Recent work by architects on material life cycles and carbon sequestration has produced a large body of technical prowess but this knowledge struggles to scale. Synthesizing this emerging body of research with larger discourse about Post-Environmental Policy could produce a new model of practice that straddles the border between urban planning, resource management, and architecture. This new model will test the idea of every act of building as a phased development and test new outcomes, benefits and drawbacks of increased entanglements and time frames of what constitutes "building". / 0 / SPK / specialcollections@tulane.edu

Solid particles tend to adhere to fluid interfaces under the action of capillary force. This adsorption process is robust and has been exploited in lots of applications from stabilisation of emulsions to micro fluidic fabrications. The resulting particle laden fluid interfaces can manifest solid-like behaviours. The modifi cation of the surface tension and the emergence of surface shear elasticity of a particle-covered drops are attributed to the particle-induced surface stress. This stress represents at the continuum level the microscopic effect of particle-particle interactions. Understanding the link between the surface stress and the particle arrangement are crucial for creating novel soft materials in the future. A challenge remains when carrying out numerical simulations of particle-laden fluid interfaces: the large separation of scales makes the direct numerical simulations extraordinary expensive. Physical features present in the system come from both the liquid meniscus on the surface of each particle and the fluid interfaces containing thousands of particles. Motivated by the need for a fast simulation method to study problems involving particle-laden fluid interface, this thesis presents a new numerical formulation named Fast Interface Particle Interaction (FIPI) that can be used to simulate a large number of solid particles absorbed on fluid interfaces at a moderate computational cost. The outstanding performance of this new method is attributed to the fact that particle-level phenomena are modelled with analytical or semi-empirical expressions while hydrodynamics and fluid interface morphology at larger scales are fully resolved. Two important studies of particle-covered drops have been carried out with FIPI. In the first one a particle-covered pendant drop is simulated. The result reveals that the FIPI can successfully capture the modulation of surface tension made by absorbed particles. Moreover, the information of anisotropic surface stress is now directly available on the fluid interfaces. This capability has not been achieved previously in both experiments and simulations. The anisotropic stress emerged on the surface of a pendant drop is caused by anisotropic arrangement of the particles on the interface which in turn is induced by stretching of the interface due to gravity. Once the surface tension of the fluid interface is reduced below zero, the Laplace pressure inside the drop becomes negative and the drop can buckle like a thin solid elastic shell under compression. In the second study, the behaviours of a particle covered spherical drop under compression have been explored. The simulation results indicate the possibilities of particle desorption as well as fluid interface buckling. The onset of desorption is highly correlated to small-scale monolayer undulations which can greatly amplify the normal forces pushing particles out of the interface. The behaviours of a particle-covered drop under compression depend on the combination of several parameters related to the properties of the particle and the surface pressure created by the monolayer.

The development of sustainable and green technologies powered by renewable energy sources is highly desired to address the growing global energy need and water scarcity problems. Heterogeneous photocatalysis emerged in the past decades as promising solar-powered technology for environmental remediation applications such as wastewater treatment. The photoactivity of the materials is believed to be governed by complex mechanisms, still it was shown that it may be critically dependent on the following material properties (i) ability and effectiveness to absorb incident photons, (ii) charge separation efficiency, (iii) charge utilization efficiency, (iv) morphology including the size and shape of the nanostructure and its distribution and (v) the crystal structure, phase composition and crystallinity ... etc. Hence, most strategies aiming to improve the performance of photocatalytic materials may focus on one or more of the aforementioned aspects. Beside developing new materials or modifying existing systems, the development of sustainable, easy-to-operate systems are highly desired for developing countries such as Africa where almost half of the population are affected by water scarcity of some sort. For this motivation the immobilization of powder catalyst could be one attractive solution. In this thesis three experimental systems are presented. In the first two the effect of material properties on the photoactivity whereas in the third chapter the immobilization of powder catalyst was investigated. The first experimental project aimed to study the effect of synthesis parameters of WO3 nanostructures on its morphology, phase composition, optical properties and ultimately on the photoactivity. Understanding the role of process parameters to gain control over the material properties is still a challenge but is of great interest in photocatalysis. Here, a hydrothermal synthesis method was employed to synthesize WO3 nanostructures with various morphologies, crystal phases and optical properties. The effect of the solution pH, the polymeric surface modulator and the added EtOH was investigated on the material properties and on the photocatalytic activities. It was found that the crystal structure and the morphology of WO3 was influenced by the solution pH in the first place. It was proposed that stabilization effects between the crystal phase and the morphology could also influence the crystallization process beside supersaturation. It was revealed that despite the highest surface area of W-2.01-P20E, reduced oxidation state did not promote high photo-response. Instead the photoactivity of WO3 was seen as the compromise of the material properties including the optical, structural properties and the oxidation state. In the second experimental project the effect of Ag co-catalysis was studied on TiO2- Cu2O heterostructure formation. Coupling a wide band gap (TiO2) and a narrow band gap (Cu2O) semiconductor could benefit from extended light absorption properties and additionally from enhanced charged separation. In this study a facile wet chemical synthesis method was coupled with a UV treatment step to fabricate TiO2-Ag-CuxO ternary hybrid nano-materials. The effect of the Ag loading (1-5%) and the synthesis sequence of the Ag deposition step was evaluated on the material properties as well as on the visible photocatalytic activity. It was revealed that both the amount and the order of the Ag-deposition altered the material properties considerably. Typically TiO2/CuxO/Ag (TCA) catalysts had better visible light absorption properties but reduced affinity to adsorb methyl orange (MO) to their surface. Whereas, TiO2/Ag/CuxO (TAC) catalysts in general had better dye adsorption properties relative to TCA and had more efficient decoloration properties under visible light. TOC and HPLC-MS analysis revealed that MO and possibly its degradation products were mainly mineralized and/or adsorbed to the surface of TAC catalyst with 5% nominal Ag content in the visible process generating limited amount of byproducts in the final solution. The third experimental project focused on the immobilization of the previously prepared powder TiO2-Cu2O nanostructure. In this work a fluorine-doped tin oxide (FTO) glass sheet was used as a substrate and the doctor-blade coating technique has been employed to make TiO2-Cu2O thin films. Although this technique has a widespread use in the fabrication of solar cells to the best of our knowledge this is the first report on supported TiO2-Cu2O photocatalytic systems prepared by this method. To optimize the performance of the TiO2- Cu2O thin film under visible light irradiation, the chemical composition of the doctor-blading paste and the temperature of the final thermal treatment step was studied. It was found that both the paste composition and the heat treatment step played an important role in the material properties. When the film contained ethyl cellulose the minimum temperature to remove organic additives was 350 °C. Whereas for the films containing only alpha terpineol 300 °C was sufficient. It was revealed that the higher temperature treatment resulted in more oxidized films which were also shown in their deeper colour. The most effective film under visible light irradiation was TC-0-300 which contained no cellulose and was treated at the lowest temperature.

The basis of prosperity of 20th centrury is oil. As oil is going to be used up, people need to find alternatives to meet the earth’s energy demand in 21st centrury. For each second, there are about 1.2×1017 J energy hitting the earth. The energy in 1 hour of sunlight is about 4.32×1020 J, which almost meets the energy consumed on earth in 2016. It determines solar energy may be a potential candidate to solve the energy crisis. As for techniques to utilize solar energy, the most popular one is using photovoltaic (PV) cells. PV cell is a device to convert solar energy into electricity. There are also some other techniques trying to utilize solar energy. Photocatalysis is one of them, which is to convert solar energy into chemical energy. Applications of photocatalysis have extended from hydrogen evolution via water splitting to environemtnal remediation, CO2/ N2 reduction and so on. Photocatalysis, as an advanced oxidation process, has been extensively studied and applied to the purification and remediation of contaminated water and wastewater, and exhibits advantages over conventional treatment technologies. When considering solar energy as an energy source for photocatalysis, it is key to prepare visible light-responsive materials. Bismuth-based semiconductors are promising materials as visible light-responsive photocatalysts primarily due to their suitable band gaps, well-dispersed valence bands, and commercial availabilities at reasonable costs, as well as the possibility of preparing them under mild conditions. Recent work focusing on the preparation, characterization and activity testing of bismuth-based photo-active materials as well as their associated photoreactor designs are introduced herein. In order to enhance the photocatalytic activities of the new materials, different precursors, additives, preparation procedures and process parameters, as well as surface treatments were explored to obtain binary and ternary heterostructures, with different doping, surface modification, nanoparticle sizes and morphologies. It was found that formation of heterojunction and loading metal nanoparticle on the surface are very effective to imrove the photocatalytic activity of the support. In this work, we found that palladium nanoparticles modified BiVO4 exhibited excellent activity in the decomposition of phenol, which was even higher than TiO2. To facilitate the separation process of catalysis particels from a slurry system, magnetically separable composites were also prepared, and it was found that it is very effective to remove the particles from the slurry system using external magnets. To further scale up this process, two different types of immbolized photoreactors (flat-plate and packed beads photoreactor) were also developed. Suggestions were made for further work in this research area.

CoordenaÃÃo de AperfeiÃoamento de Pessoal de NÃvel Superior / Os semicondutores magnÃticos atraÃram a atenÃÃo de muitos cientistas nos Ãltimos anos devido, principalmente, a aplicaÃÃes tecnolÃgicas no ramo da spintrÃnica. Esses semicondutores podem ser desenvolvidos por meio de um processo chamado dopagem, onde alguns Ãtomos da matriz semicondutora sÃo substituÃdos aleatoriamente por Ãtomos magnÃticos. Esta propriedade possibilita a fabricaÃÃo de uma variedade de dispositivos eletrÃnicos a partir do mesmo material semicondutor. Neste trabalho utilizou-se a tÃcnica de moagem mecÃnica de altas energias para realizar a dopagem dos Ãxidos TiO2, SnO2 e In2O3 com Fe2O3, que foram caracterizados estruturalmente por difraÃÃo de raios-x e espectroscopia MÃssbauer. A sÃntese foi realizada em trÃs tipos de ferramentas de moagem que influenciaram no desenvolvimento da reaÃÃo. Foram formados compostos com fÃrmulas Sn(1-x)Fe(x)O2, Ti(1-x)Fe(x)O2 e {(In(1-x)Fe(x)}2O3, com valores de concentraÃÃo do dopante magnÃtico x de 2, 5 e 10% em Ãtomos. Utilizando jarra de poliacetal e esferas de zircÃnia foram sintetizadas amostras de TiO2 dopadas com Fe2O3. No entanto, a energia produzida por estas ferramentas nÃo foi suficiente para completar a formaÃÃo do composto. Com uma jarra e esferas de aÃo inox foram produzidas amostras de TiO2 dopadas com Fe2O3, que por sua vez foram contaminadas com impurezas de ferro metÃlico proveniente das ferramentas utilizadas. AlÃm disso, essas impurezas contribuÃram para a formaÃÃo de outra fase, a ilmenita (FeTiO3). Para alcanÃar um grau de pureza, essas amostras foram submetidas à lavagem com soluÃÃo de HCl para a retirada do ferro metÃlico, porÃm a fase referente a ilmenita nÃo foi eliminada. Compostos formados por TiO2, SnO2 e In2O3 dopados com Fe2O3 foram sintetizados em uma jarra de alumina com esferas de zircÃnia. Estas amostras nÃo apresentaram impurezas indesejÃveis e nÃo houve formaÃÃo de outras fase. Enquanto os compostos baseados em TiO2 e SnO2 mantiveram suas estruturas cristalinas originais, o composto {In(1-x)Fe(x)}2O3 sofreu uma mudanÃa de fase cristalina, da estrutura cÃbica original do In2O3 para hexagonal do tipo corundum. Resultados obtidos das medidas de espectroscopia MÃssbauer e difraÃÃo de raios-x mostraram que, com o aumento do tempo de moagem, o Fe^{3+} entra na matriz dos compostos semicondutores substituindo o Ti^{4+}, Sn^{4+} ou In^{3+} em sÃtios octaÃdricos. Foi observado tambÃm a formaÃÃo de um sÃtio com deficiÃncia de oxigÃnio nos compostos finais que pode ser atribuÃdo ao processo e longos tempos de moagem ou ainda ao desbalanÃo estequiomÃtrico dos compostos precursores usados na moagem. / Magnetic semiconductors have attracted the attention of scientists in recent years due, mainly, to technological applications in the field of spintronics. These semiconductors can be developed by a process called doping, where some atoms of the semiconductor matrix are randomly replaced by magnetic atoms. This property enables the fabrication of a manifold of electronic devices from the same semiconductor material. In this work the technique of high energy mechanical milling was applied to synthesize TiO_2, SnO2 and In2O3 doped with Fe2O3. The samples were structurally characterized by x-ray diffraction and MÃssbauer spectroscopy. The synthesis was performed using three types of milling tools which influenced the outcome of the reactions. Compounds with formulas Sn(1-x)Fe(x)O2, Ti(1-x)Fe(x)O2 and {In(1-x)Fe(x)2}O3 were formed, with values of magnetic dopant concentration x of 2, 5 and 10% in atoms. Samples of Fe2O3-doped TiO2 were processed using a jar of polyacetal and zirconia spheres. However, the energy produced by these tools was not sufficient to complete the formation of the compound. Samples of TiO2 doped with Fe2O3 were successfully produced using stainless steel jar and spheres. The final compound was find to be contaminated with metallic iron impurities from the tools used. Furthermore, these impurities contributed to the formation of another phase, ilmenite (FeTiO3). To achieve purity, the samples were HCl washed for removal of metallic iron, but the phase related to ilmenite was not eliminated. Moreover, samples of Fe2O3-doped TiO2, SnO2, and In2O3 were synthesized using an alumina jar and zirconia spheres. These simples showed no undesirable impurities and no formation of other phases. While compounds based on TiO2 and SnO2 maintained their original crystalline structures, the compound {In(1-x)Fe(x)2O3} underwent a change in crystal phase, from its original cubic structure to a hexagonal corundum structure type. Results obtained from X-ray diffraction and MÃssbauer spectroscopy showed that with increasing milling time Fe^{3+} enters in the semiconductor matrices substituting Ti^{4+}, Sn^{4+} or In^{3+} in octahedral sites. It was also observed the formation of oxygen deficient sites in the final compounds that may be attributed to long milling times or to stoichiometric imbalance between the precursor compounds used in the milling processes.

This study aims to synthesize nanostructured hematite films using spray pyrolysis at different deposition temperatures. L-arginine was used to transform the irregular shaped nanoparticles to uniform nanospheres by chemical bath deposition at 90°C for 48 h. We also investigated the variation of L-arginine: iron precursor concentrations from 1:1 to 3:1, respectively. Likewise, hematite films doped with zinc (Zn), silver (Ag), and Zn/Ag were synthesized using spray pyrolysis. All the films were annealed at temperatures ranging from 450 to 500°C for complete hematite phase transformation. The films were used as photoanodes in photoelectrochemical (PEC) water splitting experiments. X-ray diffraction confirmed the formation of the corundum hexagonal structure of hematite with space group. Raman spectroscopy further confirmed the polycrystalline hematite symmetry with two Eg and five A1g vibrational phonon modes. UV-Vis absorption showed a variation of absorbance with bandgaps that ranged from 2.10 to 1.90 eV. Scanning electron microscopy reported the shape transformation of nanoparticles to nanospheres that ranged in size from 6 to 100 nm. The study showed that the nanostructured films synthesized at temperatures of 430 and 400°C have the highest photocurrent densities of 6 and 1.52 µAcm-2, respectively. There was an improvement of the photocurrent density from 6.4 to 10 µAcm-2 after the transformation of pristine irregularly shaped hematite nanoparticles to spherical hematite. However, on the variation of L-arginine: iron precursor concentrations, a photocurrent of 9.8 µAcm-2 was obtained for 3:1 sample. Also, an improvement of photocurrent from 17 to 89 µAcm-2 was observed for films prepared at 30 and 50 mM iron precursor concentration, respectively. In addition, there was a significant increase in the photocurrent density from 40 to 813 µAcm-2 for pristine and Zn/Ag hematite films, respectively. Ultrafast transient absorption spectroscopy was used to study the electron-hole recombination rates and lifetimes. The results indicated four lifetimes obtained from global analysis with a reduction in the electron-hole recombination rate in the femtosecond and nanosecond range, both for L-arginine/hematite and doped samples. From this study, we were able to prove that the nanostructured and doped hematite films had a longer charge carrier lifetime compared to bulk hematite. / Thesis (PhD)--University of Pretoria, 2021. / African Laser Center (ALC) National Research Foundation (NRF) Grant no. N0115/115463 (SARChI, M.D.) University of Pretoria / Physics / PhD / Restricted

Organic Photovoltaic (OPV) solar cells provide a promising alternative for harnessing solar energy. However, the efficient design of OPV materials that achieve better performance requires support by better-tailored visualization tools than are currently available, which is the goal of this thesis. One promising approach in the OPV field is to control the effective material of the OPV device, which is known as the Bulk-Heterojunction (BHJ) morphology. The BHJ morphology has a complex composition. Current BHJ exploration techniques deal with the morphologies as black boxes with no perception of the photoelectric current in the BHJ morphology. Therefore, this method depends on a trial-and-error approach and does not efficiently characterize complex BHJ morphologies. On the other hand, current state-of-the-art methods for assessing the performance of BHJ morphologies are based on the global quantification of morphological features. Accordingly, scientists in OPV research are still lacking a sufficient understanding of the best material design. To remove these limitations, we propose a new approach for knowledge-assisted visual exploration and analysis in the OPV domain. We develop new techniques for enabling efficient OPV charge transport path analysis. We employ, adapt, and develop techniques from scientific visualization, geometric modeling, clustering, and visual interaction to obtain new designs of visualization tools that are specifically tailored for the needs of OPV scientists. At the molecular scale, the user can use semantic rules to define clusters of atoms with certain geometric properties. At the nanoscale, we propose a novel framework for visual characterization and exploration of local structure-performance correlations. We also propose a new approach for correlating structural features to performance bottlenecks. We employ a visual feedback strategy that allows scientists to make intuitive choices about fabrication parameters. We furthermore propose a visual analysis framework to help answer domain science questions through parameter space exploration for local morphology features. This framework is built on the shape-based clustering of local regions (patches), which for the first time enables local analysis of BHJ morphologies. Using our proposed system, domain experts can interactively create and visualize new BHJ structures of interest at both the molecular and nanoscale levels in a relatively short time.

No description available.

<p>The development of highly formable aluminum alloy sheets is of great interest to the automotive industry, because they provide a lightweight alternative to steel sheet for structural panels. Finding ways to improve the formability of Al alloys is the main subject of the present investigation. This issue is tackled from two angles. First, a possibility of fabricating a two-phase material containing newly discovered ductile intermetallic compounds is considered. The Al-La-Mg system is thermodynamically optimized accompanied with a differential thermal analysis (DTA) experiment to validate the optimization results. A new approach is introduced to deal with the incompatibility of phase models in binary Al-La and La-Mg systems. This approach is successfully applied to the Laves and B2 phases in the binary La-Mg system. A utilization of the thermodynamic description of the Al-La-Mg system to model solidification at low and high cooling rates shows that it is impossible to fabricate such a two-phase material by casting.</p> <p>Second, the effect of small additions of cerium and lanthanum on Fe-bearing intermetallics in a wrought heat-treatable Al alloy is examined. Fe-containing intermetallics are known to deteriorate the formability of Al alloys by acting as void nucleation sites. It is found that in alloys containing 0.1-0.2 wt. % of lanthanum, the fraction of less harmful Chinese script particles is pronouncedly higher than that in the reference alloy. In addition to this advantage, much smaller grains are seen in the alloy with 0.2 wt. % La. Despite similarities between La and Ce, the latter metal neither modifies the microstructure nor noticeably affects the gram size. Hot rolling and solutionizing nullifies the beneficial effect of small La additions resulting in no improvement in the formability of the alloy.</p> <p>In order to understand how lanthanum affects the phase portrait of the alloy, a socalled direct thermal analysis experiment is performed. Solidification paths are derived for slowly cooled alloys by coupling the results of this investigation with microstructural observations. The likelihood of two modification mechanisms is speculated using these solidification paths.</p> / Thesis / Doctor of Philosophy (PhD)

This thesis explores a range of photoactive metal halide perovskite materials for use in photovoltaic applications. These materials are of huge interest due to their outstanding optoelectronic properties which result in high photovoltaic power conversion efficiencies. In particular, this thesis discusses perovskites with stoichiometry ABX₃ where A is a singly charged cation, for example methylammonium (MA), B is predominantly lead (Pb²⁺), and X is iodide (I-) and/or bromide (Br^-). At present the commercial applications of these materials are limited by the chemical instability of the A-site cation. In this thesis, the effect of chemical substitution of the A-site is investigated as a way to increase the stability of the perovskite material. Full replacement with the inorganic cation caesium (Cs⁺) is shown to significantly improve the chemical stability. However, the inorganic lead halide perovskites with ideal bandgaps for photovoltaic applications exhibit structural instability. Routes to achieve both chemical and structural stability for these perovskites are discussed. Consequently, this thesis represents pioneering work in the field of inorganic halide perovskites and will greatly assist the development of stable inorganic perovskite materials for optoelectronic applications such as tandem photovoltaics and LEDs. Chapters 1 and 2 of this thesis present the motivation for perovskite materials to be used in solar cells, along with relevant background information about these materials and solar cell operation in general. Chapter 3 details the methods utilised in the experimental results chapters which follow. The first experimental results chapter, Chapter 4, shows how incorporation of Br^- in place of I^- in CsPbI₃ leads to increased ambient stability of the perovskite structure, and the first solar cells with CsPbI₂Br as the absorbing photovoltaic material are reported. Chapter 5 remedies the deficit of information about the optoelectronic properties of the CsPbI_3-xBr_x (0 &le; x &le; 3) perovskites through magneto-optical measurements on thin-films. These measurements raise questions about the room temperature perovskite structure of the CsPbI_3-xBrx compositions with small x, previously thought to be cubic perovskite, which is shown in Chapter 6 to be an orthorhombic perovskite polymorph. This finding motivates preliminary work presented in Chapter 7 aimed at chemical stabilisation of this orthorhombic perovskite polymorph. Finally, Chapter 8 summarises the work presented in this thesis, and recommends further research for the development of stable perovskite materials for photovoltaics.