The study of the structure-activity relationship of electrode surfaces is fundamentally important in electrocatalysis research. Yet, the methods and techniques used for the examination of structure-activity relationship so far are limited by their capabilities, and the exploration of electrochemistry at complex surfaces is very challenging. In this study, the correlation between the electrode surface structure and its corresponding activity in two electrochemical reactions were investigated: an electrochemical etching reaction and an electrocatalysis reaction. A polycrystalline Pt electrode was galvanically etched to expose the underlying well-defined crystallites serving as pseudo-single-crystal electrodes. Atomic force microscopy (AFM) complemented with electron backscatter diffraction (EBSD) was employed for the elucidation of the effects of electrode surface structure on its etching rate. Electrochemical measurements of the electrocatalytic activity of the hydrogen oxidation reaction on individual grain surfaces were performed with high spatial resolution scanning electrochemical microscopy (SECM) coupled with electron backscatter diffraction (EBSD). The etching experiment and surface characterization results show the more deeply etched regions on polycrystalline Pt surface correspond to Pt(100). The etching rate of the Pt catalyst is Pt(111), Pt(100), and Pt(110) in increasing order. The structure-reactivity relationship showed that the catalytic activity for hydrogen oxidation reaction (HOR) increases in the order Pt(100) < Pt(110) < Pt(111), where the Miller index plane represents the terrace orientation of the high-index facets. A clear correlation is observed between the increase in HOR activity and step sites density on a given base orientation. Quantitative kinetic measurements at crystal domains were made from current-potential plots and SECM approach curves.

<p>The morphologies and growth behavior of Cu₆Sn₅ intermetallic compound (IMC) formed between Sn-based solder and large-grain polycrystalline Cu substrate were systematically investigated. Hexagonal Cu₆Sn₅ grains were observed to form at certain reflow condition, which matches well with the literature results for IMC growing on single crystal substrate. The kinetics of IMC growth was also investigated and different mechanisms were proposed for different evolution stages. It was observed that facet formation should be a growth shape rather than an equilibrium shape, and the orientation relationship between Cu and Cu₆Sn₅ was studied using scanning electron microscope (SEM) and Electron backscatter diffraction (EBSD), and were visualized on inverse pole figure. </p>

O desgaste abrasivo de dois aços austeníticos ao manganês, materiais com grande utilização na mineração, foi estudado empregando metodologia multiescala (escalas: macro, meso e micro). Na macroescala foram estudados os mecanismos de dano e de desgaste de revestimento de britador utilizado em campo. Na mesoescala foram realizados ensaios de britador de mandíbula e de esclerometria linear. Na microescala o ensaio de esclerometria linear foi utilizado para avaliar os efeitos da camada encruada em campo e da orientação cristalográfica dos grãos austeníticos dos aços com 12 %Mn e 20 %Mn. As técnicas de caracterização utilizadas nesta pesquisa foram: macro e microdureza, nanodureza instrumentada, MO, MEV, DRX, EBSD, FIB e MET. A pesquisa foi dividida em três Capítulos, intitulados: \"Desgaste abrasivo dos aços austeníticos com 12 %Mn e 20 %Mn via ensaio de britador de mandíbula\"; \"Efeito do encruamento e da orientação cristalográfica no desgaste por riscamento dos aços austeníticos 12 %Mn e 20 %Mn\"; e \"Microestrutura da subsuperfície do aço austenítico com 12 %Mn deformado por desgaste abrasivo\". O primeiro Capítulo mostrou, a partir do ensaio de britador de mandíbulas (mesoescala), que o aço com 20 %Mn tem tendência de maior resistência ao desgaste que o aço com 12 %Mn. Este resultado foi obtido para a mandíbula fixa do britador, na qual a severidade de desgaste foi superior a mandíbula móvel, por apresentar microcorte e microsulcamento como micromecanismos predominantes, enquanto na mandíbula móvel o micromecanismo predominante foi a microendentação. No segundo Capítulo observou-se que o desgaste por riscamento (mesoescala e microescala) não depende do perfil de encruamento gerado em campo. Entretanto, foi identificado o efeito da orientação cristalográfica, planos (001), (111) e (101), no desgaste por riscamento dos aços com 12 %Mn e 20 %Mn. No último Capítulo a análise multiescala mostrou que a microestrutura deformada na subsuperfície sofre alterações semelhantes em diferentes intensidades. Nas três escalas de análise foram observadas uma camada com grãos ultrafinos (nanométricos), na subsuperfície, e uma de transição com maclas de deformação. A formação dos grãos ultrafinos foi associada à recristalização dinâmica por deformação plástica, na qual faz parte do mecanismo de auto reparação superficial. Além dos resultados apresentados, o desenvolvimento desta pesquisa de doutorado permitiu a elaboração de duas metodologias: i. análise do efeito da orientação cristalográfica no desgaste por microesclerometria; e ii. análise de microestrutura revelada por ataque iônico - FIB. / The abrasive wear of two manganese austenitic steels, materials broadly used in mining industry, was studied using multiscale methodology (scales: macro, meso and micro). In the macroscale the mechanisms of damage and wear of in-service crusher liner were studied. In the mesoscale, jaw crusher and linear scratch tests were performed. In the microscale the linear scratch test was used to evaluate the effects of the hardening layer and the crystallographic orientation of the austenitic grains of steels with 12 %Mn and 20 %Mn. The characterization techniques used in this research were: macro and microhardness, instrumented nanohardness, OM, MEV, DRX, EBSD, FIB and TEM. The research was divided into three chapters, entitled: \"Abrasive wear of steels with 12 %Mn and 20 %Mn via jaw crusher test\"; \"The effect of the in-service workhardening and crystallographic orientation on the micro-scratch wear of austenitic steels with 12 %Mn and 20 %Mn\"; and \"Subsurface microstructure of the deformed austenitic steel with 12 %Mn by abrasive wear\". The first chapter showed, from the jaw crusher tests (i.e. mesoscale), that the steel with 20 %Mn tends to be more wear resistant than the steel with 12 %Mn. This result was obtained to the fixed jaw crusher, in which the wear severity was superior to the movable jaw, since it presents microcutting and microploughing as predominant micromechanisms, whereas in the mobile jaw the predominant micromechanism was microendentation. In the second chapter, it was observed that scratch wear (i.e. meso and microscale) does not depend on the in-service work-hardening profile. However, it was identified the effect of crystallographic orientation, (001), (111) and (101) planes, on the scratch wear of the steels with 12% Mn and 20% Mn. In the last chapter, the multiscale analysis showed that the subsurface deformed microstructure changes with different intensities. At the three analysis scales, a layer with ultrafine grains was observed in the subsurface and mechanical twins. The formation of this layer, with nanometric grains, was associated with dynamic recrystallization by plastic deformation, in which it is part of the self healing effect. In addition to the results found, the development of this doctoral research allowed for the elaboration of two methodologies: i. Analysis of the effect of crystallographic orientation on the scratch wear; and ii. Microstructure analysis revealed by ion etching - FIB.

Pulsed laser deposition has been used to grow Pb(Zr₀.₅₂Ti₀.₄₈)O₃ (PZT)/LaNiO₃ (LNO) heterostructures with restricted crystallographic orientations on bare Si(001) and SiO₂-coated Si(001) substrates, using TiN buffer layers. The effect of background gas pressure on orientation of the thin films was investigated in detail. XRD analyses showed that under optimized conditions, (001)-oriented PZT/LNO/TiN heterostructures could be grown on either Si(001) or SiO₂/Si substrates. The (001)-textured PZT films had remnant polarizations as high as 23µC/cm², and also had a low coercive field. Up to 10¹⁰ switching cycles have been achieved in these PZT films. / Singapore-MIT Alliance (SMA)

O desgaste abrasivo de dois aços austeníticos ao manganês, materiais com grande utilização na mineração, foi estudado empregando metodologia multiescala (escalas: macro, meso e micro). Na macroescala foram estudados os mecanismos de dano e de desgaste de revestimento de britador utilizado em campo. Na mesoescala foram realizados ensaios de britador de mandíbula e de esclerometria linear. Na microescala o ensaio de esclerometria linear foi utilizado para avaliar os efeitos da camada encruada em campo e da orientação cristalográfica dos grãos austeníticos dos aços com 12 %Mn e 20 %Mn. As técnicas de caracterização utilizadas nesta pesquisa foram: macro e microdureza, nanodureza instrumentada, MO, MEV, DRX, EBSD, FIB e MET. A pesquisa foi dividida em três Capítulos, intitulados: \"Desgaste abrasivo dos aços austeníticos com 12 %Mn e 20 %Mn via ensaio de britador de mandíbula\"; \"Efeito do encruamento e da orientação cristalográfica no desgaste por riscamento dos aços austeníticos 12 %Mn e 20 %Mn\"; e \"Microestrutura da subsuperfície do aço austenítico com 12 %Mn deformado por desgaste abrasivo\". O primeiro Capítulo mostrou, a partir do ensaio de britador de mandíbulas (mesoescala), que o aço com 20 %Mn tem tendência de maior resistência ao desgaste que o aço com 12 %Mn. Este resultado foi obtido para a mandíbula fixa do britador, na qual a severidade de desgaste foi superior a mandíbula móvel, por apresentar microcorte e microsulcamento como micromecanismos predominantes, enquanto na mandíbula móvel o micromecanismo predominante foi a microendentação. No segundo Capítulo observou-se que o desgaste por riscamento (mesoescala e microescala) não depende do perfil de encruamento gerado em campo. Entretanto, foi identificado o efeito da orientação cristalográfica, planos (001), (111) e (101), no desgaste por riscamento dos aços com 12 %Mn e 20 %Mn. No último Capítulo a análise multiescala mostrou que a microestrutura deformada na subsuperfície sofre alterações semelhantes em diferentes intensidades. Nas três escalas de análise foram observadas uma camada com grãos ultrafinos (nanométricos), na subsuperfície, e uma de transição com maclas de deformação. A formação dos grãos ultrafinos foi associada à recristalização dinâmica por deformação plástica, na qual faz parte do mecanismo de auto reparação superficial. Além dos resultados apresentados, o desenvolvimento desta pesquisa de doutorado permitiu a elaboração de duas metodologias: i. análise do efeito da orientação cristalográfica no desgaste por microesclerometria; e ii. análise de microestrutura revelada por ataque iônico - FIB. / The abrasive wear of two manganese austenitic steels, materials broadly used in mining industry, was studied using multiscale methodology (scales: macro, meso and micro). In the macroscale the mechanisms of damage and wear of in-service crusher liner were studied. In the mesoscale, jaw crusher and linear scratch tests were performed. In the microscale the linear scratch test was used to evaluate the effects of the hardening layer and the crystallographic orientation of the austenitic grains of steels with 12 %Mn and 20 %Mn. The characterization techniques used in this research were: macro and microhardness, instrumented nanohardness, OM, MEV, DRX, EBSD, FIB and TEM. The research was divided into three chapters, entitled: \"Abrasive wear of steels with 12 %Mn and 20 %Mn via jaw crusher test\"; \"The effect of the in-service workhardening and crystallographic orientation on the micro-scratch wear of austenitic steels with 12 %Mn and 20 %Mn\"; and \"Subsurface microstructure of the deformed austenitic steel with 12 %Mn by abrasive wear\". The first chapter showed, from the jaw crusher tests (i.e. mesoscale), that the steel with 20 %Mn tends to be more wear resistant than the steel with 12 %Mn. This result was obtained to the fixed jaw crusher, in which the wear severity was superior to the movable jaw, since it presents microcutting and microploughing as predominant micromechanisms, whereas in the mobile jaw the predominant micromechanism was microendentation. In the second chapter, it was observed that scratch wear (i.e. meso and microscale) does not depend on the in-service work-hardening profile. However, it was identified the effect of crystallographic orientation, (001), (111) and (101) planes, on the scratch wear of the steels with 12% Mn and 20% Mn. In the last chapter, the multiscale analysis showed that the subsurface deformed microstructure changes with different intensities. At the three analysis scales, a layer with ultrafine grains was observed in the subsurface and mechanical twins. The formation of this layer, with nanometric grains, was associated with dynamic recrystallization by plastic deformation, in which it is part of the self healing effect. In addition to the results found, the development of this doctoral research allowed for the elaboration of two methodologies: i. Analysis of the effect of crystallographic orientation on the scratch wear; and ii. Microstructure analysis revealed by ion etching - FIB.

In this thesis, the behavior of pearlitic steel was characterized under controlled wear conditions in the laboratory and service conditions in two ore mining stages, comminution and transportation. The thesis consists in three experimental chapters, divided according to the tribosystems analyzed. On all the chapters Electro Microscopy techniques for the microstructural analysis were employed. Scanning Electron Microscopy (SEM), Focused Ion Beam (FIB-SEM), Electron Backscatter Diffraction (EBSD) and Transmission Electron Microscopy (TEM) were used. The first experimental chapter shows the analysis of the pearlite under abrasive wear with loose abrasive particles in multi-events conditions. The sample was taken from Semi-Autogenous Grinding mills (SAG) and experimental simulation was carried out in laboratory using the Dry Sand Rubber Wheel Abrasion Test (DSRW). The results show a polycrystalline layer formation in both cases, characterized by ultra-fine grains of ferrite in the layer closer to the surface. It was also concluded that the DSRW can simulate the wear produced on field (superficial and microstructural features) in conditions of higher normal load than recommended by the ASTM Standard G65. The second experimental chapter explores the characterization of the microstructure after the indenter pass in scratch test using two conditions of normal load applied and five sequences of scratch. The microstructural analysis shows the formation of two subsuperficial layers identified by the level of the microstructural alterations. In the subsuperficial layer (close to the surface), the formation of new ultra-fine grains of ferrite was observed. A second layer was observed deeper in the sample and denominated as layer of the microstructure transition, characterized by the combination of deformed (reduction of the interlamellar spacing) and pearlite colonies not affected plastically by the mechanical loading. On this layer, the crystallographic texture in RD // in samples tested at 4 N (normal load) and one-pass scratch was determined. Later, on this chapter, the microstructure in a ground rail (industrial procedure characterized as a multi-event scratch test) was analyzed. Two grinding conditions were used for the analysis with variation of the grinding linear speed and load on the grinding stones (discs). The combination of low grinding speed and high load promotes a higher deformed layer formation beneath the patch zone and low randomized orientation of the pearlite colonies. Finally, in the third experimental chapter, the pearlitic characterization was concluded with the study of samples of railway wheel and rail under wear in service and Rolling Contact Fatigue (RCF) in laboratory. The laboratorial simulation was carried out using the twin-disc rolling contact tribometer with a variation of number of cycles. The characterization of railway wheel shows that the WEL is characterized by levels of breaking and aligned cementite and zones with dissolution of the carbon atom in the ferrite to form the supersaturated carbon ferrite. The polycrystalline ferrite formation (ultra-fine grains) in the sub-superficial layer and it was identified a preferential orientation of RD // in the layer of microstructural transition. The results of the laboratory test show surface crack nucleation and propagation at low angle in the more severe deformed layer. The microstructure of the layer consists in polycrystalline ferrite and the cementite dissolution. / Nesta tese foi caracterizado o comportamento do aço perlítico em condições controladas de desgaste em laboratório e em serviço em dois estágios do processo de mineração de minério, cominução e transporte ferroviário. A tese consiste em três capítulos experimentais divididos segundo o tribosistema analisado. Em todos os capítulos do trabalho foi utilizada a técnica de microscopia eletrônica para análise microestrutural. Foi utilizado Microscopia eletrônica de varredura (MEV), Focused Ion Beam (FIB-SEM), Electron Backscatter Diffraction (EBSD) e Microscopia eletrônica de transmissão (MET). O primeiro capítulo experimental mostra a análise da perlita in condições de desgaste abrasivo com partículas soltas em eventos múltiplos. As amostras foram tiradas de um moinho semi-autógeno (SAG) e realizada uma simulação experimental do desgaste em condições controladas usando o tribômetro de roda de borracha (RWAT). Os resultados mostraram a formação de camada branca em ambas as condições de análise, consistindo em uma camada poli cristalina caracterizada pela formação de grãos ultrafinos na camada mais próxima da superfície de desgaste. Também foi concluído que a roda de borracha pode simular o desgaste produzido nos moinhos SAG tanto nas características superficiais quanto microestruturais em condições de maior severidade as comumente utilizadas na norma ASTM G65 (procedimento B). O Segundo capítulo experimental explora a caracterização da microestrutura depois da passagem do endentador no ensaio de riscamento (scratch test) utilizando duas condições de carga normal aplicada e 5 sequências de riscamento. A análise microestrutural mostrou a formação de duas camadas subsuperficiais identificadas pelo nível de alteração microestrutural. Na camada mais próxima da superfície de desgaste foi observada a formação de grãos ultrafinos de ferrita. A segunda camada identificada mais profundamente na amostra, denominada como camada de transição, é caracterizada pela combinação de colônias deformadas (redução do espaçamento interlamelar) e camadas não afetadas pelos esforços produzidos no contato. Nesta camada foi determinada a texturização em direção RD // nas amostras testadas a 4 N (carga normal aplicada) e uma passada. Posteriormente à análise de riscamento foi caracterizada a microestrutura de uma amostra tirada de um trilho esmerilhado (processo industrial que pode ser considerado como aplicação do ensaio de riscamento). Foram consideradas duas condições de esmerilhamento com variação de velocidade de esmerilhamento (deslocamento linear do veículo esmerilhador) e potência dos motores dos rebolos usada no procedimento. A combinação de baixa velocidade de esmerilhamento e alta potência nos motores controladores dos rebolos promoveu uma grande deformação nas camadas subsuperficiais na região de contato e uma baixa aleatoriedade das orientações cristalográficas das colônias de perlita. Finalmente, no capítulo três, a caracterização da microestrutura perlitica foi finalizada com o estudo de amostras de roda e trilho em condições de desgaste em campo e de Rolling Contact Fatigue (RCF) em ensaios de laboratório. A simulação experimental foi realizada utilizando o tribômetro twin-disc rolling (configuração disco-disco) com variação do número de ciclos. A caracterização da roda ferroviária mostrou a formação da camada branca caracterizada por níveis de cementita fraturada e alinhada em direção do movimento de rolamento/deslizamento com áreas de dissolução do átomo de carbono na ferrita formando uma ferrita supersaturada. Foi identificado a formação de policristais de ferrita (grãos ultrafinos) na camada mais superficial e uma orientação preferencial RD // na camada de transição. Os resultados dos ensaios de laboratório mostraram a nucleação de trincas superficiais se propagando a baixo ângulo na camada branca. A transformação microestrutural dessa camada após ensaios de laboratório consiste em policristais de ferrita e dissolução da cementita.

Built on the recent successes in understanding the crystallographic mechanism for short fatigue crack (SFC) growth across a grain boundary (GB) and developing an experimental method to quantify the GB resistance against short crack growth, a microstructure-based model was developed in this study to simulate the growth behaviors of SFCs in 3-D, by taking into account both the driving force and resistance along at each point along the crack front in an alloy. It was found that the GB resistance was a Weibull function of the minimum twist angle of crack deflection at the boundary in AA2024-T3 Al alloys. In the digital microstructure used in the model, the resistance at each GB that the short crack interacted with could be calculated, as long as the orientations of grains and the crack were known. In the model, an influence function accounting for the overlapping effect of the resistance from the neighboring grain boundaries was proposed, allowing for calculation of the total resistance distribution along the crack front. In order to overcome the time consuming problem for the existing equations to derive the distribution of stress intensity factor along the crack front under cyclic loading, an analytical equation was proposed to quantify the stress intensity factor distribution along an irregular shape planar crack. By introducing two shape-dependent factors, the fractured area and the perimeter of the crack front, the newly proposed equation could readily and accurately derive the stress intensity factor distribution along the crack front that had large curvatures and singularities. Finally, a microscopic-scale Paris’ equation was proposed that took into account both the driving force, i.e., stress intensity factor range, and the total resistance to calculate the growth rate at each point along crack front. The model developed in this work was able to incorporate microstructure, such as grain size and shape, and texture into simulation of SFC growth in 3-D. It was capable of simulating all the anomalous growth behaviors of SFCs, such as the marked scatters in growth rate measurement, retardation and arrest at grain boundaries, and crack plane deflection at grain boundaries, etc. The model was used to simulate the growth behaviors of SFCs initiated from prefractured constituent particles in order to interpret the multi-site fatigue crack initiation observed in AA2024-T351 Al alloys. Three types of SFCs were observed initiating from these particles, namely, type-I non-propagating cracks; type-II cracks which were arrested soon after propagating into the matrix; and type-III propagating cracks. To quantitatively study the 3-D effects of particle geometry and micro-texture on the growth behaviors of micro-cracks in these particles, rectangular micro-notches with different dimensions were fabricated using focused ion beam in the selected grains on the T-S planes in AA2024-T351 Al alloys, to mimic the pre-fractured particles in these alloys. Knowing the notch dimensions or particle shape, grain orientation and GB geometry, the simulated crack growth behaviors were consistent with the experimental observations, and the model was able to verify that the three types of cracks evolved from these particles were mainly associated with the thickness and width of the pre-fractured particles, though the particle geometry and grain orientation could also affect the behaviors of fatigue crack initiation at the particles. When the widths of the particles were less than 15 μm, like in most high strength Al alloys, the simulated results confirmed that the crack type was only associated with the particle thickness, consistent with the experimental results in AA2024-T351 alloys with a strong rolling texture. The lives for the SFCs to reach 0.5 mm in length were quantified with the model in the AA2024 alloy, revealing that there was a bimodal distribution in the life spectrum calculated, with the longer life peak being related to larger twist angles of crack deflection at the first GB the cracks encountered and the shorter life peak being associated with small twist angles (< 5°) at the first GB. The model further demonstrated the influence of grain structure on SFC growth by considering two different grain structures with the same initial short crack, namely, a layered grain structure with only the primary GBs perpendicular to the surface and the layered grains with both primary and secondary GBs. Depending on their positions and geometry, the secondary GBs could still exert a strong retarding effect on SFC growth on surface. The model was validated by matching to the growth rate measured on surface of a SFC in an AA8090 Al-Li alloy. Good consistency was achieved between the simulated and experimentally measured growth rates when both the primary and secondary GBs were considered in the model. The model developed in this study exhibits its potential applications to optimizing the microstructure and texture in alloys to enhance their fatigue resistance against fatigue crack growth, and to satisfactory life prediction of engineering alloys.

The aim of this study is to evaluate a methodology for modeling the influence of crystallographic grain orientation on key parameters in normal and sliding contacts. The simulations of interfering cylindrical asperities, using finite element analysis, were conducted using two different plasticity models for copper: a conventional isotropic, homogeneous J2 plasticity model and a continuum crystal plasticity model. A normal contact study was conducted in which crystallographic orientation effects on different parameters were investigated. The model was then adapted for sliding contacts, which allowed other parameters such as energy dissipation to be investigated. Using crystal plasticity, the dependence of crystallographic orientation on plastic deformation and energy dissipation can be determined. The relative trends predicted using crystal plasticity are consistent with experiments that show friction depends on crystallographic orientation when plastic deformation is one of the primary energy dissipation mechanisms.

In this thesis, the behavior of pearlitic steel was characterized under controlled wear conditions in the laboratory and service conditions in two ore mining stages, comminution and transportation. The thesis consists in three experimental chapters, divided according to the tribosystems analyzed. On all the chapters Electro Microscopy techniques for the microstructural analysis were employed. Scanning Electron Microscopy (SEM), Focused Ion Beam (FIB-SEM), Electron Backscatter Diffraction (EBSD) and Transmission Electron Microscopy (TEM) were used. The first experimental chapter shows the analysis of the pearlite under abrasive wear with loose abrasive particles in multi-events conditions. The sample was taken from Semi-Autogenous Grinding mills (SAG) and experimental simulation was carried out in laboratory using the Dry Sand Rubber Wheel Abrasion Test (DSRW). The results show a polycrystalline layer formation in both cases, characterized by ultra-fine grains of ferrite in the layer closer to the surface. It was also concluded that the DSRW can simulate the wear produced on field (superficial and microstructural features) in conditions of higher normal load than recommended by the ASTM Standard G65. The second experimental chapter explores the characterization of the microstructure after the indenter pass in scratch test using two conditions of normal load applied and five sequences of scratch. The microstructural analysis shows the formation of two subsuperficial layers identified by the level of the microstructural alterations. In the subsuperficial layer (close to the surface), the formation of new ultra-fine grains of ferrite was observed. A second layer was observed deeper in the sample and denominated as layer of the microstructure transition, characterized by the combination of deformed (reduction of the interlamellar spacing) and pearlite colonies not affected plastically by the mechanical loading. On this layer, the crystallographic texture in RD // in samples tested at 4 N (normal load) and one-pass scratch was determined. Later, on this chapter, the microstructure in a ground rail (industrial procedure characterized as a multi-event scratch test) was analyzed. Two grinding conditions were used for the analysis with variation of the grinding linear speed and load on the grinding stones (discs). The combination of low grinding speed and high load promotes a higher deformed layer formation beneath the patch zone and low randomized orientation of the pearlite colonies. Finally, in the third experimental chapter, the pearlitic characterization was concluded with the study of samples of railway wheel and rail under wear in service and Rolling Contact Fatigue (RCF) in laboratory. The laboratorial simulation was carried out using the twin-disc rolling contact tribometer with a variation of number of cycles. The characterization of railway wheel shows that the WEL is characterized by levels of breaking and aligned cementite and zones with dissolution of the carbon atom in the ferrite to form the supersaturated carbon ferrite. The polycrystalline ferrite formation (ultra-fine grains) in the sub-superficial layer and it was identified a preferential orientation of RD // in the layer of microstructural transition. The results of the laboratory test show surface crack nucleation and propagation at low angle in the more severe deformed layer. The microstructure of the layer consists in polycrystalline ferrite and the cementite dissolution. / Nesta tese foi caracterizado o comportamento do aço perlítico em condições controladas de desgaste em laboratório e em serviço em dois estágios do processo de mineração de minério, cominução e transporte ferroviário. A tese consiste em três capítulos experimentais divididos segundo o tribosistema analisado. Em todos os capítulos do trabalho foi utilizada a técnica de microscopia eletrônica para análise microestrutural. Foi utilizado Microscopia eletrônica de varredura (MEV), Focused Ion Beam (FIB-SEM), Electron Backscatter Diffraction (EBSD) e Microscopia eletrônica de transmissão (MET). O primeiro capítulo experimental mostra a análise da perlita in condições de desgaste abrasivo com partículas soltas em eventos múltiplos. As amostras foram tiradas de um moinho semi-autógeno (SAG) e realizada uma simulação experimental do desgaste em condições controladas usando o tribômetro de roda de borracha (RWAT). Os resultados mostraram a formação de camada branca em ambas as condições de análise, consistindo em uma camada poli cristalina caracterizada pela formação de grãos ultrafinos na camada mais próxima da superfície de desgaste. Também foi concluído que a roda de borracha pode simular o desgaste produzido nos moinhos SAG tanto nas características superficiais quanto microestruturais em condições de maior severidade as comumente utilizadas na norma ASTM G65 (procedimento B). O Segundo capítulo experimental explora a caracterização da microestrutura depois da passagem do endentador no ensaio de riscamento (scratch test) utilizando duas condições de carga normal aplicada e 5 sequências de riscamento. A análise microestrutural mostrou a formação de duas camadas subsuperficiais identificadas pelo nível de alteração microestrutural. Na camada mais próxima da superfície de desgaste foi observada a formação de grãos ultrafinos de ferrita. A segunda camada identificada mais profundamente na amostra, denominada como camada de transição, é caracterizada pela combinação de colônias deformadas (redução do espaçamento interlamelar) e camadas não afetadas pelos esforços produzidos no contato. Nesta camada foi determinada a texturização em direção RD // nas amostras testadas a 4 N (carga normal aplicada) e uma passada. Posteriormente à análise de riscamento foi caracterizada a microestrutura de uma amostra tirada de um trilho esmerilhado (processo industrial que pode ser considerado como aplicação do ensaio de riscamento). Foram consideradas duas condições de esmerilhamento com variação de velocidade de esmerilhamento (deslocamento linear do veículo esmerilhador) e potência dos motores dos rebolos usada no procedimento. A combinação de baixa velocidade de esmerilhamento e alta potência nos motores controladores dos rebolos promoveu uma grande deformação nas camadas subsuperficiais na região de contato e uma baixa aleatoriedade das orientações cristalográficas das colônias de perlita. Finalmente, no capítulo três, a caracterização da microestrutura perlitica foi finalizada com o estudo de amostras de roda e trilho em condições de desgaste em campo e de Rolling Contact Fatigue (RCF) em ensaios de laboratório. A simulação experimental foi realizada utilizando o tribômetro twin-disc rolling (configuração disco-disco) com variação do número de ciclos. A caracterização da roda ferroviária mostrou a formação da camada branca caracterizada por níveis de cementita fraturada e alinhada em direção do movimento de rolamento/deslizamento com áreas de dissolução do átomo de carbono na ferrita formando uma ferrita supersaturada. Foi identificado a formação de policristais de ferrita (grãos ultrafinos) na camada mais superficial e uma orientação preferencial RD // na camada de transição. Os resultados dos ensaios de laboratório mostraram a nucleação de trincas superficiais se propagando a baixo ângulo na camada branca. A transformação microestrutural dessa camada após ensaios de laboratório consiste em policristais de ferrita e dissolução da cementita.

In this thesis, the surface properties of cassiterite due to the changes of two material properties, i.e. crystallographic orientation, and Fe as a minor element in the lattice, and their implication for selective separation are studied. In the study of the crystallographic orientation of cassiterite, the physicochemical behaviors of the surfaces SnO2(110), SnO2(100), as well as SnO2(001) were investigated by using high-resolution direct force spectroscopy. The measurements were conducted between a silica sphere and sample surfaces in 10 mmol/L KCl between pH 3.1 and 6.2 using colloidal probe atomic force microscopy (cp-AFM-hydrophilic). Dissimilar interactions were detected on different-oriented surfaces. The pH values where the force switched from positive to negative can be clearly distinguished and be ordered as SnO2(100) < SnO2(001) ≈ SnO2(110). The most potent attractive force was found to be on the (110) cassiterite surface compared to the (100) and (001) cassiterite surfaces at lower pH. By fitting the force curves in the DLVO theory framework, anisotropic surface potentials were computed between the three sample surfaces following a similar trend as force interaction. This differential surface potential might be due to the difference in Sn cation density and electron affinity. To study the implication of crystallographic orientation to surfactant adsorption, we used Aerosol22 (sulfosuccinamate) as an anionic collector for cassiterite flotation to functionalize the different samples at pH 3. The contact angle measurements, the topography visualizations by AFM, and the force measurement using cp-AFM with hydrophobized spheres (cp-AFM-hydrophobized) have shown that Aerosol22 was adsorbed on the sample surfaces inhomogeneously. The adsorption followed the order of SnO2(110) > SnO2(100) > SnO2(001) in the concentration from 1 × 10−6 mol/L to 1 × 10−4 mol/L. In the study of Fe as a minor element in the lattice of cassiterite, synthetic pure cassiterite, and cassiterite doped with two different Fe contents were successfully recrystallized by means of sintering. Their crystal structure and chemical compositions are characterized by X-ray powder diffraction (XRD) as well as scanning electron microscopy (SEM) combined with energy-dispersive X-ray (EDX) analysis. Their floatability was studied by microflotation with a diphosphonic acid surfactant named Lauraphos301 as a collector. Unlike the addition of ferric ions in solution, which strongly depressed the floatability of all the cassiterite samples, a much higher flotation efficiency of the Fe-doped cassiterite samples was found especially at lower collector concentrations. The cassiterite floatability is proportional to the Fe content in the cassiterite at a broad range of pH, and the recovery has the following order: Cassiterite with 1417 ppm Fe > cassiterite with 1165 ppm Fe > pure cassiterite The electrokinetic behavior of the cassiterite samples with and without the collector was studied by electrophoretic measurements and revealed that the chemical interaction dominated the adsorption. With the help of the particle shape analysis, a more angular shape was found for the Fe-doped cassiterite samples. Moreover, without the influence of particle shape, abundant adsorption of Lauraphos301 was found on the Fe-doped cassiterite samples by AFM topography imaging. The minor amount of Fe in the cassiterite lattice and a more angular shape of the Fe-doped cassiterite samples were believed to enhance floatability collectively. The study reveals that the influence of the chemical composition of the minerals on flotation was almost inextricably bound up with particle morphology and emphasizes the importance of considering both factors and investigating them individually for the flotation study.