Made available in DSpace on 2014-10-09T12:36:00Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:59:33Z (GMT). No. of bitstreams: 0 / No presente trabalho foram desenvolvidos compósitos à base de alumina, com adição de carbetos de metais de transição, NbC, TaC e TiC, como reforço. Os carbetos, na forma de partículas, foram adicionados em 1,5% em volume à matriz de alumina durante a moagem em attritor. O processamento foi realizado por moagem em attritor, secagem em rotoevaporadora e desaglomeração em peneira. A dinâmica de oxidação dos carbetos e das composições dos compósitos foi estudada para a definição de parâmetros de sinterização e processamento dos compósitos. A cinética de sinterização foi estudada por dilatometria, com taxa de 10°C/min. até 1600°C em atmosfera de ar sintético, e até 1800°C, em atmosfera de argônio, com esta etapa foi possível verificar que o NbC e o TiC dificultaram a sinterização da alumina e que o TaC auxiliou nos processos de retração. Nas amostras que foram sinterizadas em dilatômetro ao ar foram detectadas fases resultantes de fusão congruente nos compósitos Al2O3/NbC e Al2O3/TaC, foram também observadas evidências de formação de líquido no compósito com adição de TaC. Com base nesses resultados foram estudadas duas técnicas de produção das ferramentas de corte: prensagem uniaxial seguida de sinterização sem pressão e sinterização por prensagem a quente. Todas as amostras foram caracterizadas microestruturalmente e quanto às propriedades mecânicas, tendo-se determinado que as amostras produzidas por prensagem a quente possuem microestrutura mais controlada e propriedades mecânicas superiores às produzidas por sinterização sem pressão. Pelos processos estudados foi observado que os carbetos influenciam diferentemente a sinterização da alumina. De maneira geral a presença destas fases nos contornos de grãos promove alterações na microestrutura modificando o tamanho de grãos da alumina. Foi proposta a hipótese de que esse comportamento é afetado pela formação de uma camada superficial resultante da oxidação dos reforços, com isto, de acordo com os diagramas de fase é possível a formação de soluções sólidas entre alumina e Ta2O5 e Nb2O5 além da formação de fase líquida, estes mecanismos alterariam a mobilidade dos contornos de grão da alumina. Para o processamento das ferramentas de corte foi utilizada prensagem a quente, escolhido pelo critério da microestrutura e propriedades mecânicas. Os testes de usinagem foram realizados com ferramentas de corte de geometria quadrada, em peças de ferro fundido cinzento e vermicular. O tempo de vida útil da ferramenta produzida com o compósito Al2O3/ NbC foi 13% superior quando comparado à uma ferramenta cerâmica comercial no teste de usinagem de ferro fundido cinzento. / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

The magnetic properties, coercivity, Hc, and weight-specific magnetic saturation, CoM, are two important quality characteristics in cemented carbides and ceramic metals, cermets. These properties give information about grain size and binder phase content, and are influenced by the different stages in the sintering process. This master thesis aim to investigate how the magnetic properties in cemented carbides are influenced by the top temperature during sintering and how the sintering processes used for cermets can be optimized in order to gain better magnetic properties in the final products. During the first part of the project, the temperature range investigated was 1380°C–1520°C. The results indicate that Hc in cemented carbides has a strong temperature dependence, where increasing top temperature results in lower Hc. In order to have approval limits for the furnace control pieces that follow the process directives, the limits used today need to become narrower. Furthermore, the results show that CoM also has a temperature dependence, although not as strongly as Hc. During the second part of the project, already existing data of the magnetic properties in four different cermet grades were evaluated. The results indicate that the two sintering processes used in the DDK furnace are generating too high results in Hc and CoM. Optimization tests were conducted and changes implemented in order to gain better results, where the DJ1430 process now has an increased time during the solid state sintering and the DF1480 process now has an increased time during the liquid phase sintering.

A thesis submitted to the Faculty of Engineering, University of the Witwatersrand, Johannesburg, in fulfilment of the requirements for the degree of Master of Science in Engineering Johannesburg, 1993 / The formation of VC, NbC, and Cr-carbide coatings on steels immersed in molten borax baths containing carbide-forming constituents has been known for some time. A study was made of the formation of carbide coating on steel specimens treated in molten borax cont.ad.Lnr.q ferro-vanadium and V20S as bath additives. The prevalence of oxidizing or reducing conditions in the bath was found to playa decisive role in the formation of the VC layer. The influence of treatment factors such as time, temperature, and bath composition on the thickness of the coating was investigated. A detailed investigation into the behaviour of baths containing V205 and Al was carried out in this regard. Microstructural examination of coated specimens was performed using optical and electron microscopy. Microhardness tests, X-ray diffraction (XRD) and energy dispersive spectroscopy (EDS) analyses were carried out in order to characterise the layers produced. The corrosion behaviour of the vanadf.um carbide coating was evaluated by accelerated electrochemical means. Samples of mild steel and EN9(O.5% C) steel were treated for various lengths of time in order to obtain coatings of various thicknesses. The corrosion resLst.ance of the carbide coating was found to be superior to that of the untreated base alloys. Five diffet"ent tool steel materials were a.lso treated. Microscopy examination and hardness testing of the VC coated tool steels was performed in order to assess the effects of treatment by this process on the bas~ material. The austenitizing temperature and the nature of the carbides in the matrix of the tool steels was found to play an important role in this respect. / MT2017

To sustain future population and economic growth, the global energy supply is expected to increase by 60% by 2040, but the associated CO₂ emissions are a major concern. Converting CO2 into a commodity through a CO₂-neutral process has the potential to create a sustainable carbon energy economy; however, the high stability of CO₂ requires the discovery of active, selective and stable catalysts. To initially probe the performance of catalysts for CO₂ reduction, CO₂ is activated with H₂, which produces CO and CH₄ as the primary products. For this study, CO is desired for its ability to be used in the Fischer-Tropsch process, while CH₄ is undesired because of its low volumetric energy density and abundance. Precious bimetallic catalysts synthesized on a reducible support (CeO₂) show higher activity than on an irreducible support (γ-Al₂O₃) and the selectivity, represented as CO:CH₄ ratio, is correlated to electronic properties of the supported catalysts with the surface d-band center value of the metal component. Because the high cost of precious metals is unsuitable for a large-scale CO₂ conversion process, further catalyst development for CO₂ reduction focuses on active, selective and low-cost materials. Molybdenum carbide (Mo₂C) outperforms precious bimetallic catalysts and is highly active and selective for CO₂ conversion to CO. These results are further extended to other transition metal carbides (TMCs), which are found to be a class of promising catalysts and their activity is correlated with oxygen binding energy (OBE) and reducibility as shown by density functional theory (DFT) calculations and in-situ measurements. Because TMCs are made from much more abundant elements than precious metals, the catalysts can be manufactured at a much lower cost, which is critical for achieving a substantial reduction of CO₂ levels. In the aforementioned examples, sustainable CO₂ reduction requires renewable H₂, 95% of which is currently produced from hydrocarbon based-feedstocks, resulting in CO₂ emissions as a byproduct. Alternatively, CO₂ can be reduced with ethane from shale gas, which produces either synthesis gas (CO + H₂) or ethylene with high selectivity. Pt/CeO₂ is a promising catalyst to produce synthesis gas, while Mo₂C based materials preserve the C-C bond of ethane to produce ethylene. Ethylene and higher olefins are desirable for their high demand as commodity chemicals; therefore, future studies into CO₂ reduction must identify new low-cost materials that are active and stable with higher selectivity toward the production of light olefins.

Lo, Kwok Cheung. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2009. / Includes bibliographical references (leaves 114-118). / Abstracts in English and Chinese. / Thesis / Assessment Committee --- p.ii / ABSTRACT --- p.iii / ACKNOWLEDGEMENTS --- p.v / TABLE OF CONTENT --- p.vi / Chapter Chapter 1 --- Introduction --- p.1 / Chapter Chapter 2 --- Theoretical Background --- p.5 / Chapter Chapter 3 --- Results --- p.38 / Chapter Chapter 4 --- Discussion and Concluding Remarks --- p.85 / LIST OF TABLES / Table / Table la Electronic energies and geometrical parameters of scandium dicarbide by B3LYP/LANL2DZ and B3LYP/LANL2DZ-d --- p.41 / Table lb Comparison of literature results with current computational results of cyclic scandium dicarbide at equilibrium state by B3LYP/LANL2DZ and B3LYP/LANL2DZ-d --- p.42 / Table lc Comparison of literature results with current computational results of linear scandium dicarbide at equilibrium state by B3LYP/LANL2DZ and B3LYP/LANL2DZ-d --- p.43 / Table 2a Electronic energies and geometrical parameters of titanium --- p.46

The design and development of nanoparticles is of great interest in the current energy and electronic industry. However, based on the current materials available the production cost can be high with insignificant magnetic and mechanical properties. Specifically, rare-earth magnetic materials composed of neodymium and samarium are known for their high magnetic performance, however, due to the cost of development there is a need to develop a versatile and cost effective material. Alternatively, cobalt carbide nanomaterials have shown to be a promising alternative for rare-earth free magnets as they exhibit comparable properties as hexaferrite magnetic materials. The primary goal of this dissertation focuses on the development of nanoparticles for permeant magnetic, and magnetic refrigeration applications. The first part of this work focuses on the synthesis of cobalt carbide (CoxC, x=2,3) nanoparticles using a novel polyol synthesis method by introducing a small amount of Ru, Cu, or Au as nucleating agent. It was found that the morphology and magnetic properties of the as-synthesized CoxC nanoparticles change as a result of directional growth of nanoparticles using nucleating agents. Needle-like particle morphology ranges from 20-50 nm in width and as long as 1 µm in length were synthesized using Ru as nucleating agent. These particles exhibit magnetization saturation of 33.5 emu/g with a coercivity of 2870 Oe and a maximum energy product 1.92 MGOe (BHmax) observed. Particle morphology is a critical aspect in the development of magnetic nanoparticles as anisotropic particles have shown increased coercivity and magnetic properties. These CoxC nanomaterials have a higher maximum energy product compared to previous work providing further insight into the development of non-rare earth magnetic material. The second part of this dissertation work focuses on the sol-gel synthesis of perovskite LaCaMnO3 (LCMO) nanomaterials. In this process, various chain lengths of polyethylene glycol (PEG) was added into a solution consisting of La, Ca, and Mn salts. The solution was left for the gelation process, and high temperature sintering to obtain the final product. By varying the polymer chain of the PEG, the size of the as synthesized LaCaMnO3 nanomaterials were altered. The as-synthesized LCMO nanomaterials have shown a maximum change in magnetic entropy (-ΔSM) was found to be 19.3 Jkg-1K-1 at 278 K for a field change of 0-3 T and 8.7 Jkg-1K-1 for a field change of 0-1 T. This is a significant improvement in comparison to current literature of the material suggesting that this is a promising alternative to Gd materials that is prone to oxidation. With additional development, LCMO or related maganites could lead to application in commercial technologies.

Iron-based alloys containing 15% chromium, 2-3% molybdenum and 0.02-1.7% carbon, consisting of M23C6 and M6C carbides in an austenitic matrix were oxidised at 8500C to study their oxidation resistance and a precipitate-free zone formation. Alloy design was carried out using a thermodynamic software Thermo-Calc. Carbides in these alloys were expected to dissolve during oxidation, releasing chromium required for the protective oxide formation. Decarburisation of the matrix was expected to trigger the carbide dissolution, and form a precipitate-free zone. Transformation of the austenitic into ferritic matrix in the precipitate-free zone was expected be essential for providing a fast chromium supply to the oxide/alloy interface. Upon exposure to pure oxygen, most of the alloys oxidised non-protectively due to the fast oxidation attack and low chromium content in the matrix, while carbide dissolution was too slow. The alloys were then pre-oxidised in H2+10%H2O to grow a purely chromia scale. In this low oxygen partial pressure environment, carbides in the alloy's sub-surface dissolved and formed a ferritic precipitate-free zone. The precipitate dissolution model developed by previous investigators was then tested and proven to be valid in this iron-based alloy system. The endurance of the pre-formed chromia scale with its underlying precipitate-free zone was then tested in pure oxygen environment. All of the alloys that had successfully developed a ferritic precipitate-free zone in the pre-oxidation stage, survived the subsequent oxidation in pure oxygen up until 3 weeks observation. Although x-ray diffraction found some minor iron oxides, the oxide consisted of mainly Cr2O3. Since iron activity had increased and iron oxides had become stable after the pure oxygen gas was introduced, the growth of the precipitate-free zone had to compete with the rate at which it was consumed by oxidation. It was concluded that the transformation from austenite to ferrite at the subsurface region of the alloy could be achieved provided that the volume fraction of the carbides did not exceed 0.2. Evidence indicated that the chromia scale grew by chromium provided by the dissolving carbides. Pre-oxidation led to a promising use of the alloys at atmospheric oxygen pressure.

Thesis (Ph.D.)--University of Delaware, 2006. / Principal faculty advisor: Jingguang G. Chen, Dept. of Chemical Engineering. Includes bibliographical references.

Cemented carbides based on tungsten carbide and cobalt arecommonly produced by a powder metallurgy route including liquidphase sintering. The pressed compact densifies to almost halfits volume during sintering due to pore elimination. Thesintering behaviour changes with material composition, such ascarbide grain size, binder fraction, carbon content andaddition of cubic carbides. This thesis is devoted to the study of constitutivebehaviour, in particular densification, and the microstructuralevolution during cemented carbide sintering. Dimensionalchanges are monitored using dilatometry with and withoutapplied external load. The microstructural evolution isinvestigated with light optical microscopy and scanningelectron microscopy. Thermodynamic calculations are used asreference. Constitutive relations are derived for uniaxial viscosity,viscous equivalent of Poisson’s ratio and sintering stressbased on relative density and temperature. The relations areextended to a model describing sintering shrinkage withexplicit dependencies on carbide grain size and binder content.The model is divided in three stages of which two pertain tothe solid state and the third to liquid phase sintering. Solidstate shrinkage is suppressed in a material with coarsecarbides and in the stage of liquid phase sintering grain sizestrongly influences the uniaxial viscosity. The binder contentaffects primarily the later densification. The effects of carbon content and grain size distribution onshrinkage have been studied. High carbon content enhancesshrinkage rate, but the effect of grain size distribution israther small. The mean carbide grain size is insufficient todescribe densification for very broad distributions only. Shrinkage occurs through rearrangement andsolution-reprecipitation. Rearrangement is studied through theevolution of the pore size distribution and simulatedgenerically using a discrete element method. Keywords:Cemented carbides, Sintering, Constitutiverelations, Microstructure, Densification, Modelling

The aim of this thesis work was to design and evaluate a wear test method for cemented carbides inserts used in rotary drilling. An appropriate in-house wear test method would provide a better understanding of the wear mechanisms limiting tool life in real drilling. The test method should be easy to use and be able to distinguish between wear of insert materials with different microstructure and properties. The literature study showed few published articles about wear tests and mechanisms concerning rotary drill bit inserts. These methods included two standard wear tests; ASTM G65 and ASTM B611. Furthermore, a modified ASTM G65 test was found as well as an impact-abrasion test. In this work the modified ASTM G65 test, using a rock counter surface, was evaluated in order to understand if the method would mimic the wear of cemented carbides used in rotary drilling. The test method was further developed and showed high repeatability. Measured weight losses showed that the test could distinguish between two common rotary grade materials with a small difference in hardness but with different microstructures. The wear of the tested materials was analyzed with scanning electron microscopy and compared with rotary drill bit inserts collected from the field. The modified test method proved able to produce wear by mechanisms very similar to those found on field worn inserts. Identified wear mechanisms included cracking, fragmentation and spalling of WC grains as well as embedded fragments of WC grains on the surface. In addition, the binder phase was removed and adhered material from the counter surface was detected.