Spelling suggestions: "subject:"stabilized zirconium""
1 |
Synthesis of Mesoporous Metal Oxide MaterialsJanuary 2012 (has links)
abstract: Nanoporous crystalline oxides with high porosity and large surface areas are promising in catalysis, clean energy technologies and environmental applications all which require efficient chemical reactions at solid-solid, solid-liquid, and/or solid-gas interfaces. Achieving the balance between open porosity and structural stability is an ongoing challenge when synthesizing such porous materials. Increasing porosity while maintaining an open porous network usually comes at the cost of fragility, as seen for example in ultra low density, highly random porous aerogels. It has become increasingly important to develop synthetic techniques that produce materials with these desired properties while utilizing low cost precursors and increasing their structural strength. Based on non-alkoxide sol-gel chemistry, two novel synthetic methods for nanoporous metal oxides have been developed. The first is a high temperature combustion method that utilizes biorenewable oil, affording gamma alumina (Al2O3) with a surface area over 300 cm3/g and porosity over 80% and controllable pore sizes (average pore width 8 to 20 nm). The calcined crystalline products exhibit an aerogel-like textural mesoporosity. To demonstrate the versatility of the new method, it was used to synthesize highly porous amorphous silica (SiO2) which exhibited increased mechanical robustness while achieving a surface area of 960 m2/g and porosity of 85%. The second method utilizes sequential gelation of inorganic and organic precursors forming an interpenetrating inorganic/organic gel network. The method affords yttria-stabilized zirconia with surface area over 90 cm3/g and porosity over 60% and controllable pore sizes (average pore width 6 to 12 nm). X-ray diffraction, gas sorption analysis, Raman spectroscopy, nuclear magnetic resonance spectroscopy and electron microscopy were all used to characterize the structure, morphology, and the chemical structure of the newly afforded materials. Both novel methods produce products that show superior pore properties and robustness compared to equivalent commercially available and currently reported materials. / Dissertation/Thesis / Ph.D. Chemistry 2012
|
2 |
Zero-direct emission silicon production via solid oxide membrane electrolysisVillalon Jr., Thomas Anthony 03 July 2018 (has links)
Currently, industrial processes that produce silicon occur in batch units which are
energy intensive, capital intensive, and emit harmful pollutants into the atmosphere. A
new technology, solid oxide membrane (SOM) processing, seeks to produce silicon
without direct emissions and with lower energy and capital costs. Previous studies have
shown that this technology can produce silicon; however, the proof-of- concept cell was
incapable of producing large volumes of silicon due to restrictions in the molten salt.
Current research has engineered an oxyfluoride molten salt to be more efficient in
four main ways: higher amount of silica in the molten salt, chemistry stable with the
yttria-stabilized zirconia (YSZ) membrane, low volatility, and high electrical
conductivity. The newly designed salt allows for up to 25 at% of silicon oxide to dissolve
into the flux, removing mass transfer limitations. The mixture utilizes calcium oxide to
stabilize the presence of silicon oxide, giving the flux a volatility of less than 0.1 µg/cm 2
*s. The presence of calcium oxide also increases the optical basicity of the system,
allowing the flux to be compatible with the YSZ membrane showing no signs of
corrosion. Lastly, the new flux composition has a conductivity of 2.87 and 4.38 S/cm, at
1050 °C and 1100 °C, respectively, which is above the desired value of 1 S/cm.
vii
Combining these improvements in the salt with pre-existing techniques, silicon
crystals were produced in the new SOM cell. Two distinct SOM cell configurations were
attempted, one with a liquid cathode (tin) and one with a solid cathode (molybdenum).
Both cells were able to successfully make silicon metal. The tin cathode was able to
produce high purity silicon crystals extracted via acid etching. The molybdenum cathode
produced a plated layer of molybdenum disilicide. Samples were examined by using
scanning electron microscopy (SEM) and energy dispersive x-ray spectroscopy (EDS).
An equivalent circuit model for the SOM process was developed to calculate polarization
losses during the electrolysis process.
|
3 |
Modeling and Evaluating the Thermal Conductivity of Porous Thermal Barrier Coatings at Elevated Temperatures for Industrial ApplicationsAlotaibi, Moteb 19 August 2019 (has links)
The thermal conductivity of various porous thermal barrier coating (TBC) systems used in elevated temperature for industrial applications has been evaluated using a proposed six-phase model. These porous TBC systems rely on microstructural properties and yield different types of porosity. These microstructural properties can influence the thermal conductivity of TBC systems. The purpose of this thesis is to assess the thermal conductivity of TBC systems based on microstructural attributes, particularly the effect of different types of porosity. Thus, the first component of this thesis investigates the microstructural characterization of various TBC systems using image analysis (IA) technique. In this technique, scanning electron microscopy (SEM) and light optical microscopy (LOM) micrographs were used to measure the porosity level of different TBC materials. The volumetric fraction of porosity along with orientation, shape, and morphology have a considerable impact on the total thermal conductivity of TBCs.
The second component of this thesis evaluates the thermal conductivity of these porous TBC systems by taking into account the effect of the heat treatment process. The IA results reveal that as long as the porosity content increases, the thermal conductivity decreases for all of the TBC materials studied in this thesis. Further, while the content of microcracks and non-flat porosity play a crucial role in reducing the thermal conductivity of TBC materials, the other types of porosity (open randomly oriented, penny-shaped, and interlamellar) exert less impact on the thermal conductivity of TBCs. Comparing the results of the proposed six-phase model to experimental values and finite element analysis (FEA) values showed a relatively good agreement.
The proposed six-phase model can predict the thermal conductivity of porous microstructure of TBC systems close to real measured values; therefore, the proposed six-phase model may be utilized to fabricate the porous microstructure of TBCs.
|
4 |
Efeitos da adição do NiO na densificação, na microestrutura e na condutividade elétrica da zircônia totalmente estabilizada com ítría / Effects of NiO addition on the densification, microstructure and electrical conductivity of yttria fully-stabilized zirconiaBatista, Rafael Morgado 24 February 2010 (has links)
Os efeitos decorrentes da adição de NiO na densificação, na microestrutura e na condutividade elétrica da zircônia totalmente estabilizada com ítria foram sistematicamente estudados. Zircônia-8% mol de ítria (8YSZ) comercial e acetato, trihidróxi-carbonato, nitrato e óxido de níquel foram utilizados como materiais de partida. Os teores de Ni variaram entre 0,5% e 5% em mol e as composições foram preparadas por mistura dos materiais precursores a partir das concentrações estequiométricas. Estudos de densificação realizados por meio de medidas de densidade geométrica e dilatometria revelaram que a retração total até 1400ºC varia de ~16 até ~20% dependendo do precursor de níquel. No segundo estágio de sinterização a retração linear aumentou com o aumento no teor do aditivo (precursor: trihidróxi-carbonato de níquel). No estágio inicial de sinterização a energia de ativação para a difusão via contornos de grão varia de acordo com o precursor de níquel utilizado sendo menor para o óxido e maior para o trihidróxi-carbonato. No estágio secundário de sinterização prevalece a sinterização volumétrica. Neste estágio, as temperaturas de máxima retração são independentes do precursor de níquel, exceto para o acetato. O tamanho médio de cristalito variou com o tipo de precursor empregado sendo menor para o trihidróxi-carbonato e maior para o óxido de níquel. O limite de solubilidade do NiO determinado por difração de raios X é 1,48% em mol a 1350ºC. Para teores acima do limite de solubilidade o aditivo permanece aleatoriamente distribuído como uma fase secundária na forma de NiO. O principal efeito do aditivo na microestrutura é aumentar o tamanho médio de grãos. Os resultados de medidas elétricas revelaram que a adição de NiO não produz alterações significativas na condutividade intragranular da 8YSZ para diversos tempos de sinterização, exceto quando o precursor é o óxido de níquel, para o qual a condutividade elétrica aumenta com o tempo de sinterização evidenciando a dificuldade na formação de solução sólida, quando o material precursor possui tamanho de cristalito superior ao da matriz. Entretanto, a condutividade intragranular nas amostras preparadas com o trihidróxi-carbonato de nickel é pouco inferior à das demais amostras. Nas amostras sinterizadas por 15 h a 1350ºC um terceiro semicírculo foi associado com a formação de fase tetragonal na 8YSZ, devido à aceleração pelo níquel na cinética da transformação de fase cúbica para tetragonal. A condutividade intergranular varia com o tempo de sinterização devido à diminuição na fração de interfaces (contornos de grão) que ocorre com o aumento no tamanho médio de grãos. A condutividade intergranular microscópica da 8YSZ não varia significativamente com a adição de NiO. / The effects produced by NiO addition to yttria fully-stabilized zirconia were systematically investigated. Commercial zirconia-8 mol% yttria, nickel acetate, nitrate, trihydroxicarbonate and nickel oxide were used as starting materials. The NiO content varied from 0.5 to 5 mol%, and the compositions were prepared by mechanically mixing the starting materials in the stoichiometric proportions. Densification studies carried out by density and dilatometry measurements revealed that the maximum shrinkage (~16-~20%) depends on the type of nickel precursor. In the second sintering stage the linear shrinkage increased with increasing NiO content (precursor: nickel trihydroxi-carbonate). In the first sintering stage, the activation energy for grain boundary diffusion changed according to the additive precursor, being lower for the oxide and higher for the trihydroxi-carbonate. In the second stage, when the major part of porosity is eliminated, the maximum shrinkage rate temperatures were found to be independent on the precursor except when nickel acetate is used. The solubility limit at 1350ºC is 1.48% as determined by X-ray diffraction. Above the solubility limit the excess NiO is retained as a second randomly distributed phase. The main effect of the additive in the ceramic microstructure is to increase the average grain size. The electrical measurements showed that the additive did not produce any significant effect in the grain conductivity irrespective of the sintering time, except when the precursor material was nickel oxide. In this case, the grain conductivity increased with increasing sintering time. This effect is attributed to the crystallite size of the nickel oxide precursor, which is higher than that of 8YSZ, slowing down the formation of solid solution. However, the grain conductivity of samples prepared with nickel trihydroxi-carbonate precursor is slightly lower than those of other samples. The samples sintered for 15 h exhibited an additional semicircle in the impedance diagram, which is assigned to the tetragonal phase of zirconia-yttria, resulting from thermal decomposition of the cubic structure. Hence, NiO additive accelerates the kinetics of cubic-to-tetragonal phase transformation in 8YSZ. The grain boundary conductivity depends on the sintering time due to reduction of the fraction of interfaces as a consequence of grain growth. The microscopic grain boundary conductivity of 8YSZ does not vary with NiO addition.
|
5 |
Efeitos da adição do NiO na densificação, na microestrutura e na condutividade elétrica da zircônia totalmente estabilizada com ítría / Effects of NiO addition on the densification, microstructure and electrical conductivity of yttria fully-stabilized zirconiaRafael Morgado Batista 24 February 2010 (has links)
Os efeitos decorrentes da adição de NiO na densificação, na microestrutura e na condutividade elétrica da zircônia totalmente estabilizada com ítria foram sistematicamente estudados. Zircônia-8% mol de ítria (8YSZ) comercial e acetato, trihidróxi-carbonato, nitrato e óxido de níquel foram utilizados como materiais de partida. Os teores de Ni variaram entre 0,5% e 5% em mol e as composições foram preparadas por mistura dos materiais precursores a partir das concentrações estequiométricas. Estudos de densificação realizados por meio de medidas de densidade geométrica e dilatometria revelaram que a retração total até 1400ºC varia de ~16 até ~20% dependendo do precursor de níquel. No segundo estágio de sinterização a retração linear aumentou com o aumento no teor do aditivo (precursor: trihidróxi-carbonato de níquel). No estágio inicial de sinterização a energia de ativação para a difusão via contornos de grão varia de acordo com o precursor de níquel utilizado sendo menor para o óxido e maior para o trihidróxi-carbonato. No estágio secundário de sinterização prevalece a sinterização volumétrica. Neste estágio, as temperaturas de máxima retração são independentes do precursor de níquel, exceto para o acetato. O tamanho médio de cristalito variou com o tipo de precursor empregado sendo menor para o trihidróxi-carbonato e maior para o óxido de níquel. O limite de solubilidade do NiO determinado por difração de raios X é 1,48% em mol a 1350ºC. Para teores acima do limite de solubilidade o aditivo permanece aleatoriamente distribuído como uma fase secundária na forma de NiO. O principal efeito do aditivo na microestrutura é aumentar o tamanho médio de grãos. Os resultados de medidas elétricas revelaram que a adição de NiO não produz alterações significativas na condutividade intragranular da 8YSZ para diversos tempos de sinterização, exceto quando o precursor é o óxido de níquel, para o qual a condutividade elétrica aumenta com o tempo de sinterização evidenciando a dificuldade na formação de solução sólida, quando o material precursor possui tamanho de cristalito superior ao da matriz. Entretanto, a condutividade intragranular nas amostras preparadas com o trihidróxi-carbonato de nickel é pouco inferior à das demais amostras. Nas amostras sinterizadas por 15 h a 1350ºC um terceiro semicírculo foi associado com a formação de fase tetragonal na 8YSZ, devido à aceleração pelo níquel na cinética da transformação de fase cúbica para tetragonal. A condutividade intergranular varia com o tempo de sinterização devido à diminuição na fração de interfaces (contornos de grão) que ocorre com o aumento no tamanho médio de grãos. A condutividade intergranular microscópica da 8YSZ não varia significativamente com a adição de NiO. / The effects produced by NiO addition to yttria fully-stabilized zirconia were systematically investigated. Commercial zirconia-8 mol% yttria, nickel acetate, nitrate, trihydroxicarbonate and nickel oxide were used as starting materials. The NiO content varied from 0.5 to 5 mol%, and the compositions were prepared by mechanically mixing the starting materials in the stoichiometric proportions. Densification studies carried out by density and dilatometry measurements revealed that the maximum shrinkage (~16-~20%) depends on the type of nickel precursor. In the second sintering stage the linear shrinkage increased with increasing NiO content (precursor: nickel trihydroxi-carbonate). In the first sintering stage, the activation energy for grain boundary diffusion changed according to the additive precursor, being lower for the oxide and higher for the trihydroxi-carbonate. In the second stage, when the major part of porosity is eliminated, the maximum shrinkage rate temperatures were found to be independent on the precursor except when nickel acetate is used. The solubility limit at 1350ºC is 1.48% as determined by X-ray diffraction. Above the solubility limit the excess NiO is retained as a second randomly distributed phase. The main effect of the additive in the ceramic microstructure is to increase the average grain size. The electrical measurements showed that the additive did not produce any significant effect in the grain conductivity irrespective of the sintering time, except when the precursor material was nickel oxide. In this case, the grain conductivity increased with increasing sintering time. This effect is attributed to the crystallite size of the nickel oxide precursor, which is higher than that of 8YSZ, slowing down the formation of solid solution. However, the grain conductivity of samples prepared with nickel trihydroxi-carbonate precursor is slightly lower than those of other samples. The samples sintered for 15 h exhibited an additional semicircle in the impedance diagram, which is assigned to the tetragonal phase of zirconia-yttria, resulting from thermal decomposition of the cubic structure. Hence, NiO additive accelerates the kinetics of cubic-to-tetragonal phase transformation in 8YSZ. The grain boundary conductivity depends on the sintering time due to reduction of the fraction of interfaces as a consequence of grain growth. The microscopic grain boundary conductivity of 8YSZ does not vary with NiO addition.
|
6 |
Zero-direct-carbon-emission aluminum production by solid oxide membrane-based electrolysis processSu, Shizhao 21 June 2016 (has links)
The traditional aluminum production process (Hall-Héroult process) involves electrolyzing the alumina dissolved in the molten cryolite salt. This process is energy intensive and emits massive amounts of CO2 and other greenhouse gases. The market demand of aluminum and the environmental impact of the current aluminum production process justify research and development of alternative electrolytic processes for aluminum production that can both reduce the cost and eliminate adverse environment impacts.
Solid oxide membrane (SOM) based electrolysis process is an innovative technology that has been demonstrated to successfully produce many energy-intensive metals directly from their oxides in an efficient, economical and environmentally sound way. During the SOM electrolysis process, an oxygen-ion-conducting SOM tube made of ytteria-stabilized zirconia (YSZ) separates the pre-selected molten flux with dissolved metal oxide from the inert anode assembly inside the YSZ tube. When the applied DC potential between the cathode and the anode exceeds the dissociation potential of desired metal oxide, the metal is reduced at the cathode while oxygen ions migrate through the YSZ membrane and are oxidized at the anode. Employing the inert anode allows the oxygen to be collected at the anode as a value added byproduct.
In this work, a zero-direct-carbon-emission aluminum production process utilizing SOM electrolysis is presented. The molten flux used in the electrolysis process is optimized through careful measurements of its physio-chemical properties. The liquidus temperature, volatilization rate, alumina solubility, aluminum solubility, YSZ membrane degradation rate and electrical conductivity of various flux compositions were measured, and the flux chosen for SOM electrolysis was a eutectic MgF2-CaF2 system containing optimized amounts of YF3, CaO and Al2O3. Laboratory scale SOM electrolysis employing the inert anode were performed at 1100 ~ 1200oC to demonstrate the feasibility of producing and collecting aluminum while producing pure oxygen as a byproduct. The aluminum product was characterized by scanning electron microscopy (SEM) and energy dispersive x-ray spectroscopy (EDS). An equivalent circuit model for the electrolysis process was developed in order to identify the polarization losses in the SOM electrolysis cell. / 2016-12-21T00:00:00Z
|
7 |
Electrochemical Promotion of Gold Nanoparticles Supported on Yttria-Stabilized ZirconiaKim, Jong Min 23 November 2011 (has links)
The feasibility of highly dispersed gold nanocatalyst supported on yttria-stabilized zirconia (YSZ) for the model reactions of C2H4 and CO oxidation is demonstrated for the first time. Gold nanoparticles are synthesized on YSZ powder by chemical reduction of the precursor salt in the mixture of ethanol, water and polyvinylpyrrolidone (PVP). Resulting metal loading of the catalysts are 1 wt.% with average particle sizes ranging from 6 to 9 nm. Results of CO and C2H4 oxidation display catalytic activity at 65 0C and 25 0C for CO and C2H4 oxidation, respectively. The catalytic properties of the catalysts are different due to their average particle size. Electrochemical Promotion of Catalysis (EPOC) of C2H4 oxidation is demonstrated. Application of constant potential difference between two electrodes in the bipolar electrochemical cell led to increase in C2H4 conversion. A proposed mechanism explains the bipolar EPOC phenomenon through formation of O2- flux across the electrochemical cell, resulting in the change of Work Function of gold nanoparticles placed in between the electrodes and is electronically isolated.
|
8 |
Electrochemical Promotion of Gold Nanoparticles Supported on Yttria-Stabilized ZirconiaKim, Jong Min 23 November 2011 (has links)
The feasibility of highly dispersed gold nanocatalyst supported on yttria-stabilized zirconia (YSZ) for the model reactions of C2H4 and CO oxidation is demonstrated for the first time. Gold nanoparticles are synthesized on YSZ powder by chemical reduction of the precursor salt in the mixture of ethanol, water and polyvinylpyrrolidone (PVP). Resulting metal loading of the catalysts are 1 wt.% with average particle sizes ranging from 6 to 9 nm. Results of CO and C2H4 oxidation display catalytic activity at 65 0C and 25 0C for CO and C2H4 oxidation, respectively. The catalytic properties of the catalysts are different due to their average particle size. Electrochemical Promotion of Catalysis (EPOC) of C2H4 oxidation is demonstrated. Application of constant potential difference between two electrodes in the bipolar electrochemical cell led to increase in C2H4 conversion. A proposed mechanism explains the bipolar EPOC phenomenon through formation of O2- flux across the electrochemical cell, resulting in the change of Work Function of gold nanoparticles placed in between the electrodes and is electronically isolated.
|
9 |
Establishment of Relationships between Coating Microstructure and Thermal Conductivity in Thermal Barrier Coatings by Finite Element ModellingGupta, Mohit January 2010 (has links)
Plasma sprayed Thermal Barrier Coating systems (TBCs) are commonly used for thermal protection of components in modern gas turbine application such as power generation, marine and aero engines. The material that is most commonly used in these applications is Yttria Partially Stabilized Zirconia (YPSZ) because of this ceramic’s favourable properties, such as low thermal conductivity, phase stability to high temperature, and good erosion resistance. The coating microstructures in YPSZ coatings are highly heterogeneous, consisting of defects such as pores and cracks of different sizes which determine the coating’s final thermal and mechanical properties, and the service lives of the coatings. Determination of quantitative microstructure–property correlations is of great interest as experimental procedures are time consuming and expensive. Significant attention has been given to this field, especially in last fifteen years. The usual approach for modelling was to describe various microstructural features in some way, so as to determine their influence on the overall thermal conductivity of the coating. As the analytical models over-simplified the description of the defects, various numerical models were developed which incorporated real microstructure images.This thesis work describes two modelling approaches to further investigate the relationships between microstructure and thermal conductivity of TBCs. The first modelling approach uses a combination of a statistical model and a finite element model which could be used to evaluate and verify the relationship between microstructural defects and thermal conductivity. The second modelling approach uses the same finite element model along with a coating morphology generator, and can be used to design low thermal conductivity TBCs. A tentative verification of both the approaches has been done in this work.
|
10 |
Electrochemical Promotion of Gold Nanoparticles Supported on Yttria-Stabilized ZirconiaKim, Jong Min 23 November 2011 (has links)
The feasibility of highly dispersed gold nanocatalyst supported on yttria-stabilized zirconia (YSZ) for the model reactions of C2H4 and CO oxidation is demonstrated for the first time. Gold nanoparticles are synthesized on YSZ powder by chemical reduction of the precursor salt in the mixture of ethanol, water and polyvinylpyrrolidone (PVP). Resulting metal loading of the catalysts are 1 wt.% with average particle sizes ranging from 6 to 9 nm. Results of CO and C2H4 oxidation display catalytic activity at 65 0C and 25 0C for CO and C2H4 oxidation, respectively. The catalytic properties of the catalysts are different due to their average particle size. Electrochemical Promotion of Catalysis (EPOC) of C2H4 oxidation is demonstrated. Application of constant potential difference between two electrodes in the bipolar electrochemical cell led to increase in C2H4 conversion. A proposed mechanism explains the bipolar EPOC phenomenon through formation of O2- flux across the electrochemical cell, resulting in the change of Work Function of gold nanoparticles placed in between the electrodes and is electronically isolated.
|
Page generated in 0.0634 seconds