Creep and fatigue of a single crystal nickel base superalloy

The introduction of single crystal casting techniques has led to the development of existing nickel-base superalloys to produce materials with optimum mechanical properties in the single crystal condition. As single crystals are known to be anisotropic, a study is needed to determine the general mechanical properties of these materials, and determine the effects of crystal orientation upon them. A study has been carried out to identify the effect of orientation and temperature on the creep and fatigue properties of a development single crystal superalloy, SRR 99. Creep testing and crystal rotation experiments have been made on SRR 99 and an earlier development alloy, SRR 9. Fatigue experiments at elevated temperatures have been carried out on both notched and un-notched specimens of alloy SRR 99. To aid in this analysis, several analytical techniques have been employed including Laue x-ray orientation analysis, measurement of strain by photographic methods and microstructural examination. Crystal rotation experiments have indicated that shear of 1 precipitates by lbrace111rbrace< 112> slip systems is operative during primary creep deformation at temperatures of 750oC and 850oC. The effect of orientation variation obtained by standard casting practices was not found to be significant. Creep rupture was found to be associated with multiple crack initiation from micropores. Fatigue crack initiation in un-notched specimens was found to be related to microporosity and microstructural defects. Failure was predominantly by crystallographic crack growth on lbrace111rbrace planes. The use of linear elastic fracture mechanics to describe fatigue crack propagation in alloy SRR 99 was found to be acceptable at temperatures up to 850oC. Variation of temperature, frequency and crystal orientation was found to have only moderate effect upon crack propagation rates.

Investigating polymer-peptide conjugates and electrospinning for the production of advanced materials

This thesis describes the production of advanced materials comprising a wide array of polymer-based building blocks. These materials include bio-hybrid polymer-peptide conjugates, based on phenylalanine and poly(ethylene oxide), and polymers with intrinsic microporosity (PIMs). Polymer-peptides conjugates were previously synthesised using click chemistry. Due to the inherent disadvantages of the reported synthesis, a new, simpler, inexpensive protocol was sought. Three synthetic methods based on amidation chemistry were investigated for both oligopeptide and polymerpeptide coupling. The resulting conjugates produced were then assessed by various analytical techniques, and the new synthesis was compared with the established protocol. An investigation was also carried out focussing on polymer-peptide coupling via ester chemistry, involving deprotection of the carboxyl terminus of the peptide. Polymer-peptide conjugates were also assessed for their propensity to self-assemble into thixotropic gels in an array of solvent mixtures. Determination of the rules governing this particular self-assembly (gelation) was required. Initial work suggested that at least four phenylalanine peptide units were necessary for self-assembly, due to favourable hydrogen bond interactions. Quantitative analysis was carried out using three analytical techniques (namely rheology, FTIR, and confocal microscopy) to probe the microstructure of the material and provided further information on the conditions for self-assembly. Several polymers were electrospun in order to produce nanofibres. These included novel materials such as PIMs and the aforementioned bio-hybrid conjugates. An investigation of the parameters governing successful fibre production was carried out for PIMs, polymer-peptide conjugates, and for nanoparticle cages coupled to a polymer scaffold. SEM analysis was carried out on all material produced during these electrospinning experiments.

Direct activation of microcrystalline zeolites

In this work a direct activation route of zeolites is assessed. It consists of NH4-exchanging the as-synthesized solids before removing the organic template. Calcination afterwards serves to combust the organic template and creates the Brønsted sites directly; thus applying merely a single thermal step. This method simplifies their activation and the material suffers less thermal stress. The approach was particularly effective for microcrystalline beta and ferrierite zeolites. Thorough investigation of the template content and materials' texture points out to three relevant effects that can explain the effective exchange process: partial removal of the template during exchange creates substantial microporosity (ferrierite), the remaining template is reorganized within the pores (ferrierite) and finally, void space can exist due to the non-perfect matching between the network and template (beta). This shorter method appears suited for microcrystalline zeolites; it was ineffective for crystalline MFI types. © 2013 Elsevier B.V. All rights reserved.

Atributos do solo sob modelos em estágio inicial de restauração de floresta subtropical

The replacement of native vegetation by other land uses is one of the main degrading ecosystem agents, being the most important component of terrestrial environments, natural or with different levels of human disturbance, besides being the main substrate used by plants to obtain conditions soil for its development. In this context, there is the need to adopt the use and sustainable management of land systems. The study aimed to evaluate what is forest restoration system more efficient degraded areas, based on the potential recovery of physical, chemical, carbon and biological activity in the soil. The work was conducted in a forest restoration area UTFPR- Campus two neighbors, whose experiment was established in October 2010. The experimental design is completely randomized, with four replications and experimental plot of 40 m wide by 54 m long ( 2160 m2) were collected and six sampling points per plot. The soil is classified as a Typic. The models evaluated are: 1 - natural or passive regeneration; 2 - Nucleation; 3 - Planting trees in the total area under lines fill and diversity (total planting); 4 - Reference area (forest). The collection of soil samples in layers of 0.0-0.05, 0.05-0.10, 0.10-0.20 and 0.20-0.40 m was carried out in October 2013 and evaluated physical attributes of texture, bulk density, total porosity, microporosity and soil macroporosity and stability of water in households, chemical properties, and total organic carbon (TOC) and physical particle size fractionation and soil biological activity. To find the best forest restoration model, we designed a Restoration Quality Weighted Index for each variable analyzed. Natural regeneration and total plantation showed generally better soil aggregation over 0.10 m and nucleation volume of similar porosity the forest for these layers. There were no differences between the models below 0.10 m for the variables aggregation and soil porosity. The nucleation template had the lowest bulk density, but being greater than the density in the layer forest 0.05-0.10 m, however, was similar to below 0.10 m above the ground. The models had chemical properties similar to or greater than the forest. The forest had the highest stock of COT and carbon associated with minerals (CAM), but natural regeneration was similar to the particulate organic carbon (POC) in the superficial layers of the soil (0-0.10 m), below 0, 10 m, the forest showed higher stock of COT and COP on the ground. The highest peak of C-CO2 emissions occurred in the 28-35 day range where the total plantation was similar to forest. After four years of experiments, it was found that the effect of restoration methods on physical attributes and soil carbon restricted to 0.10 m deep.

Porosity in ion-exchanged and acid activated clays evaluated using n-nonane pre-adsorption

The applicability of the n-nonane pre-adsorption method for characterising the porosity in clays is presented. Na-SD, a Na+-exchanged purified bentonite, and materials obtained by Al3+-exchange and acid treatments of Na-SD and SAz-1 were used. Nitrogen adsorption isotherms, at -196 ºC, were determined before and after n-nonane pre-adsorption on each of the samples. In all materials, n-nonane remained adsorbed in ultramicropores after outgassing at 25 ºC. Outgassing at higher temperatures (50, 75 and 200 ºC) removed nonane and ultramicropores became available for nitrogen adsorption. All treatments on Na-SD led to increase in micropore volume. Larger ultramicropore and supermicropore volumes were obtained for Na-SD acid activated with HCl at 95 ºC than for treatments at 25 ºC with HCl or following Al3+-exchange (Al-SD), and increased with increasing acid concentration to 3 M. Activation with 4 M HCl led to the largest pore volume with contribution from mesopores. However, the specific external surface area was the same as that obtained for Na-SD, Al-SD and for most of the other acid activated samples. Treatments at 95 ºC with 1 M and 6 M HCl promoted increase in specific external surface area. The micropore volumes and specific external surface area for SAz-1 treated with 1 M HCl at 95 ºC were larger than those of Al-SAz-1, but lower than those obtained for corresponding materials derived from Na-SD. The n-nonane pre-adsorption method enabled micropore volumes and specific external surface areas to be obtained for all samples.

Analysis of β-tricalcium phosphate granules prepared with different formulations by nano-computed tomography and scanning electron microscopy

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The use of animal models in multiple myeloma

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Numerical estimation of Carbonate properties using a digital rock physics workflow

Digital rock physics combines modern imaging with advanced numerical simulations to analyze the physical properties of rocks -- In this paper we suggest a special segmentation procedure which is applied to a carbonate rock from Switzerland -- Starting point is a CTscan of a specimen of Hauptmuschelkalk -- The first step applied to the raw image data is a nonlocal mean filter -- We then apply different thresholds to identify pores and solid phases -- Because we are aware of a nonneglectable amount of unresolved microporosity we also define intermediate phases -- Based on this segmentation determine porositydependent values for the pwave velocity and for the permeability -- The porosity measured in the laboratory is then used to compare our numerical data with experimental data -- We observe a good agreement -- Future work includes an analytic validation to the numerical results of the pwave velocity upper bound, employing different filters for the image segmentation and using data with higher resolution

Novel synthesis of a micro-mesoporous nitrogen-doped nanostructured carbon from polyaniline

Nanostructured carbons with relatively high nitrogen content (3–8%) and different micro and mesoporosity ratio were prepared by activation of polyaniline (PANI) with a ZnCl2–NaCl mixture in the proportion of the eutectic (melting point 270 °C). It was found that the activated carbons consisted of agglomerated nanoparticles. ZnCl2 plays a key role in the development of microporosity and promotes the binding between PANI nanoparticles during heat treatment, whereas NaCl acts as a template for the development of mesoporosity of larger size. Carbons with high micropore and mesopore volumes, above 0.6 and 0.8 cm3/g, respectively, have been obtained. Furthermore, these materials have been tested for CO2 capture and storage at pressures up to 4 MPa. The results indicate that the nitrogen groups present in the surface do not seem to affect to the amount of CO2 adsorbed, not detecting strong interactions between CO2 molecules and nitrogen functional groups of the carbon, which are mainly pyridinic and pyrrolic groups.

Improvement of carbon materials performance by nitrogen functional groups in electrochemical capacitors in organic electrolyte at severe conditions

N-doped activated carbon fibers have been synthesized by using chemically polymerized aniline as source of nitrogen. Commercial activated carbon fibers (A20) were chemically modified with a thin film of polyaniline (PANI) inside the microporosity of the carbon fibers. The modified activated carbon fibers were carbonized at 600 and 800 °C, respectively. In this way, activated carbon fibers modified with surface nitrogen species were prepared in order to analyze their influence in the performance of electrochemical capacitors in organic electrolyte. Symmetric capacitors were made of activated carbon fibers and N-doped activated carbon fibers and tested in a two-electrode cell configuration, using triethylmethylammonium tetrafluoroborate/propylene carbonate (TEMA-BF4/PC) as electrolyte. The effect of nitrogen species in the degradation or stabilization of the capacitor has been analyzed through floating durability tests using a high voltage charging (3.2 V). The results show higher stabilizing effect in carbonized samples (N-ACF) than in non-carbonized samples and pristine activated carbon fibers, which is attributed to the presence of aromatic nitrogen group, especially positively charged N-functional groups.

Throughfall and soil properties in shaded and unshaded coffee plantations and a secondary forest: a case study from Southern Colombia

In Colombia coffee production is facing risks due to an increase in the variability and amount of rainfall, which may alter hydrological cycles and negatively influence yield quality and quantity. Shade trees in coffee plantations, however, are known to produce ecological benefits, such as intercepting rainfall and lowering its velocity, resulting in a reduced net-rainfall and higher water infiltration. In this case study, we measured throughfall and soil hydrological properties in four land use systems in Cauca, Colombia, that differed in stand structural parameters: shaded coffee, unshaded coffee, secondary forest and pasture. We found that throughfall was rather influenced by stand structural characteristics than by rainfall intensity. Lower throughfall was recorded in the shaded coffee compared to the other systems when rain gauges were placed at a distance of 1.0 m to the shade tree. The variability of throughfall was high in the shaded coffee, which was due to different canopy characteristics and irregular arrangements of shade tree species. Shaded coffee and secondary forest resembled each other in soil structural parameters, with an increase in saturated hydraulic conductivity and microporosity, whereas bulk density and macroporosity decreased, compared to the unshaded coffee and pasture. In this context tree-covered systems indicate a stronger resilience towards changing rainfall patterns, especially in mountainous areas where coffee is cultivated.

Preparação, caracterização e modificação de adsorventes para remoção de pesticidas de águas

O objectivo principal deste trabalho de mestrado consistiu em avaliar a potencial utilização de materiais adsorventes, nomeadamente, de carvões activados (AC) preparados por activação química com KOH, a partir de PET reciclado, e de materiais com estrutura mesoporosa ordenada, do tipo MCM-41 e SBA-15, na remoção de ácido 4 - cloro - 2 - metilfenoxiacético (MCPA) e de azul de metileno (MB), presentes nas águas. Nesta tese apresentam-se estudos de preparação e caracterização de materiais micro e mesoporosos e também estudos de avaliação da capacidade adsortiva em fase líquida. Prepararam-se três materiais microporosos, nomeadamente, PET-2-700, PET-2-700ox (AC oxidado) e PET-2-700red (AC reduzido), dois materiais constituídos exclusivamente por mesoporos, Si-MCM-41 e Ti-MCM-41-50 e dois materiais contendo maioritariamente mesoporos, mas que também possuem alguma microporosidade, tais corno, Si-SBA-15 e Ti-SBA-15-50. A caracterização textural dos adsorventes foi inferida por adsorção de azoto a 77K e por de difracção de raios X. Recorreu-se a três métodos de análise das isotérmicas, nomeadamente, Dubinin-Radushkevich, Brunauer-Ernrnett-Teller e alfa-s (as). A caracterização química dos AC foi realizada recorrendo-se a técnicas de análise elementar (AE) e espectroscopia de infravermelho com transformadas de Fourier (FTIR) e à determinação do ponto de carga zero. Os três carvões activados possuem valores de área superficial externa idênticos, o PET-2-700 possui o maior volume microporoso e o PET-2-700ox exibe o maior diâmetro de poros. Por outro lado, o PET-2-700ox possui um carácter fortemente ácido, o PET-2-700 exibe carácter ligeiramente ácido e o PET-2-700red apresenta propriedades ligeiramente alcalinas. Com base na AE, todas as amostras possuem percentagens de carbono elevadas, sendo que o PET-2-700red apresenta o valor mais elevado. Os resultados obtidos para a caracterização estrutural dos revelaram a obtenção de materiais mesoporosos de alta qualidade, definida pela elevada regularidade e uniformidade da estrutura porosa. A análise dos parâmetros de caracterização textura! permitiu inferir que os quatro materiais mesoporosos possuem valores de área superficial elevados, e que os materiais SBA-15 apresentam valores de volume poroso total e de tamanho de poros superiores aos manifestados pelos MCM-41. A incorporação de titânio não conduziu a uma perda significativa de qualidade dos materiais substituídos em relação às correspondentes amostras de sílica. Efectuaram-se estudos de adsorção em fase líquida de forma a avaliar a possível aplicação dos vários adsorventes na remoção de MCPA e de MB de efluentes líquidos. concluiu-se que o tempo de equilíbrio de 72 horas seria adequado e que a capacidade de adsorção dos vários AC era superior em meio ácido. Com base nas isotérmicas de adsorção do MCPA e do MB e na aplicação da representação de Langmuir e de Freundlich, foi possível concluir que o PET-2-700 possui a maior capacidade de adsorção do MCPA, 1.42 mmol/g, enquanto que o PET-2-700ox revelou a maior capacidade de adsorção do MB, 1.43 mmol/g. Na realidade, os materiais microporosos estudados apresentaram percentagens de remoção elevadas, tanto do MCPA como do MB. Relativamente aos materiais mesoporosos ordenados preparados neste trabalho, a percentagem de remoção de para os poluentes em estudo foi relativamente baixa, constatando-se que nesta fase dos estudos não constituem uma alternativa viável à utilização dos AC. No entanto, uma funcionalização criteriosa dos mesmos pode eventualmente proporcionar um aumento da capacidade adsortiva. ABSTRACT: The work presented in this master thesis, consisted of evaluating the potential use of different adsorbents materials, like activated carbon (AC) prepared by chemical activation with KOH, from recycled poly (ethylene terephthalate) (PET) and materials with ordered mesoporous structure such as MCM-41 and SBA-15, for removing acid 4-chlorine-2-metilfenoxiacétic and methylene blue from aqueous phase. We had prepared three microporous materials, PET-200-700, PET-2-700ox (AC oxidized) and PET-2-700red (reduced AC), two materials consisting exclusively of mesopores, Si-MCM-41 and Ti-MCM-41-50 and two materials containing mainly mesopores, but also having some microporosity, such as Si-SBA-15 and Ti-SBA-15-50. The textural characterization of the adsorbents was inferred by nitrogen adsorption at 77K and X-ray diffraction. Three methods were used to analyse the isotherms, namely, Dubinin-Radushkevich, Brunauer-Emmett-Teller and alpha-s (as). The chemical characterization of AC was performed using the elementary analysis, Fourier transform infrared spectroscopy (FTIR) and determination of the point of zero charge. Concerning the AC, the three present almost the same externa! surface area, PET-2-700 has a high micropore volume and PET-2-700ox shows the largest pore size diameter. On the other hand, PET-2-700ox had a strong acid character, PET-2-700 exhibits just a slightly acid character and PET-2-700red presents alkaline properties. The AE analysis allows confirming the high carbon content of theses AC, with PET-2-700red exhibiting the highest carbon proportion. The results from the structural characterization of the mesoporous materials, had disclosed the attainment of materials with high quality, defined by the raised regularity and uniformity of the porous structure. The analysis of the textural parameters allowed inferring that the four studied mesoporous materials possess high superficial area. The SBA-15 type materials present higher values of total porous volume and pores size diameter as the MCM-41. Also, the titanium incorporation did not lead to a significant loss of quality of the materials substituted in relation to the corresponding silica samples. The adsorption studies in liquid phase allow evaluating the possibility of using the different adsorbents for the MCPA and the MB removal. The kinetic studies had allowed to state the equilibrium time as 72 hours and a higher adsorption capacity was achieved in an acid medium. The influence of the pH of the medium, on the MCPA adsorption was evaluated. The MCPA and MB isotherms were analysed based on the Langmuir and Freundlich equation, the representations presented an excellent linearity, indicating the applicability of these equations to these systems. Also, it allows concluded that PET-2-700 had a higher adsorption capacity for MCPA, 1.42 mmol/g, and PET-2-700ox had a higher adsorption capacity for MB, 1.43 mmol/g. The AC used presented high removal percentages for MCPA and MB. Concerning the mesoporous materials prepared in this work, the percentage removal for the pollutants in study was relatively low, and evidencing that at the moment these mesoporous materials do not constitute a viable alternative to the AC. However, an astute funcionalisation of the same ones can, eventually provide an increase of the adsorption capacity.