required to excite the molecules in the core of the fiber is less thereby utilising the pump power effectively. In 1987, Muto et.al investigated a dye doped step index polymer fiber laser. Afterwards, numerous researches have been carried out in this area demonstrating laser emission from step index, graded index and hollow optical fibers incorporating various dyes. Among various dyes, Rhodamine6G is the most widely and commonly used laser dye for the last four decades. Rhodamine6G has many desirable optical properties which make it preferable over other organic dyes such as Coumarin, Nile Blue, Curcumin etc. The research focus on the implementation of efficient fiber lasers and amplifiers for short fiber distances. Developing efficient plastic lasers with electrical pumping can be a new proposal in this field which demands lowest possible threshold pump energy of the gain medium in the cavity as an important parameter. One way of improving the efficiency of the lasers, through low threshold pump energy, is by modifying the gain of the amplifiers in the resonator/cavity. Success in the field of Radiative Decay Engineering can pave way to this problem. Laser gain media consisting of dye-nanoparticle composites can improve the efficiency by lowering the lasing threshold and enhancing the photostability. The electric field confined near the surface of metal nanoparticles due to Localized Surface Plasmon Resonance can be very effective for the excitation of active centers to impart high optical gain for lasing. Since the Surface Plasmon Resonance of nanoparticles of gold and silver lies in the visible range, it can affect the spectral emission characteristics of organic dyes such as Rhodamine6G through plasmon field generated by the particles. The change in emission of the dye placed near metal nanoparticles depend on plasmon field strength which in turn depends on the type of metal, size of nanoparticle, surface modification of the particle and the wavelength of incident light. Progress in fabrication of different types of nanostructures lead to the advent of nanospheres, nanoalloys, core-shell and nanowires to name a few. The thesis deals with the fabrication and characterisation of polymer optical fibers with various metallic and bimetallic nanostructures incorporated in the gain media for efficient fiber lasers with low threshold and improved photostability.

Effect of boiling on deposition of metallic colloids

In this study the relationship between heterogeneous nucleate boiling surfaces and deposition of suspended metallic colloidal particles, popularly known as crud or corrosion products in process industries, on those heterogeneous sites is investigated. Various researchers have reported that hematite is a major constituent of crud which makes it the primary material of interest; however the models developed in this work are irrespective of material choice. Qualitative hypotheses on the deposition process under boiling as proposed by previous researchers have been tested, which fail to provide explanations for several physical mechanisms observed and analyzed. In this study a quantitative model of deposition rate has been developed on the basis of bubble dynamics and colloid-surface interaction potential. Boiling from a heating surface aids in aggregation of the metallic particulates viz. nano-particles, crud particulate, etc. suspended in a liquid, which helps in transporting them to heating surfaces. Consequently, clusters of particles deposit onto the heating surfaces due to various interactive forces, resulting in formation of porous or impervious layers. The deposit layer grows or recedes depending upon variations in interparticle and surface forces, fluid shear, fluid chemistry, etc. This deposit layer in turn affects the rate of bubble generation, formation of porous chimneys, critical heat flux (CHF) of surfaces, activation and deactivation of nucleation sites on the heating surfaces. Several problems are posed due to the effect of boiling on colloidal deposition, which range from research initiatives involving nano-fluids as a heat transfer medium to industrial applications such as light water nuclear reactors. In this study, it is attempted to integrate colloid and surface science with vapor bubble dynamics, boiling heat transfer and evaporation rate. Pool boiling experiments with dilute metallic colloids have been conducted to investigate several parameters impacting the system. The experimental data available in the literature is obtained by flow experiments, which do not help in correlating boiling mechanism with the deposition amount or structure. With the help of experimental evidences and analysis, previously proposed hypothesis for particle transport to the contact line due to hydrophobicity has been challenged. The experimental observations suggest that deposition occurs around the bubble surface contact line and extends underneath area of the bubble microlayer as well. During the evaporation the concentration gradient of a non-volatile species is created, which induces osmotic pressure. The osmotic pressure developed inside the microlayer draws more particles inside the microlayer region or towards contact line. The colloidal escape time is slower than the evaporation time, which leads to the aggregation of particles in the evaporating micro-layer. These aggregated particles deposit onto or are removed from the heating surface, depending upon their total interaction potential. Interaction potential has been computed with the help of surface charge and van der Waals potential for the materials in aqueous solutions. Based upon the interaction-force boundary layer thickness, which is governed by debye radius (or ionic concentration and pH), a simplified quantitative model for the attachment kinetics is proposed. This attachment kinetics model gives reasonable results in predicting attachment rate against data reported by previous researchers. The attachment kinetics study has been done for different pH levels and particle sizes for hematite particles. Quantification of colloidal transport under boiling scenarios is done with the help of overall average evaporation rates because generally waiting times for bubbles at the same position is much larger than growth times. In other words, from a larger measurable scale perspective, frequency of bubbles dictates the rate of collection of particles rather than evaporation rate during micro-layer evaporation of one bubble. The combination of attachment kinetics and colloidal transport kinetics has been used to make a consolidated model for prediction of the amount of deposition and is validated with the help of high fidelity experimental data. In an attempt to understand and explain boiling characteristics, high speed visualization of bubble dynamics from a single artificial large cavity and multiple naturally occurring cavities is conducted. A bubble growth and departure dynamics model is developed for artificial active sites and is validated with the experimental data. The variation of bubble departure diameter with wall temperature is analyzed with experimental results and shows coherence with earlier studies. However, deposit traces after boiling experiments show that bubble contact diameter is essential to predict bubble departure dynamics, which has been ignored previously by various researchers. The relationship between porosity of colloid deposits and bubbles under the influence of Jakob number, sub-cooling and particle size has been developed. This also can be further utilized in variational wettability of the surface. Designing porous surfaces can having vast range of applications varying from high wettability, such as high critical heat flux boilers, to low wettability, such as efficient condensers.

Ceramic Materials Development for Intermediate Temperature Solid Oxide Fuel Cell (IT-SOFC)

Solid oxide fuel cell (SOFC) is an electrochemical device that converts chemical energy into electric power with high efficiency. Traditional SOFC has its disadvantages, such as redox cycling instability and carbon deposition while using hydrocarbon fuels. It is because traditional SOFC uses Ni-cermet as anode. In order to solve these problems, ceramic anode is a good candidate to replace Ni. However, the conductivity of most ceramic anode materials are much lower than Ni metal, and it introduces high ohmic resistance. How to increase the conductivity is a hot topic in this research field. Based on our proposed mechanism, several types of ceramic materials have been developed. Vanadium doped perovskite, Sr1-x/2VxTi1-xO3 (SVT) and Sr0.2Na0.8Nb1-xVxO3 (SNNV), achieved the conductivity as high as 300 S*cm-1 in hydrogen, without any high temperature reduction. GDC electrolyte supported cell was fabricated with Sr0.2Na0.8Nb0.9V0.1O3 and the performance was measured in hydrogen and methane respectively. Due to vanadium’s intrinsic problems, the anode supported cell is not easy. Fe doped double perovskite Sr2CoMoO6 (SFCM) was also developed. By carefully doping Fe, the conductivity was improved over one magnitude, without any vigorous reducing conditions. SFCM anode supported cell was successfully fabricated with GDC as the electrolyte. By impregnating Ni-GDC nano particles into the anode, the cell can be operated at lower temperatures while having higher performance than the traditional Ni-cermet cells. Meanwhile, this SFCM anode supported SOFC has long term stability in the reformate containing methane. During the anode development, cathode improvement caused by a thin Co-GDC layer was observed. By adding this Co-GDC layer between the electrolyte and the cathode, the interfacial resistance decreases due to fast oxygen ion transport. This mechanism was confirmed via isotope exchange. This Co-GDC layer works with multiple kinds of cathodes and the modified cell’s performance is 3 times as the traditional Ni-GDC cell. With this new method, lowering the SOFC operation temperature is feasible.

Anomalous magnetic behavior of La0.6Sr0.4MnO3 nano-tubes constituted with 3-12 nm particles

Uniform La0.6Sr0.4MnO3 (LSMO) nanotubes of an average diameter 180 nm were synthesized by a modified sol-gel method employing nanochannel porous anodic alumina templates. The nanotubes were characterized chemically and structurally by XRD, SEM, EDX, and TEM. Postannealed (700 degrees C for 1 h hour) nanotubes were found to be polycrystalline from XRD and SAED studies. To get further insight into the nanotube structure, HRTEM studies were done, which revealed that obtained LSMO nanotubes were structurally constituted with nanoparticles of 3-12 nm size. These constituent nanoparticles were randomly aligned and self-knitted to build the nanotube wall. Investigation of magnetic properties at this structured nanoscale revealed remarkable irreversibility between the zero field cooling (ZFC) and field cooling (FC) magnetization curves accompanied with a peak in the ZFC curve indicating spin-glass-like behavior. Structural defects and compositional variations at surfaces and grain-boundaries of constituent nanoparticles might be responsible for this anomalous magnetic behavior.

Temperature dependent magnetic ordering and electrical transport behavior of nano zinc ferrite from 20 to 800 K

The nano ZnFe2O4 compound was prepared by eco-friendly hydrothermal method. The characterization of the sample for its structure, morphology and composition were done by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), dynamic light scattering, Fourier transform infrared spectroscopy, zeta surface profiler and UV-Visible spectroscopy studies. The PXRD measurement reveals that the compound shows spinel cubic phase belong Fd (3) over barm (227) space group. Morphology of the compound from SEM and surface profile shows nearly spherical agglomerated particles with well defined grains and grain boundaries. The material shows the semiconducting behavior with E-g of 2.3 eV at room temperature (RT). The variation in the magnetic ordering was observed for wide range of temperature. The compound behaves like a soft magnetic material with ferrimagnetic at various temperatures except at RT. Both magnetic and EPR studies supports the superparamagnetic behavior of the the sample. The DC conductivity, dielectric and AC conductivity behavior of the 1000 degrees C pellets sintered for 2 h shows good frequency dependent transport properties. The present study facilitate in selecting the suitable materials for the nanoelectronics and spintronic applications. (C) 2013 Elsevier B.V. All rights reserved.

Magnetic and dielectric interactions in nano zinc ferrite powder: Prepared by self-sustainable propellant chemistry technique

The structural, magnetic and dielectric properties of nano zinc ferrite prepared by the propellant chemistry technique are studied. The PXRD measurement at room temperature reveal that the compound is in cubic spinel phase, belong to the space group Fd (3) over barm. The unit cell parameters have been estimated from Rietveld refinement. The calculated force constants from FTIR spectrum corresponding to octahedral and tetrahedral sites at 375 and 542 cm(-1) are 6.61 x 10(2) and 3.77 x 10(2) N m(-1) respectively; these values are slightly higher compared to the other ferrite systems. Magnetic hysteresis and EPR spectra show superparamagnetic property nearly to room temperature due to comparison values between magnetic anisotropy energy and the thermal energy. The calculated values of saturation magnetization, remenant magnetization, coercive field and magnetic moment supports for the existence of multi domain particles in the sample. The temperature dependent magnetic field shows the spin freezing state at 30 K and the blocking temperature at above room temperature. The frequency dependent dielectric interactions show the variation of dielectric constant, dielectric loss and impedance as similar to other ferrite systems. The AC conductivity in the prepared sample is due to the presence of electrons, holes and polarons. The synthesized material is suitable for nano-electronics and biomedical applications. (C) 2014 Elsevier B.V. All rights reserved.

Incorporation of Cr3+ ions in tuning the magnetic and transport properties of nano zinc ferrite

Cost effective and low temperature synthesis methods namely solution combustion and hydrothermal methods were used to prepare chromium incorporated nanocrystalline zinc ferrites. The effect of incorporation of low concentration Cr3+ ions on the structural, morphological, magnetic and transport properties of the zinc ferrite compounds were investigated. The crystalline nature and size variation with chromium content were valid from powder x-ray diffraction. Particles size and crystallite size variation were valid from scanning electron microscopy and transmission electron microscopy respectively. With the increase in chromium incorporation, the crystallite and particles sizes were decreased. Fourier transform infrared spectroscopy (FTIR) studies confirmed the presence of strong metal-oxygen bonds. The elastic properties of the materials in both the methods were estimated by FTIR studies. Magnetic properties namely saturation magentization, remanent magnetization and coercivity values were decreased with increase in Cr3+ ions concentration. The dielectric properties of the samples decreased with increase in the Cr3+ ions. The dielectric constant was observed to be of the order of 10(6) at low frequency and almost 1 at higher frequency range. The activation energy estimated using Arrhenius plots was of the order of 0.182 eV and 0.368 eV respectively for the compounds prepared by solution combustion and hydrothermal methods. The emission spectra of the samples excited at 344 nm were reported using photoluminescence (PL) spectroscopy. Further, the approximate energy band gap(E-g) was estimated from PL studies. The E-g of the materials were lie in the range of 2.11-1.98 eV. (C) 2015 Elsevier B.V. All rights reserved.

Large enhanced dielectric permittivity in polyaniline passivated core-shell nano magnetic iron oxide by plasma polymerization

Commercial samples of Magnetite with size ranging from 25–30nm were coated with polyaniline by using radio frequency plasma polymerization to achieve a core shell structure of magnetic nanoparticle (core)–Polyaniline (shell). High resolution transmission electron microscopy images confirm the core shell architecture of polyaniline coated iron oxide. The dielectric properties of the material were studied before and after plasma treatment. The polymer coated magnetite particles exhibited a large dielectric permittivity with respect to uncoated samples. The dielectric behavior was modeled using a Maxwell–Wagner capacitor model. A plausible mechanism for the enhancement of dielectric permittivity is proposed

Magnetic properties of spindle-type iron fine particles obtained from hematite

Spindle-type iron fine particles have been prepared by reduction of silica-coated-hematite particles. Hydrogen reduction of the coated-hematite cores yielded uniform spindle-type iron particles, which were stabilized by surface oxidation. Narrow particle distributions are observed from TEM measurements. X-ray, Mössbauer and magnetization data are in agreement with the presence of nanosized α-Fe particles, having surface layer of spinel structure oxide. Mössbauer spectra show that the oxide surface is superparamagnetic at room temperature. © 2001 Elsevier Science B.V. All rights reserved.

CONTROL OF SIZE AND MAGNETIC PROPERTIES OF CARBOXYL-FUNCTIONALIZED MAGNETITE PARTICLES: SYNTHESIS PROCEDURES, CHARACTERIZATIONS, AND APPLICATIONS

Magnetic nanoparticles (MNPs) are known for the unique properties conferred by their small size and have found wide application in food safety analyses. However, their high surface energy and strong magnetization often lead to aggregation, compromising their functions. In this study, iron oxide magnetic particles (MPs) over the range of nano to micro size were synthesized, from which particles with less aggregation and excellent magnetic properties were obtained. MPs were synthesized via three different hydrothermal procedures, using poly (acrylic acid) (PAA) of different molecular weight (Mw) as the stabilizer. The particle size, morphology, and magnetic properties of the MPs from these synthesis procedures were characterized and compared. Among the three syntheses, one-step hydrothermal synthesis demonstrated the highest yield and most efficient magnetic collection of the resulting PAA-coated magnetic microparticles (PAA-MMPs, >100 nm). Iron oxide content of these PAA-MMPs was around 90%, and the saturation magnetization ranged from 70.3 emu/g to 57.0 emu/g, depending on the Mw of PAA used. In this approach, the particles prepared using PAA with Mw of 100K g/mol exhibited super-paramagnetic behavior with ~65% lower coercivity and remanence compared to others. They were therefore less susceptible to aggregation and remained remarkably water-dispersible even after one-month storage. Three applications involving PAA-MMPs from one-step hydrothermal synthesis were explored: food proteins and enzymes immobilization, antibody conjugation for pathogen capture, and magnetic hydrogel film fabrication. These studies demonstrated their versatile functions as well as their potential applications in the food science area.