" This work investigated the long-term stability of sulfur tolerant Pd/Cu alloy membranes for hydrogen separation by performing characterizations lasting several thousand hours in H2, He and H2S/H2 atmospheres ranging in concentration from 0.2 – 50 ppm and temperatures ranging from 250 - 500ºC. Two methods were used for fabricating the Pd/Cu membranes so that the sulfur tolerant fcc alloy would remain on the surface and minimize the decrease in hydrogen permeance inherent with fcc Pd/Cu alloys. The first method consisted of annealing a Pd/Cu bi-layer at high-temperatures and the second consisted of depositing a Pd/Cu/Pd tri-layer with an ultra-thin surface alloy. High temperature X-ray diffraction (HT-XRD) was employed to study the kinetics of the annealing process and atomic adsorption spectroscopy (AAS) was used to investigate the kinetics of the Cu deposition and Pd displacement of Cu. Upon the introduction of H2S, the permeance decrease observed was dependent upon the H2S feed concentration, and not the time of poisoning. However, after the recovery in pure H2 there was a portion of the permeance which could not be recovered due to adsorbed sulfur blocking H2 adsorption sites. The amount of recoverable permeance was dependent on the time of exposure to H2S and reached a limiting value which decreased with temperature. X-ray photoemission spectroscopy (XPS) was used to investigate poisoned samples and it was observed that the permeance not recovered at a given temperature in H2 was caused mostly by Cu sulfides. Both bi-layer and tri-layer membranes had hydrogen permeances which were higher than homogeneous Pd/Cu membranes of the same surface concentration. However, the tri-layer membranes performed as well as Pd membranes thus eliminating the disadvantage of alloying Pd with Cu without sacrificing sulfur tolerance. "

"A ¡°mixed cathodes¡± LIB recycling process was first proposed and developed in the CR3 center at Worcester Polytechnic Institute. This process can efficiently and economically recover all the valuable metal elements in LIB waste. In the end of the recovery process, lithium, nickel, manganese, and cobalt ions will be recovered in the leaching solution. The objective of this work is to utilize the leaching solution to synthesis NixMnyCoz(OH)2 precursors and their corresponding LiNixMnyCozO2 cathode materials. The synthesized cathode materials can be used to build new LIBs, allowing the overall process to be a ¡°closed loop¡±. "

The Cu-Sb-S compounds (Cu12Sb4S13, CuSbS2, Cu3SbS3 and Cu3SbS4) have the advantages of earth-abundance, low-toxicity and low-cost, compared with conventional thermoelectric materials. This work provides a comprehensive study on the synthesis methods, crystal structures and thermoelectric properties of Cu-Sb-S compounds. All of the samples were prepared by mechanical alloying combined with SPS, which had high density, high purity and very fine microstructure. The lone-pair electrons of Sb and the [CuS3] plane play important roles in realizing very low lattice thermal conductivity of these compounds. Except for Cu12Sb4S13, which is known as a good thermoelectric material, the other three compounds showed very poor thermoelectric performance due to their high electrical resistivities. A phase transition at 398 K was found in Cu3SbS3, which makes it unsuitable for applications and attempts to optimize electrical properties of CuSbS2 failed. Different p-type dopants were studied to improve the electrical properties of Cu3SbS4. Both Ge-doping and Sn-doping on Sb sites increased the carrier concentration of Cu3SbS4 significantly. The electrical transport properties were analyzed using SPB model, and a large effective mass of 3.0 me was found for all of the samples. A maximum zT value of 0.69 was obtained at 623 K in 5 mol. % Sn-doped sample which was about 6 times higher than that of undoped sample. The solid-solutions of Cu3SbS4(1-y)Se4y were studied to further improve the thermoelectric properties. The lattice thermal conductivity was reduced in solid-solution due to the local mass contrast and alloying scattering, but there was no further improvement in zT value due to the decrease in Seebeck coefficient. Another solid solution of Cu3Sb1-xBixS4 was studied, but Bi had very low solubility and a second phase was formed instead of forming the solid solution. Future work should focus on reducing the lattice thermal conductivity of Cu3SbS4 without impacting its electrical properties.

Made available in DSpace on 2014-06-12T17:40:06Z (GMT). No. of bitstreams: 2 arquivo7607_1.pdf: 2211073 bytes, checksum: b41804eead923399b6fc86851c635dc3 (MD5) license.txt: 1748 bytes, checksum: 8a4605be74aa9ea9d79846c1fba20a33 (MD5) Previous issue date: 2006 / Este trabalho teve por objetivo estudar alguns tratamentos térmicos para se eliminar ou inibir o processo de estabilização da martensita que é um fenômeno indesejado nas aplicações tecnológicas das ligas com memória de forma, provocando importantes alterações nos fenômenos de memória de forma, resultando em importantes modificações nos comportamentos físicosmecânicos do material. A estabilização da martensita pode ser eliminada ou atenuada através do emprego de tratamentos térmicos específicos ou a utilização de novos elementos de ligas. O estudo do envelhecimento envolve também os comportamentos das interfaces martensita/martensita e austenita/martensita, e da tensão crítica de indução da transformação. Foi estudada uma liga de composição nominal Cu-10%Al-8,4%Mn, que tem temperaturas críticas das transformações martensíticas em torno da temperatura ambiente, obtida a partir da fusão dos elementos químicos num forno de indução de 24 KVa. Amostras foram preparadas para estudo da microestrutura (microscopia ótica), da estrutura cristalina (difração de raios-X), para caracterização das temperaturas de transformação de fase (resistividade elétrica e ensaio de flexão). As amostras foram submetidas aos seguintes tratamentos térmicos de betatização: Têmpera em água a 25°C (BT25), Têmpera em água a 100°C (BT100) e Têmpera ao Ar (BTAr). Em seguida a liga foi caracterizada microestruturalmente apresentando a fase martensítica β 1, que após aquecimento apresenta as características da transformação martensítica inversa, com a fase austenítica ou matriz com estrutura de super-rede DO3. Na difração de raios-X foram obtidas características da fase martensítica β 1, com planos característicos da estrutura ordenada ortorrômbica 18R (β 1). Na resistividade elétrica a baixa temperatura analisou-se o comportamento das curvas de resistividade elétrica versus temperatura, para os diferentes procedimentos de tratamentos térmicos, e a partir das curvas foram determinadas às temperaturas críticas de transformação (AS, AF, MS e MF), as amplitudes térmicas (AT) e as histereses térmicas (HT). Foram realizados ensaios de flexão do tipo viga engastada para simular o efeito memória de forma com uma carga de 13 MPa aplicada à amostra através de um sistema de polia sendo realizada a ciclagem térmica. As curvas da deformação versus temperatura após carregamento da amostra na fase martensítica apresenta uma deformação, em seguida é aquecida e depois resfriada. No aquecimento há um comportamento linear da deformação em função da temperatura. No resfriamento a amostra apresenta um aumento da deformação pseudoplástica. Na resistividade elétrica a alta temperatura verificou-se as modificações nas curvas de temperaturas elevadas onde ocorrem às reações de transição ordem-desordem e de precipitação de fases. Difrações de raios-X foram realizadas a fim de se observar as modificações estruturais da fase martensítica. Os resultados foram analisados em função dos fenômenos da estabilização martensítica tais como supersaturação de lacunas de têmpera e transições ordem-desordem. Os resultados indicam alguns parâmetros que devem ser utilizados para minimizar os problemas causados pelo envelhecimento das ligas Cu-Al-Mn com memória de forma

Trabalho de investigação desenvolvido na Chalmers University of Technology. Department of Chemical and Biological Engineering. Division of Chemical Engineering. Competence Centre for Catalysis / Tese de mestrado integrado. Engenharia Química. Faculdade de Engenharia. Universidade do Porto. 2012

Introduction. Callous-unemotional (CU) traits predict socially debilitating outcomes including Antisocial Personality Disorder and violent crime in adulthood. Despite significant research, the etiology of CU traits is not well understood. This dissertation incorporates genetic, physiological, neuroanatomical, and self-report measures to investigate the etiology of CU traits. Specifically, this project focuses on measures previously found to associate with impaired fear-processing observed in individuals high on CU. Brain morphometry for paralimbic regions of interest (ROIs) and electromyographic facial eyeblink reflex to startle and fear-potentiated startle probes were investigated as potential endophenotypes for CU traits. Methods. Two genetically informative (ages 9-20) twin samples (N=1696 individuals; 848 twin pairs) were used to estimate the changing heritable and environmental influences on CU over the age range of 9-20 using age-moderated biometric structural equation modeling (SEM). To determine potential endophenotypes, shared genetic variance with CU was examined for baseline and fear-potentiated startle reflex and morphometric measures of brain ROIs. Results. The heritability of CU increases over the ages of 9-20, from approximately 34% at age 9 to 47% at age 20. Therefore, environmental mechanisms for CU are most influential at younger ages. Although there were no significant associations after correction for multiple testing, there was some evidence to suggest potential positive associations between CU traits and baseline and fear-potentiated startle in younger (9-14) females. There was also evidence suggesting potential negative associations between CU traits and right anterior cingulate cortex thickness as well as right posterior cingulate cortex thickness in females only. There was no genetic covariance between CU and any of the examined physiological or neuroanatomical phenotypes. Discussion. These results suggest that middle childhood may be the most salient time for environmental interventions associated with preventing or ameliorating CU traits. Furthermore, these results suggest that the cingulate cortex may play a role in the development of CU traits, possibly in females specifically. The cingulate cortex may influence CU traits through its roles in emotional processing, learning, and memory. Larger samples will likely be needed to determine the genetic relationship between CU traits and the structural development of the cingulate cortex.

This thesis describes new methods of carbon-carbon bond formation using metalated nitriles generated via metal exchange reactions. Sulfinylnitriles undergo a sulfinyl-metal exchange to yield lithiated, magnesiated and zincated nitriles, which can trap a range of electrophiles. The sulfinyl-metal exchange is effective with vinylic, quaternary and tertiary substitution patterns and addresses the long-standing problem of alkylating secondary nitriles. This method was then further extended to other oxidation states of sulfur, namely sulfonyl-metal exchange and relatively unknown sulfide-metal exchange. The sulfide metal exchange overcomes the problem related to the propensity of highly substituted sulfinylnitriles to eliminate. Sulfide-metal exchange is synthetically attractive because of the numerous methods for generating arylsulfides and the high tolerance of arylsulfides to numerous reagents. <br>A copper-catalyzed arylation reaction of aryl iodides and metalated nitriles was developed using catalytic Cu (I) and an amine ligand. A proof of principle has been established, providing a sound basis for developing the reaction. A new strategy has been developed for alkylation of alkenenitrile using LDA as base in presence of catalytic CuCN. Subsequent trapping with an electrophile, affords alkylated alkenenitriles in which the olefin is no longer in conjugation with the nitrile. <br>The distinct structural differences between N- & C-metalated nitriles have been harnessed in a series of chemoselective alkylations. Lithiated nitriles are found to be particularly reactive toward alkyl halides whereas magnesiated nitriles react selectively with oxygenated electrophiles. Using this strategy allows chemoselective alkylation of metalated nitriles. / Bayer School of Natural and Environmental Sciences; / Chemistry and Biochemistry / PhD; / Dissertation;

The energy carrier hydrogen is expected to solve some energy challenges. Since its oxidation does not emit greenhouse gases (GHGs), its use does not contribute to climate change, provided that it is derived from clean energy sources. Thermochemical water splitting using a Cu-Cl cycle, linked with a nuclear super-critical water cooled reactor (SCWR), which is being considered as a Generation IV nuclear reactor, is a promising option for hydrogen production. In this thesis, a comparative environmental study is reported of the three-, four- and five-step Cu-Cl thermochemical water splitting cycles with various other hydrogen production methods. The investigation uses life cycle assessment (LCA), which is an analytical tool to identify and quantify environmentally critical phases during the life cycle of a system or a product and/or to evaluate and decrease the overall environmental impact of the system or product. The LCA results for the hydrogen production processes indicate that the four-step Cu-Cl cycle has lower environmental impacts than the three- and five-step Cu-Cl cycles due to its lower thermal energy requirement. Parametric studies show that acidification potentials (APs) and global warming potentials (GWPs) for the four-step Cu-Cl cycle can be reduced from 0.0031 to 0.0028 kg SO2-eq and from 0.63 to 0.55 kg CO2-eq, respectively, if the lifetime of the system increases from 10 to 100 years. Moreover, the comparative study shows that the nuclear-based S-I and the four-step Cu-Cl cycles are the most environmentally benign hydrogen production methods in terms of AP and GWP. GWPs of the S-I and the four-step Cu-Cl cycles are 0.412 and 0.559 kg CO2-eq for reference case which has a lifetime of 60 years. Also, the corresponding APs of these cycles are 0.00241 and 0.00284 kg SO2-eq. It is also found that an increase in hydrogen plant efficiency from 0.36 to 0.65 decreases the GWP from 0.902 to 0.412 kg CO2-eq and the AP from 0.00459 to 0.00209 kg SO2-eq for the four-step Cu-Cl cycle. / UOIT

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