During this study, the correlation between the evolution of the prior austenitic grain size and of the precipitation state during thermal treatment performed on steels is presented. To do this, the precipitation state has been finely characterized. Precipitate volume fractions were measured by plasma spectroscopy. Transmission Electron Microscopy (TEM) was used to determine the precipitate size distributions (HAADF images) and the precipitate chemical composition (EDX, EELS for carbon and nitrogen). In order to treat ELLS spectra obtained on complex carbonitrides (V,Nb,Ti)(C,N), a routine based on the Least Mean square Fitting have been developed. Results obtained with this method are in gopd agreement with those obtained by EDX analysis for metallic elements (Nb, V, Ti, ...). Then, grain size distributions were determined using a special etching called "Bechet-Beaujard", which reveals the prior austenite grain boundaries. Two alloys have been characterized in this study. (i) A model alloy, the FeVNbCN, which presents two precipitate types, NbC and VCN. This alloy was chosen to study the role of nitrogen on the precipitation state during reversion treatments. A model predicting the precipitation kinetics, coupled with a model for grain growth, give a good agreement with experimental results on grain sizes, precipitate sizes and on precipitate volume fraction. (ii) An industrial steel, the 16MnCr5+Nb was also studied. This alloy exhibits the presence of AlN and NbC precipitates. The correlation obtained between the Prior Austenite Grain Size and the evolution of the precipitation state shows that a large volume fraction of small precipitates allows a great pinning of grain boundaries. Finally, during thermo-mechanical treatments performed in the industry, some large grains may grow faster than smaller grains, leading to the so-called abnormal grain growth. This kind of growth can lead to undesirable mechanical instabilities. We have developed a criterium for abnormal grain growth which predicts the risk of such growth for a given precipitation state. This model presents a good agreement with all experimental results for both studied alloys.

ABSTRACT Comparative study of established test methods for aggregate strength and durabilityof Archean rocks from Botswana In the current situation, river sand is used for building of roads and as raw material forconcrete in Botswana. River sand is a finite resource and important to preserve as itacts as natural water purification, groundwater aquifer and protection against soil erosion.Mining of bedrock may be a good alternative to replace the river sand with crushed rock(aggregates) in concrete and as road materials.The main purpose of this thesis was to determine if the rock grain size can be usedas a parameter to indicate durability and rock strength. It was also of interest to find outif the grain size correlates with established technical analysis and strength test methods.This knowledge can be used as a prospecting tool when searching for new quarry sites inthe future.In this master’s thesis, rock samples from the Gaborone granite complex have beenanalysed to examine how established test methods and the mineral grain size correspondswith the rock strength. By comparing technical properties (Los Angeles (LA) value ,aggregate crushing value (ACV), aggregate impact value (AIV) and 10 percent fines aggregatecrushing test (10 % FACT)) with quantitative analysis (mineral grain size andmineral grain size distribution), it is possible to determine the mineral grain size correspondenceto rock strength. Generally the result show that more fine-grained granitesshow better technical properties than more coarse-grained granites. The calculated meangrain size show weak negative correlation to ACV value, and a positive correlation to LA-, AIV- and 10 % FACT values. Best correlation can be seen between mean grain size andLA values (R2= 0.61) and AIV values (R2= 0.58). Low mean grain size tend to give bettertechnical properties in form of lower LA- and AIV values. The cumulative distributioncurve show that a high concentration of very fine material or fine material tend to contributeto a lower LA value. The results indicate that equigranular rocks with low meangrain size contributes to good technical properties, but when it comes to uneven grainedrock more factors must be taken into account to estimate technical properties.

This thesis focuses on a number of aspects governing the transformation of gibbsite, via intermediate phases, to a-alumina. These aspects include the size and morphology of the gibbsite grains, the influence of additions of foreign elements, the effect of a mechanical treatment of the gibbsite prior to calcination, and combinations of these factors. The materials were characterisedb y scanninge lectron microscopy, X-ray diffraction and surfacea rea measurementsF. or someo f the calcined materials an attempt was made to sinter the powders to a dense body to investigate if any of the treatments during calcination had an effect on this process. The literature review covers the current state of understanding of the production of bulk alumina powder by the Bayer process and the phase changes seen on calcination of precursors to the stable a-alumina phase. A detailed description of the phase changes is given and the various routes and conditions necessary for the transformations to occur are considered. The transformations are examined in relation to the morphology of the crystals and the variables controlling the phase transformation route are discussed. Calcination in air showed that the size of the gibbsite grain governs the calcination route taken to reach a-alumina. The standard gibbsites used in this work show a mixed calcination sequence transforming both via the boehmite phase, followed by the y, 8 and 0 phases, and via the x and K phases. The formation of boehmite is attributed to retention of water vapour within the grainDifferences in morphology of the starting materials showed that for the range of materials seen, the morphology of the grain is less important than its size. The super fine material confirmed that a small grain size transforms via the non-boehmite route only, with the other gibbsites taking intermediate routes as for the standard gibbsites. Of the additions made prior to calcination, aluminium fluoride was found to reduce the transformation temperature to a-alumina by approximately 300°C. Other additions had little effect on the transformation temperature although a reduction in grain size was seen with aluminium chloride. It was found that good mixing of the alumina fluoride was essential to obtain reliable and reproducible results. This is due to the small amounts of additive that are needed and the sensitivity of the process to concentration variations. Mineralisation of a range of gibbsites showed that the presence of sodium in the starting material was crucial in reducing the calcination temperature. This led to the conclusion that the sodium and fluoride react to form a liquid phase. The presence of a liquid phase increases the mobility of the aluminium and oxygen atoms resulting in a reduction of the transformation temperature. Fluoride additions to the gibbsites with different morphologies showed that the presence of sodium was the governing factor in reduction of the transformation temperature. Milling of the starting materials showed that there was a small reduction in the transformation temperature between some of the phases. The energy involved in milling leads to activation of the gibbsite. This activation takes the form of a reduction in the grain size and in a reduction of the crystallinity seen in the XRD patternFluoride additions during the calcination of sapphire with a standard gibbsite powder showed preferential grain growth. It was possible to initiate growth of small plate-like crystals on the polished surface of a piece of sapphire parallel to the basal plane. Crystal growth was also seen in scratches on a polished surface perpendicular to the basal plane

Investigations on post service material showed that Alloy 800H pigtails from methanol producer Methanex have service lives ranging from 3 to 18 years. Because of this variability in service life, Alloy 800H creep performance was assessed and a new criterion for its procurement developed. The current criterion recommends an ASTM grain size of 5 (72µm) or coarser with no consideration given to grain size distribution, grain boundary types, or grain boundary network topology. Results from the investigation showed that this current criterion may produce variations in steady state creep rates of an order of magnitude between ASTM grain size 1 and 5, and a 2.5 times variation in creep ductility. The ability to accurately reveal grain boundaries and assess grain boundary types is fundamental to the identification and quantification of coherent twin boundaries, and the measurement of average grain size and grain size distribution. EBSD mapping has the ability to distinguish grain boundary types using crystal orientation measurement. Grain size measurement from optical micrographs relies on morphological indicators to identify coherent twins. However, it is shown that many of the boundaries observed as straight line morphology on 2D sections did not possess {111} (coherent) interfaces. 3D reconstructions of Alloy 800H revealed the deficiencies in classifying geometry from two-dimensional (2D) sections. Σ3 Crystal volumes can be categorized as lamellar or edge structures. Lamellar structures are characterized by the appearance of parallel Σ3 boundary planes while an edge structure contains a single Σ3 interface. Sectioning plane location alters the perception of morphology. For simple twin structures, the tradition 2D classifications of morphology (complete parallel, incomplete parallel and corner Σ3) may all appear on a section plane from a single lamellar structure.

No description available.

The purpose of this study was to evaluate Lewis (2016) simple method to determine hydraulic conductivity in soil samples. This was conducted by comparing Lewis method to a slug-test, Guelph permeameter and calculations from grain size analysis in order to find out if the method is a reliable source for measuring hydraulic conductivity. Other parameters to compare is time consumption, cost effectiveness and area of use. Four different samples were used in the testing, a sand, two tills and pyrite ash (which is a rest product from manufacturing sulfite pulp). The results indicated that measurements in the homogenic sand all methods was in a good range of each other, while in the more heterogenic till the slug-test and Lewis method was close and the calculations from grainsize analysis was much lower. Only grainsize analysis was performed on the pyrite ash and the results was similar to Lewis method. This study shows that Lewis method works well as a reliable source for K measurements and is less time consuming than all the other methods. The material required for the method can be obtained in a hardware store.

The industrial practice of grain refinement of aluminium alloys involves the addition of inoculant particles to initiate alpha-aluminium grains at small undercoolings. This results in a uniformly fine, equiaxed as-cast microstructure and is commonly achieved using Al-Ti-B additions. The phase responsible for initiation of grains in aluminium melts inoculated with Al-Ti-B was determined during the 1990s; since that time, scientific understanding of grain refinement has advanced rapidly. However, one of the main problems of addition inoculants is impurities which is added to the melt and may affect the desired characteristics of the product. With regards to this problem other methods of refinement and the mechanisms of refining have not been fully understood and prediction of as-cast Microstructures in aluminium alloys has much scope for improvement. In this thesis: 1-Factors in establishing equiaxed microstructure were analysed and the origin of equiaxed grains were explored. Then the nucleation process and the involved mechanisms were investigated in depth and control of nucleation process to achieve a fine and uniform structure was set as target. 2-Refinement of microstructure with introduction of shearing was evaluated and the process of refinement in the mushy zone (semisolid state) as a base line was established. Then introduction of shearing above liquidus as a development was analysed and outstanding refinement was seen with shearing above liquidus which have not been investigated properly elsewhere. 3- The mechanisms of refinement by introducing shearing were investigated and the refining mechanisms below and specifically above liquidus were investigated systematically. As results an appropriate understanding about the mechanisms of nucleation and refinement above liquidus was established. 4- Finally, with simulation the most dominant factor in approaching fine grain size by applying shear was identified and the results of experimental examination was verified by simulation.

A solução sólida céria-samária é uma das principais candidatas para aplicação como eletrólito sólido em células a combustível de óxido sólido, devido sua alta condutividade iônica em temperaturas intermediárias (500-750 ºC) de operação. Um dos problemas ainda não solucionados com relação a este material é sua relativamente baixa sinterabilidade. Nesse trabalho foi utilizado o método de sinterização em duas etapas visando melhorar a densificação com reduzido tamanho médio de grãos. Soluções sólidas comercial e obtida por mistura de óxidos de composição Ce0,8Sm0,2O1,9 foram utilizadas. Para fins comparativos também foi utilizado o método denominado sinterização em duas etapas tradicional que visa a obtenção de amostras densas independentemente do tamanho médio de grãos. Resultados de densidade aparente e retração linear revelaram que ambos os tipos de amostras têm comportamento distinto. Para a solução sólida comercial, a retração total até 1400 ºC foi de ~18%. Só foram obtidos resultados de densidade significativos ao utilizar temperaturas elevadas (igual ou superior a 1300 ºC). Para o material obtido por mistura de óxidos não foi possível atingir densidades maiores que 90% da densidade teórica. A sinterização em duas etapas tradicional produziu amostras densas, da mesma forma, que a não-tradicional, mas com tamanhos de grãos consideravelmente maiores. Amostras sinterizadas por ambos os processos foram analisadas por espectroscopia de impedância para a determinação da condutividade elétrica em função da temperatura, e não apresentaram variação significativa nas condutividades intra e intergranular. A sinterização em duas etapas não resultou em melhorias na densificação e nem na condutividade elétrica das amostras. Entretanto, a redução obtida no tamanho médio de grãos pode melhorar as propriedades mecânicas. / Samaria-doped ceria solid solution has been proposed to be used as solid electrolyte in Solid Oxide Fuel Cells due to its high ionic conductivity at intermediate temperatures (500-750 ºC). One of the main problems related to this solid solution is the relatively low sinterability. In this work, sintering of powder compacts was carried out by the two-step sintering method to improve the densification with simultaneous reduction of the mean grain size. Samaria-doped ceria, both commercial and prepared by solid state reactions, with composition Ce0.8Sm0.2O1.9 were investigated. For comparison purposes, the traditional two-step sintering method, by which dense specimens are produced, was also utilized. Apparent density and linear shrinkage results showed distinct features depending on the type of specimen. Total linear shrinkage for commercial solid solution up to ~ 1400 ºC was 18%, but high density values were obtained only for sintering experiments conducted at high temperatures ( 1300 ºC). Specimens prepared by solid state reactions did not attain density values higher than 90% of the theoretical one. The traditional method produced dense specimens as well as the two-step sintering, although the grain size was considerably higher in the former. Specimens sintered by the two methods were used for electrical conductivity measurements. No significant variation in both the grain and the grain boundary conductivities was obtained. The two-step sintering did not allow any improvement in the densification and in the electrical conductivity of samaria-doped ceria. However, the decrease in the mean grain size may contribute to improve the mechanical properties of this solid solution.

A remoção do surfactante Alquilbenzeno Linear Sulfonado (LAS) de água residuária de lavanderia comercial foi estudada em EGSB (Expanded granular sludge bed). Essa água residuária foi diluída em esgoto sanitário. O volume útil do reator era de 1,8 L. Toda a operação ocorreu em condições mesofílicas, para TDH (tempo de detenção hidráulica) de 36 horas, velocidade ascensional de 4 m/h e vazão de recirculação de 8,5 L/h. A água residuária de lavanderia era diluída até que se atingisse aproximadamente 20 mg/L de LAS na alimentação do reator. O sistema foi operado em três fases. Na primeira fase de operação usou-se água de abastecimento para diluir a água residuária de lavanderia; na segunda fase utilizou-se uma mistura de água de abastecimento e esgoto sanitário para diluição da água residuária de lavanderia, sendo que 50 % da composição era esgoto sanitário; e, por fim, na última fase de operação utilizou-se apenas esgoto sanitário como diluente da água residuária. Na primeira fase foi necessária adição de bicarbonato de sódio como agente tamponante. Em todas as fases aplicou-se DQO (demanda química de oxigênio) e LAS afluente de 341 ± 216 mg/L e 18,8 ± 7,3 mg/L, respectivamente. A adição do esgoto sanitário afetou a remoção do surfactante, o que na fase inicial (Fase I) representou 77,2 ± 14,9 % e na fase final (Fase III) passou a ser 55,3 ± 18,4 % de remoção de LAS. No entanto, ao passo que a remoção de LAS diminuiu, a remoção de DQO aumentou de 57 ± 16 % para 65 ± 10 %, respectivamente, para a Fase I e Fase III. Além disso, devido a adição de esgoto sanitário verificou-se aumento do tamanho dos grânulos, de 3,67 ± 1,83 mm (Fase I) para 4,97 ± 1,99 mm (Fase II); e também da concentração de sólidos totais no reator, de 5,79 g/L (Etapa I) para 9,50 g/L (Fase III). Por meio do balanço de massa de LAS verificou-se remoção de 69 % de LAS, sendo que 67 % foram removidos por degradação e 2 % por adsorção do mesmo na biomassa. Por fim, por meio das análises por CG/EM (Cromatografia gasosa acoplada a espectrometria de massas) observou-se 17 substâncias no afluente e apenas 4 no efluente, tais como, mercaptanas, hidrocarbonetos, aminas e amidas. A maioria delas são tóxicas aos organismos aquáticos e estão presentes em produtos de limpeza e higiene pessoal. / The removal of the surfactant Linear Alkylbenzene Sulfonate (LAS) of wastewater of a commercial laundry was studied in an EGSB (Expanded granular sludge bed). This wastewater was diluted in sewage. The useful volume of the reactor was of 1,8 L. The whole operation occurred on mesophilic conditions, to HRT (Hydraulic Retention Time) was 36 hours, the upflow speed of 4 m/h and recirculation flow of 8,5 L/h. The laundry waste water was diluted until achieve 20 mg/L of LAS on the reactor feed. The system was operated in three stages. In the first operation stage water supply was used to dilute the wastewater laundry; in the second stage used a mixture of water supply and sewage for dilution of wastewater laundry and 50 % of the composition was sewage; and finally, in the last stage of operation is only used sewage as a diluent of wastewater. In the first stage was required addition of sodium bicarbonate as buffering agent. All the stages was applied COD (Chemical oxygen demand) and LAS influent 341 ± 216 mg/L and 18,8 ± 7,3 mg/L, respectively. The addition of sewage affected the surfactant removal, which on the first stage (Stage I) represented 77,2 ± 14,9 % and on the final stage (Stage III) became 55,3 ± 18,4 % of LAS removal. However, while removing of LAS decreased the COD removal increased from 57 ± 16 % to 65 ± 10 %, respectively, to Stage I and Stage III . Furthermore, due to the addition of sewage was checked an increased on the size of the grain from 3,67 ± 1,83 mm (Stage I) to 4,97 ± 1,99 mm (Stage II); and also the concentration of total solids into the reactor, from 5,79 g/L (Stage I) to 9,50 g/L (Stage III). By mass balance LAS was found a remove of 69 % of LAS, wherein 67 % were removed by degradation and 2 % by adsorption of the surfactant in the biomass. Finally, through analysis by GC/MS (gas chromatograph/mass spectrometry) 17 substances were observed in the influent and only 4 in the effluent, such as, mercaptans, hydrocarbons, amines and amides. Most of them are toxic to aquatic organisms and are present in cleaning products and personal hygiene.

Beach grain size plays a major role in controlling beach slope and sediment transport rates and is a crucial criterion in selecting the appropriate fill material for beach nourishment. Yet, little is known about how and why beach grain size (and sorting) varies both spatially and temporally on high-energy sandy beaches. Therefore, in this PhD research project, the presence, magnitude and predictability of any spatio-temporal sediment variability was investigated on a number of contrasting high-energy (average significant wave height = 0.8 to 3.5 m), predominantly macrotidal (MSR = 3.1 – 6.2 m), sandy (0.26 – 0.64 mm) beach sites around the southwest peninsula of the United Kingdom (UK). The spatial extent of the data collected ranges from regional (one off snapshot of the sediment conditions on 53 beaches over 485 km of coastline) to local scales (repeated high-resolution samples from across the inter- and subtidal zone of a single high-energy sandy beach; Perranporth, UK). The temporal scales of the sampling ranges from tidal scale (~12 hours) up to monthly (long-term monitoring since 2008). A combination of traditional and modern field data collection methods has provided new insights into the sediment dynamics of sandy beaches. Surface and 0.25 m core sediment samples from the 53 beaches around the southwest UK and high-resolution digital measurements with longer 1 m sand cores from the intertidal zone, plus grab samples from the subtidal zone, at Perranporth, indicated the presence of three quasi-permanent spatial trends. On all sandy beaches, surface sediments became coarser (and better sorted) in the seaward direction across the intertidal zone. Peak sediment sizes were observed on the lower beach around mean low water springs, which were an average 19% coarser (and 8% better sorted) than sediments sampled on the upper intertidal beach. Sediment size (and sorting) also increased (improved) with distance down the sediment column over the top 0.25 m to 1 m. Peak sediment sizes at depth were an average 16% coarser (and 16% better sorted) than surface sediments. In the subtidal zone, surface sediments became finer and poorer sorted with increasing offshore distance. Minimum sediment size occurred on the subtidal bar crest and were an average 21% finer (and 51% poorer sorted) than the lower beach sediments and 5% finer (and 38% poorer sorted) than upper beach sediments. The coarsest sediments were usually the best sorted at all locations. The intertidal coarsening was deterministically linked to the location and amount of breaking wave-induced turbulence. The peak sediment sizes (and sorting) on the lower beach correlated with the location of peak wave dissipation (sediment size to amount of wave dissipation, r2 = 0.86) and the finer sediment sizes on the upper beach and bar were coincident with reduced amounts of wave dissipation in these regions. Long-term seasonal monitoring of the surface sediments at Perranporth indicated a background seasonality, where the winter months were an average 35% coarser and 22% better sorted than samples collected in summer. This seasonal pattern was punctuated by episodic storm events that promoted a significant coarsening (up to 112% in the extreme winter storms of 2014) of the surface sediments and significant beach erosion up to 175 m3/m. An empirical model forced by the degree of disequilibrium between an instantaneous and antecedent (weighted average) wave steepness time series was able to capture up to 86% of the sediment grain size and sorting variability, incorporating both the seasonal and storm driven change. The same model, applied to daily observations of sediment size and sorting changes was able to explain 72% of the variability. A conceptual model is proposed that extends the cross-shore sediment transport shape functions to include the various sediment (size and sorting) responses alongside the morphodynamic evolution during persistently high and low wave steepness conditions. Under high steepness waves, the finer material is preferentially removed from the lower intertidal beach, leaving behind coasrer sediments. This fine material is transported to the subtidal bar, which becomes finer (and more poorly sorted) inversely with the coarsening (and improved sorting) of the intertidal zone sediments. Under low steepness waves, this fine material is returned from the bar to the intertidal beach. This work provides a detailed, quantitative insight into the magnitude of sediment grain size and sorting changes exhibited by sandy beaches on a number of spatial and temporal scales. Several consistent trends were observed on a range of sandy beaches despite their different environmental conditions and geological histories. This improved understanding of sediment grain size and sorting changes on beaches will hopefully aid future research efforts and ensure that this fundamental aspect of coastal science is not overlooked or oversimplified.