In the present work further modifications are implemented to an existing test setup for the evaluation of the wear of cemented carbide drill buttons in rock drilling applications. The test setup has been evaluated in previous diploma works, which has shown that the test successfully mimics the wear seen in rock drilling applications. The new modifications include friction and normal force measurements together with the collection of rock debris. This has been made possible by redesigning the sample holder and by manufacturing equipment making rock debris collection possible. The new modifications to the test setup were evaluated by comparing the wear of three different cemented carbide grades tested against sandstone and granite with two different loads. The data collected from the new modifications were found to be robust with lower than expected spread of data. The coefficient of friction when testing against sandstone was higher than when testing against granite. More adhered material was observed on the wear surface when testing against granite than against sandstone. Load dependence on the wear of the cemented carbide buttons is only seen for the softer cemented carbide grades when testing against sandstone. The wear of the buttons indicates a high dependence on the hardness of the different grades as shouldbe expected. This diploma work has been performed for Sandvik Mining, Rock Tools,a world leading supplier of rock drill equipment.

Materials for studies related to nanoscience and nanotechnology have gained tremendous attention owing to their unique physical, chemical and electronic properties. Among various anisotropic nanostructures, one dimensional (1D) materials have received immense interest in numerous fields ranging from catalysis to electronics. Imparting multi-functionality to nanostructures is one of the major areas of research in materials science. In this direction, use of nanosized materials in energy systems such as fuel cells has been the subject of focus to achieve improved performance. Tuning the morphology of nanostructures, alloying of catalysts, dispersing catalytic particles onto various supports (carbon nanotubes, carbon nanofibers, graphene, etc.) are some of the ways to address issues related to electrochemical energy systems. It is worth mentioning that highly stable and corrosion resistant electrodes are mandatory as electrochemical cells operate under aggressive environments. Additionally, carbon, which is often used as a support for catalysts, is prone to corrosion and is subsequently implicated in reduced performance due to poor adherence of catalyst particles and loss in electrochemically active area. Hence, there is a quest for the development of stable and durable electrocatalysts / supports for various studies including fuel cells. The present thesis is structured in exploring the multi-functional aspects of titanium carbide (TiC), an early transition metal carbide. TiC, a fascinating material, possesses many favorable properties such as extreme hardness, high melting point, good thermal and electrical conductivity. Its metal-like conductivity and extreme corrosion resistance prompted us to use this material for various electrical and electrochemical studies. The current study explores the versatility of TiC in bulk as well as nanostructured forms, in electrical and electrochemical studies towards sensing, electrocatalytic reactions and active supports. 1D TiC nanowires (TiC-NW) are prepared by simple solvothermal method without use of any template and are characterized using various physico-chemical techniques. The TiC-NW comprise of 1D nanostructures with several µm length and 40 ± 15 nm diameter (figure 1). Electrical properties of individual TiC-NW are probed by fabricating devices using focused ion beam deposition (FIB) technique. The results depict the metallic nature of TiC-NW (figure 2). Figure 1. (a) SEM, (b) TEM and (c) HRTEM images of TiC-NW prepared by solvothermal method. Figure 2. (a) SEM image and (b) I-V characteristics of TiC-NW - based device as a function of temperature. The contact pads are made of Pt. Subsequently, oxidized TiC nanowires are prepared by thermal annealing of TiC-NW, leading to carbon - doped TiO2 nanowires (C-TiO2-NW) (figure 3). Photodetectors are fabricated with isolated C-TiO2-NW and the device is found to respond to visible light (figure 3) radiation with very good responsivity (20.5 A/W) and external quantum efficiency (2.7 X 104). The characteristics are quite comparable with several reported visible light photodetectors based on chalcogenide semiconductors. Figure 3. (a) HRTEM, (b) EDAX, (c) Scanning TEM-DF images of C-TiO2-NW along with (d) Ti (e) O and (f) C mapping. (g) Current – voltage curves of single C-TiO2-NW recorded in dark (black) and in presence of visible light radiation (red) of intensity 57.7 mW/cm2 at 25oC. Inset of (g) shows the SEM image of the device (top) and schematic illustration of fabricated photodetector (bottom). The next chapter deals with the electrochemical performance of TiC demonstrated for studies involving oxygen reduction and borohydride oxidation reactions. Electrochemical oxygen reduction reaction (ORR) reveal that TiC-NW possess high activity for ORR and involves four electron process while it is a two electron reduction for bulk TiC particles (figure 4). The data has been substantiated by density functional theory (DFT) calculations that reveal different modes of adsorption of oxygen on bulk and nanowire morphologies. Stable performance is observed for several hundreds of cycles that confirm the robustness of TiC. The study also demonstrates excellent selectivity of TiC for ORR in presence of methanol and thus cross-over issue can be effectively addressed in direct methanol fuel cells. In the chapter on borohydride oxidation, bare TiC electrode is explored as a catalyst for the oxidation of borohydride. One of the major issues in direct borohydride fuel cells (DBFC) is the hydrolysis of borohydride that happens on almost all electrode materials leading to low efficiency. The present study reveals that TiC is a very good catalyst for borohydride oxidation with little or no hydrolysis of borohydride [figure 5 (a)] under the experimental conditions studied. Further, shape dependant activity of TiC has been studied and fuel cell performance is followed [figure 5 (b)]. Polarization data suggests that the performance of TiC is quite stable under fuel cell experimental conditions. Figure 4. (a) Linear sweep voltammograms for ORR recorded using (i) bulk TiC particles and (ii) TiC-NW in O2-saturated 0.5 M KOH at 1000 rpm. Scan rate used is 0.005 Vs-1. (b) Variation of number of electrons with DC bias. Black dots correspond to TiC bulk particles while red ones represent nanowires. Figure 5. (a) Cyclic voltammograms of borohydride oxidation on TiC coated GC electrode in 1 M NaOH containing 0.1 M NaBH4. Scan rate used is 0.05 Vs-1. (b) Fuel cell polarization data at 70oC for DBFC assembled with (i) bulk TiC particles and (ii) TiC-NW as anode catalysts and 40 wt% Pt/C as cathode. Anolyte is 2.1 M NaBH4 in 2.5 M NaOH, and catholyte is 2.2 M H2O2 in 1.5 M H2SO4. Anode loading is 1.5 mg cm-2 and cathode loading is 2 mg cm-2. The corrosion resistance nature of TiC lends itself amenable to be used as an active support for catalytic particles (Pt and Pd) for small molecules oxidation reactions. In the present study, electro-oxidation of methanol, ethanol and formic acid have been studied. As shown in figure 6 (a), the performance of Pd loaded TiC (Pd-TiC) is found to be higher than that of Pd loaded carbon (Pd-C) suggesting the active role of TiC. The catalytic activities of TiC-based supports are further improved by tuning their morphologies. Figure 6 (c) reveals that the activities are higher in case of Pd-TiC-NW than that of Pd-TiC. Figure 6. (a) Cyclic voltammograms of Pd-TiC and Pd-C for ethanol oxidation, (b) T EM image of Pd-TiC-NW and (c) voltammograms of Pd-TiC-NW in N2-saturated 1 M ethanol in 1 M KOH medium, scan rate used is 0.05 Vs-1. The next aspect explored, is based on the preparation of C-TiO2 and its use as a substrate for surface enhanced Raman spectroscopy (SERS). Carbon doped titanium dioxide is prepared by thermal annealing of TiC. It is observed that the amount of dopant (carbon content) is dependent on the experimental conditions used. SERS studies using 4¬mercaptobenzoic acid (4-MBA) as the analyte, indicates that C-TiO2 [figure 7 (a)] enhances Raman signals based on chemical interactions between the analyte and the substrate. Raman signal intensities can be tuned with the amount of carbon content in C¬TiO2. Enhancement factors are calculated to be (7.7 ± 1.2) x 103 (for 4-MBA) and (1.7 ± 1.2) x 103 (for 4-nitrothiophenol). The SERS substrates are found to be surface renewable using visible light, a simple strategy to re-use the substrate [figure 7 (b)]. The regeneration of SERS substrates is based on self cleaning action of TiO2 that produces highly reactive oxygen containing radicals known to degrade the molecules adsorbed on TiO2. Thus, the versatility of TiC has been demonstrated with various studies. In addition to using TiC-based materials, nanoparticles of Rh, Ir and Rh-Ir alloy structures have also been used for borohydride oxidation reaction. This is explained in the last section. In Appendix-I, preliminary studies on the preparation of TiC-polyaniline (PANI) composites using liquid-liquid interfacial polymerization is explained. Raman spectroscopy results suggest that the presence of TiC-NW makes PANI to assume preferential orientation in the polaronic (conducting) form. Appendix-II discusses the role of TiC-NW as a fluorescence quencher for CdS semiconductor nanoparticles.

<div> <div> <div> <p> </p><div> <div> <div> <div> <div> <div> <p> </p><div> <div> <div> <p>Two-dimensional (2D) transition-metal dichalcogenides (TMDCs) and transition metal carbides/nitrides (MXenes), have been recently receiving attention for gas sensing applications due to their high specific area and rich surface functionalities. However, using pristine 2D materials for gas-sensing applications presents some drawbacks, including high operation temperatures, low gas response, and poor selectivity, limiting their practical sensing applications. Moreover, one of the long-standing challenges of MXenes is their poor stability against hydration and oxidation in a humid environment, which negatively influences their long- term storage and applications. Many studies have reported that the sensitivity and selectivity of 2D materials can be improved by surface functionalization and hybridization with other materials.</p><p>In this work, the effects of surface functionalization and/or hybridization of these two materials classes (TMDCs and MXenes) on their gas sensing performance have been investigated. In one of the lines of research, 2D MoS2 nanoflakes were functionalized with Au nanoparticles as a sensing material, providing a performance enhancement towards sensing of volatile organic compounds (VOCs) at room temperature. Next, a nanocomposite film composed of exfoliated MoS2, single-walled carbon nanotubes, and Cu(I)−tris(mercaptoimidazolyl)borate complexes was the sensing material used for the design of a chemiresistive sensor for the selective detection of ethylene (C2H4). Moreover, the hybridization of MXene (Ti3C2Tx) and TMDC (WSe2) as gas-sensing materials was also proposed. The Ti3C2Tx/WSe2 hybrid sensor reveals high sensitivity, good selectivity, low noise level, and ultrafast response/recovery times for the detection of various VOCs. Lastly, we demonstrated a surface functionalization strategy for Ti3C2Tx with fluoroalkylsilane (FOTS) molecules, providing a superhydrophobic surface, mechanical/environmental stability, and excellent sensing performance. The strategies presented here can be an effective solution for not only improving materials' stability, but also enhancing sensor performance, shedding light on the development of next-generation field-deployable sensors.</p> </div> </div> </div><div><div><div><div><div><div> </div> </div> </div> </div> </div> </div></div></div></div> </div> </div> </div></div></div></div><div><div><div> </div> </div> </div>

The diploma work deals with comparison of sintered carbides in product assortment of Pramet Tools a.s., Sandvik-Coromant and Ceratizit companies in term of their cutting speed, feed and depth of cut for the turning operation. The comparison of cutting parameters is made for P, M, K, N, S and H groups. For better comparison there are always two sintered carbides from each of the manufacturers mentioned for each of the groups P, M, K. They are mentioned for groups N, S and H only if they are suggested by the manufacturer.

It is an established fact that segregation during casting affects the physical properties of carbon-based ferro alloys; this motivates the study of the segregation behaviour of carbon and carbide-forming solute elements. In this context, this thesis investigates two different situations: the effects of cooling rate and turbulence on the precipitation behaviour of the graphite nodules in nodular cast iron; the nature of carbide precipitation in a bearing steel grade and the effects of subsequent soaking on these carbides. The structures of boiling water reactor inserts cast by the uphill and downhill casting of nodular cast iron were examined. The samples were taken from representative locations in the top, middle and bottom cross sections of the castings. It was observed that in uphill-cast inserts the nodules were larger but fewer in number the bottom section, whereas in downhill-cast inserts the nodules in the bottom section were smaller, but greater in number. Variation in volume fraction of the graphite nodules across the inserts was also observed. The probable cause of this variation was the difference in cooling rate in different sections of the insert. Between the steel tubes located at the central part of the casting, the fraction of graphite was lower, which could be the result of carburization of the steel tubes. To study the effects of melt stirring during the solidification of nodular cast iron, several experiments were conducted at variable cooling rates and for different stirring times. Examination of the microstructure was conducted using Light Optical Microscope (LOM) and Scanning Electron Microscope (SEM). It was observed that during stirring the melt oxidized and oxide nuclei were formed. The number of nucleation sites for the precipitation of graphite nodules increased, which raised the nodule count and the fraction of the graphite precipitated. The matrix transformed from pearlite to ferrite, which could be due to the fact that more carbon had diffused out of the matrix. The segregation behaviour in hypereutectoid bearing steel produced by ingot casting was also studied. The effects of soaking on micro and macro segregation was investigated in samples taken from as cast and soaked ingots; emphasis was laid on the bulk matrix and A-segregation channels. Samples were also taken from ingots which were soaked and then hot worked. The micro and macro examination of the microstructure was conducted using LOM and SEM. Quantitative and qualitative composition analysis was performed using Energy-dispersive X-ray spectroscopy (EDX) and an electron micro probe analyzer (EMPA). It was observed that M3C, M2C and M6C had precipitated. The carbide morphology in the bulk matrix was different to that in the A-segregation channels. All the primary carbides in the bulk matrix were found to have dissolved after 4 hours of soaking at 1200oC. / Det är ett faktum att segringar som uppstår under gjutning påverkar materialegenskaperna hos kolbaserade järnlegeringar; detta utgör motivationen till studien av segringsuppträdandet hos kol och karbidbildande ämnen. Denna avhandling behandlar två olika aspekter inom ramen för detta ämne: påverkan av kylningshastighet och turbulens på kärnbildningen av grafitnoduler i nodulärt gjutjärn samt karbidbildning i kullagerstål och dess påverkan på den efterföljande värmebehandlingen av dessa karbider. Strukturen hos rör till vattenkokare som tillverkats av nodulärt gjutjärn som gjutits med fyllning från botten eller från toppen undersöktes. Prover togs från representativa tvärsnittspositioner från toppen, mitten och botten av de gjutna ämnena. Resultaten visade att användandet av bottenfyllda kokiller gav upphov till större men färre karbider i nedre delen av ämnet, medans användandet av toppfyllda kokiller gav upphov till mindre men fler karbider i nedre delen av ämnet. Variationer av volymfraktionen av grafitnoduler längs tvärsnitten observerades också. Den mest sannolika orsaken till denna variation var skillnaden i kylhastighet i de olika områdena av tvärsnitten. Hos rör tillverkade av det centrala delen av ämnet så var fraktionen grafit lägre, vilket kan bero på en uppkolning av rören. Ett flertal experiment utfördes med varierande kylningshastigheter och olika omrörningstider för att studera inverkan av omrörning av smältan på stelningen av nodulärt gjutjärn. Studier av mikrostrukturen genomfördes med ljusoptisk mikroskopi och svepelektronmikroskopi. Resultaten visade att smältan oxiderades under omrörningen, vilket resulterade i bildandet av oxider. Detta ledde till en ökning av kärnbildningsområden för grafitnoduler, vilket ledde till en ökning av antalet noduler samt fraktionen av grafit som fälldes ut. Strukturen omvandlades från perlit till ferrit, vilket troligen orsakades av att kol hade diffunderat ut från strukturen. Segringsbeteendet hos hypereutektoida kullagerstål tillverkade genom götgjutning undersöktes också. Effekten av värmebehandling på mikro- och makrosegringar undersöktes i prover tagna från gjutna och värmebehandlade ämnen. Fokus var på att studera strukturen i ämnena samt A-segringar. Dessutom togs prover från ämnen som först värmebehandlats och därefter varmbearbetats. Både mikro- och makroundersökningar av mikrostrukturen utfördes med ljusoptisk mikroskopi och svepelektronmikroskopi. Dessutom så genomfördes kvantitativa sammansättningsbestämningar med energidispersiv röntgenspektroskopi och elektronmikroprobsanalys. Resultaten visade att M3C, M2C och M6C karbider hade fällts ut. Karbidmorfologin i huvuddelen av strukturen skiljde sig från den som återfanns i A-segringar. Samtliga primära karbider i huvuddelen av strukturen hade lösts upp efter 4 timmars värmebehandling vid 1200oC. / <p>QC 20180523</p>

This master‘s thesis is presenting the way of the optimization of grinding characteristics when grinding cemented carbides by diamond wheels. There is described the theory of grinding, including grinding wheels and basic characteristics of cemented carbides in the theoretical part. There are defined experimental metering accomplished on the CNC grinding machine Walter Helitronic Power Mini in the practical part. There were tested eight grinding wheels. The grinding rate, surface roughness Ra, theoretic guaranteed storage period of grinding wheel in number of cuts, theoretical capacity of machined material, achievement of grinding machine and behaviour of the wheels when grinding ware evaluated from the reached results.

This thesis aims to compare the relationship of physical-mechanical properties of tool materials made of WC-Co sintered carbides with their resistance to initiation and propagation of thermal cracks. The paper presents the results of testing the basic physical-mechanical properties of the three samples sintered carbides with different percentage of Co binder. Next, this thesis describes the progress and results of quench experiment and cutting tests using, which was described resistance of the tested samples to thermal and mechanical shock, depending on the values of physical-mechanical properties.

En perspective de la prolongation de la durée de vie en service des REPs, il est de plus en plus important d’obtenir une évaluation fiable de l’évolution de la microstructure des aciers constituant la cuve des REPs et de leurs propriétés correspondantes. Un mécanisme de fragilisation non-durcissante, dû à la ségrégation intergranulaire du P qui affaiblirait la cohésion des joints de grains, pourrait contribuer à la fragilisation et doit donc être étudié. Les présents travaux ont pour objectifs d’étudier la ségrégation intergranulaire du P dans un acier de cuve de réacteur afin (i) de connaître l’influence du type de joint de grain sur la ségrégation du P, (ii) de clarifier l’influence des conditions de vieillissement (vieillissement thermique et irradiation ionique) sur la ségrégation du P et (iii) de faire une comparaison avec les modèles disponibles et proposés ici.Pour cela, une méthodologie corrélative -Diffraction des Électrons Rétrodiffusés (EBSD), Diffraction de Kikuchi en Transmission (TKD) et Sonde Atomique Tomographique (APT) -a été adoptée pour étudier la ségrégation intergranulaire. Les informations cristallographiques (5 paramètres) et la composition chimique ont été collectées et systématiquement corrélées. Les aciers ont une microstructure complexe de ferrite aciculaire et de carbures intergranulaires. La ségrégation des solutés aux joints des grains (joints des grains faiblement désorientés (LAGB), joints des grains fortement désorientés généraux (HAGB) et Σ3HAGBs) et aux interfaces (interfaces carbure-ferrite M2.0-3.2C et interfaces cémentite-ferrite) a été quantifiée. Il existe une ségrégation évidente d'un élément ou de plusieurs espèces chimiques (C, P, Mn, Mo, Cr, Si et Ni) pour tous ces types de défauts plans. Tenant compte de la nature des éléments ségrégants et de la cristallographie du joint de grain, les ségrégations interstitielles et substitutionnelles ont été quantifiées et discutées. Sur la base d’un grand nombre de données, il apparaît que les niveaux moyens des segrégations en P sont plus élevés dans les HAGBs généraux ou les LAGBs que les autres types d'interfaces quel que soit le vieillissement envisagé. Par ailleurs, les résultats expérimentaux ont été comparés avec les résultats prévus par des modèles analytiques pour des systèmes binaires, ternaires et multi-composants. Bien qu'ayant un niveau de ségrégation du P prédit plus élevé, le modèle ternaire Fe-P-C se rapproche le plus des résultats expérimentaux. / With expectations for extending the service lifespans of PWRs, it is of great importance to get a reliable evaluation of the microstructural evolution and the corresponding property changes of RPV steels. A non-hardening mechanism, due to intergranular P segregation that impairs the grain boundary (GB) cohesion, may contribute to the embrittlement and thus needs to be studied. The present work aims to investigate the intergranular P segregation behavior in a RPV steel in order to (i) determine the influence of GB type on P segregation behavior, (ii) clarify the influence of ageing conditions (thermal ageing and ion irradiation) on P segregation behavior and (iii) make a comparison with the existing analytical models. To reach these objectives, a correlative - Electron Backscatter Diffraction (EBSD), Transmission Kikuchi Diffraction (TKD) and Atom Probe Tomography (APT) - methodology was adopted to study the GB segregation behavior. The crystallographic information (5 parameters) and chemical composition were collected simultaneously. The steels have a complex microstructure of acicular ferrite and intergranular carbides. The solute segregation at GBs (Low Angle Grain Boundaries (LAGBs), general High Angle Grain Boundaries (HAGBs) and Σ3 HAGBs) and interfaces (M2.0-3.2C carbide-ferrite interfaces and cementite-ferrite interfaces) were quantified. There is an obvious segregation of one element or several chemical species (C, P, Mn, Mo, Cr, Si and Ni) at all boundary types. Taking into account the nature of segregants and the five-parameter GB crystallography, both interstitial and substitutional segregation behaviors were discussed. Based on a large dataset, it appears that the average P segregation levels are higher in general HAGBs or LAGBs than in other boundary types. Besides, the experimental results were compared to the predicted ones from analytical models for binary, ternary and multicomponent systems. Though with a higher predicted P segregation level, the Fe-P-C ternary model seems to better fit the experimental results in all ageing conditions.