Comportamiento mecánico de nuevas aleaciones de wolframio en función de la temperatura

La presente memoria de tesis tiene como objetivo principal la caracterización mecánica en función de la temperatura de nueve aleaciones de wolframio con contenidos diferentes en titanio, vanadio, itria y lantana. Las aleaciones estudiadas son las siguientes: W-0.5%Y2O3, W-2%Ti, W-2% Ti-0.5% Y2O3, W-4% Ti-0.5% Y2O3, W-2%V, W- 2%Vmix, W-4%V, W-1%La2O3 and W-4%V-1%La2O3. Todos ellos, además del wolframio puro se fabrican mediante compresión isostática en caliente (HIP) y son suministradas por la Universidad Carlos III de Madrid. La investigación se desarrolla a través de un estudio sistemático basado en ensayos físicos y mecánicos, así como el análisis post mortem de las muestras ensayadas. Para realizar dicha caracterización mecánica se aplican diferentes ensayos mecánicos, la mayoría de ellos realizados en el intervalo de temperatura de 25 a 1000 º C. Los ensayos de caracterización que se llevan a cabo son: • Densidad • Dureza Vicker • Módulo de elasticidad y su evolución con la temperatura • Límite elástico o resistencia a la flexión máxima, y su evolución con la temperatura • Resistencia a la fractura y su comportamiento con la temperatura. • Análisis microestructural • Análisis fractográfico • Análisis de la relación microestructura-comportamiento macroscópico. El estudio comienza con una introducción acerca de los sistemas en los que estos materiales son candidatos para su aplicación, para comprender las condiciones a las que los materiales serán expuestos. En este caso, el componente que determina las condiciones es el Divertor del reactor de energía de fusión por confinamiento magnético. Parece obvio que su uso en los componentes del reactor de fusión, más exactamente como materiales de cara al plasma (Plasma Facing Components o PFC), hace que estas aleaciones trabajen bajo condiciones de irradiación de neutrones. Además, el hecho de que sean materiales nuevos hace necesario un estudio previo de las características básicas que garantice los requisitos mínimos antes de realizar un estudio más complejo. Esto constituye la principal motivación de la presente investigación. La actual crisis energética ha llevado a aunar esfuerzos en el desarrollo de nuevos materiales, técnicas y dispositivos para la aplicación en la industria de la energía nuclear. El desarrollo de las técnicas de producción de aleaciones de wolframio, con un punto de fusión muy alto, requiere el uso de precursores de sinterizado para lograr densificaciones más altas y por lo tanto mejores propiedades mecánicas. Este es el propósito de la adición de titanio y vanadio en estas aleaciones. Sin embargo, uno de los principales problemas de la utilización de wolframio como material estructural es su alta temperatura de transición dúctil-frágil. Esta temperatura es característica de materiales metálicos con estructura cúbica centrada en el cuerpo y depende de varios factores metalúrgicos. El proceso de recristalización aumenta esta temperatura de transición. Los PFC tienen temperaturas muy altas de servicio, lo que facilita la recristalización del metal. Con el fin de retrasar este proceso, se dispersan partículas insolubles en el material permitiendo temperaturas de servicio más altas. Hasta ahora se ha utilizado óxidos de torio, lantano e itrio como partículas dispersas. Para entender cómo los contenidos en algunos elementos y partículas de óxido afectan a las propiedades de wolframio se estudian las aleaciones binarias de wolframio en comparación con el wolframio puro. A su vez estas aleaciones binarias se utilizan como material de referencia para entender el comportamiento de las aleaciones ternarias. Dada la estrecha relación entre las propiedades del material, la estructura y proceso de fabricación, el estudio se completa con un análisis fractográfico y micrográfico. El análisis fractográfico puede mostrar los mecanismos que están implicados en el proceso de fractura del material. Por otro lado, el estudio micrográfico ayudará a entender este comportamiento a través de la identificación de las posibles fases presentes. La medida del tamaño de grano es una parte de la caracterización microestructural. En esta investigación, la medida del tamaño de grano se llevó a cabo por ataque químico selectivo para revelar el límite de grano en las muestras preparadas. Posteriormente las micrografías fueron sometidas a tratamiento y análisis de imágenes. El documento termina con una discusión de los resultados y la compilación de las conclusiones más importantes que se alcanzan después del estudio. Actualmente, el desarrollo de nuevos materiales para aplicación en los componentes de cara al plasma continúa. El estudio de estos materiales ayudará a completar una base de datos de características que permita hacer una selección de ellos más fiable. The main goal of this dissertation is the mechanical characterization as a function of temperature of nine tungsten alloys containing different amounts of titanium, vanadium and yttrium and lanthanum oxide. The alloys under study were the following ones: W-0.5%Y2O3, W-2%Ti, W-2% Ti-0.5% Y2O3, W-4% Ti-0.5% Y2O3, W-2%V, W- 2%Vmix, W-4%V, W-1%La2O3 and W-4%V-1%La2O3. All of them, besides pure tungsten, were manufactured using a Hot Isostatic Pressing (HIP) process and they were supplied by the Universidad Carlos III de Madrid. The research was carried out through a systematic study based on physical and mechanical tests as well as the post mortem analysis of tested samples. Diverse mechanical tests were applied to perform this characterization; most of them were conducted at temperatures in the range 25-1000 ºC. The following characterization tests were performed: • Density • Vickers hardness • Elastic modulus • Yield strength or ultimate bending strength, and their evolution with temperature • Fracture toughness and its temperature behavior • Microstructural analysis • Fractographical analysis • Microstructure-macroscopic relationship analysis This study begins with an introduction regarding the systems where these materials could be applied, in order to establish and understand their service conditions. In this case, the component that defines the conditions is the Divertor of magnetic-confinement fusion reactors. It seems obvious that their use as fusion reactor components, more exactly as plasma facing components (PFCs), makes these alloys work under conditions of neutron irradiation. In addition to this, the fact that they are novel materials demands a preliminary study of the basic characteristics which will guarantee their minimum requirements prior to a more complex study. This constitutes the motivation of the present research. The current energy crisis has driven to join forces so as to develop new materials, techniques and devices for their application in the nuclear energy industry. The development of production techniques for tungsten-based alloys, with a very high melting point, requires the use of precursors for sintering to achieve higher densifications and, accordingly, better mechanical properties. This is the purpose of the addition of titanium and vanadium to these alloys. Nevertheless, one of the main problems of using tungsten as structural material is its high ductile-brittle transition temperature. This temperature is characteristic of metallic materials with body centered cubic structure and depends on several metallurgical factors. The recrystallization process increases their transition temperature. Since PFCs have a very high service temperature, this facilitates the metal recrystallization. In order to inhibit this process, insoluble particles are dispersed in the material allowing higher service temperatures. So far, oxides of thorium, lanthanum and yttrium have been used as dispersed particles. Tungsten binary alloys are studied in comparison with pure tungsten to understand how the contents of some elements and oxide particles affect tungsten properties. In turn, these binary alloys are used as reference materials to understand the behavior of ternary alloys. Given the close relationship between the material properties, structure and manufacturing process, this research is completed with a fractographical and micrographic analysis. The fractographical analysis is aimed to show the mechanisms that are involved in the process of the material fracture. Besides, the micrographic study will help to understand this behavior through the identification of present phases. The grain size measurement is a crucial part of the microstructural characterization. In this work, the measurement of grain size was carried out by chemical selective etching to reveal the boundary grain on prepared samples. Afterwards, micrographs were subjected to both treatment and image analysis. The dissertation ends with a discussion of results and the compilation of the most important conclusions reached through this work. The development of new materials for plasma facing components application is still under study. The analysis of these materials will help to complete a database of the features that will allow a more reliable materials selection.

Effect of nano-Si2O and nano-Al2O3 on cement mortars for use in agriculture and livestock production

The effect of nano-silica, nano-alumina and binary combinations on surface hardness, resistance to abrasion and freeze-thaw cycle resistance in cement mortars was investigated. The Vickers hardness, the Los Angeles coefficient (LA) and the loss of mass in each of the freeze–thaw cycles to which the samples were subjected were measured. Four cement mortars CEM I 52.5R were prepared, one as control, and the other three with the additions: 5% nano-Si, 5% nano-Al and mix 2.5% n-Si and 2.5% n-Al. Mortars were tested at 7, 28 and 90 d of curing to determine compression strength, total porosity and pore distribution by mercury intrusion porosimetry (MIP) and the relationship between the CSH gel and Portlandite total by thermal gravimetric analysis (TGA). The capillary suction coefficient and an analysis by a scanning electron microscope (SEM) was made. There was a large increase in Vickers surface hardness for 5% n-Si mortar and a slight increase in resistance to abrasion. No significant difference was found between the mortars with nano-particles, whose LA was about 10.8, classifying them as materials with good resistance to abrasion. The microstructure shows that the addition of n-Si in mortars refines their porous matrix, increases the amount of hydrated gels and generates significant changes in both Portlandite and Ettringite. This produced a significant improvement in freeze–thaw cycle resistance. The effect of n-Al on mortar was null or negative with respect to freeze–thaw cycle resistance.

Resistência à abrasão de aço Hadfield para britadores: efeito do tamanho do abrasivo e do pH do meio.

Neste trabalho, foi investigado o efeito do tamanho do abrasivo e do pH do meio na resistência ao desgaste abrasivo do aço H-13 com matriz martensítica e do aço Hadfield com matriz austenítica. Ensaios de abrasão foram realizados utilizando o equipamento roda de borracha a úmido, variando o tamanho do abrasivo entre 0,15 e 2,40 mm e o pH do meio entre 5,5 e 12,8. As microestruturas dos materiais estudados foram analisadas utilizando microscopia óptica, as superfícies de desgaste e as partículas de desgaste foram analisadas em microscópio eletrônico de varredura. A macrodureza e a microdureza, antes e após os ensaios, foram obtidas utilizando durômetro Vickers. A topografia da região central da superfície de desgaste foi obtida utilizando Perfilometria 3D, visando obter valores de profundidade de penetração do abrasivo. Os resultados mostraram que o aço Hadfield é mais resistente do que o aço H-13 em todos os valores de pH e tamanhos de abrasivo utilizados. Para os dois materiais, a perda de massa aumenta linearmente até um tamanho crítico de abrasivo (TCA) e, após este, a mesma continua a aumentar, mas com uma intensidade menor. Para os dois materiais e para todos os tamanhos de abrasivo, o aumento do pH do meio resultou em menores perdas de massa, sendo este efeito maior para os dois menores tamanhos de abrasivo. Para maiores valores de pH, foram observadas menores profundidades de penetração do abrasivo. A microdureza da superfície de desgaste do aço H-13 sofreu um pequeno aumento com o aumento do tamanho do abrasivo enquanto que para o aço Hadfield esse aumento foi mais intenso. A análise das partículas de desgaste mostraram que, para todas as condições ensaiadas, os debris do aço H-13 tinham duas morfologias, contínuas e descontínuas enquanto que os cavacos do aço Hadfield foram sempre descontínuos. Para os dois materiais, foram observados dois micromecanismos de desgaste, sendo eles microcorte e microsulcamento. Por fim, os resultados apresentados neste trabalho sugerem que a análise de desempenho do aço Hadfield em serviço deve considerar o pH do meio bem como a granulometria do abrasivo em contato.

Estudo comparativo de utilização de SER, MIG/MAG e Friction Surfacing na reparação de braços de suspensão de VBTP-M113

Nas últimas décadas Friction Surfacing despertou bastante interesse por permitir revestir metais no estado sólido desenvolvendo-se a temperaturas inferiores às de fusão, evitando assim as afetações que dai advém. No presente trabalho existem dois blocos principais, um primeiro onde se caraterizou o material do braço de suspensão do M113, e um segundo onde se produziram revestimentos recorrendo às três técnicas de revestimento em estudo (FS, Fios Fluxados e SER), com o objetivo de se proceder ao seu estudo e comparação. No processo de caraterização do aço do braço, foram realizados diversos ensaios, dos quais se salientam os ensaios de durezas Vickers e os ensaios de faiscamento, concluindo-se que o aço que mais se assemelha com o do braço é o AISI 4140. Para a caraterização dos revestimentos foram definidos diferentes tipos de ensaios, Metalúrgicos e Mecânicos, com a finalidade principal de abranger uma ampla gama de solicitações semelhantes às que são requeridas ao componente em serviço. Nos ensaios Metalúrgicos foram avaliadas as ligações, a existência de defeitos, as ZTA e as alterações metalográficas. A avaliação das propriedades mecânicas foi obtida através de ensaios de dureza, desgaste, flexão em três pontos e Push-Pull. Da realização destes ensaios verificou-se que os revestimentos obtidos por FS apresentam melhores propriedades, tanto Metalúrgicas como Mecânicas Por fim, foi elaborada uma avaliação dos custos operacionais envolvidos na realização da reparação de um braço de suspensão, concluindo-se que FS, apesar de apresentar os revestimentos com melhores propriedades, é ainda uma tecnologia pouco viável economicamente, fato que se deve á baixa eficiência apresentada.

Depth of cure and surface microhardness of composite resin cured with blue LED curing lights

Objectives. This study examined the depth of cure and surface microhardness of Filtek Z250 composite resin (3M-Espe) (shades B1, A3, and C4) when cured with three commercially available tight emitting diode (LED) curing lights [E-light (GC), Elipar Freelight (3M-ESPE), 475H (RF Lab Systems)], compared with a high intensity quartz tungsten halogen (HQTH) light (Kerr Demetron Optilux 501) and a conventional quartz tungsten halogen (QTH) lamp (Sirona S1 dental unit). Methods. The effects of light source and resin shade were evaluated as independent variables. Depth of cure after 40 s of exposure was determined using the ISO 4049:2000 method, and Vickers hardness determined at 1.0 mm intervals. Results. HQTH and QTH lamps gave the greatest depth of cure. The three LED lights showed similar performances across all parameters, and each unit exceeded the ISO standard for depth of cure except GC ELight for shade B1. In terms of shade, LED lights gave greater curing depths with A3 shade, while QTH and HQTH tights gave greater curing depths with C4 shade. Hardness at the resin surface was not significantly different between LED and conventional curing lights, however, below the surface, hardness reduced more rapidly for the LED lights, especially at depths beyond 3 mm. Significance. Since the performance of the three LED lights meets the ISO standard for depth of cure, these systems appear suitable for routine clinical application for resin curing. (C) 2003 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Erosive effects of common beverages on extracted premolar teeth

Background: Dental erosion is highly prevalent today, and acidic drinks are thought to be an important cause. The aim of the present investigation was to determine the erosive potential of a range of common beverages on extracted human teeth. Methods: The beverages were tested for their individual pHs using a pH meter. The clinical effects of the most erosive beverages were determined by the degree of etching and Vickers microhardness of enamel. Results: The results showed that many common beverages have pHs sufficiently low to cause enamel erosion. Lime juice concentrate (pH 2.1) had the lowest pH, followed by Coca-cola and Pepsi (both with pH 2.3) and Lucozade (pH 2.5). The erosive potential of these beverages was demonstrated by the deep etching of the enamel after five minutes. The Vickers Hardness of enamel was reduced by about 50 per cent is the case of lime juice (p < 0.001) and 24 per cent in the case of Coca-cola (p < 0.004). Addition of saliva to 50 per cent (v/v) of Coca-cola completely reversed the erosive effects on the enamel. Conclusion: Although only a few of the beverages with the lowest pHs were tested, the present study showed that the most acidic drinks had the greatest erosive effects on enamel. While saliva was protective against erosion, relatively large volumes were required to neutralize the acidity.

Section thickness, macrohardness and yield strength in high-pressure diecast magnesium alloy AZ91

The yield strength of high-pressure diecast (hpdc) test bars of alloy AZ91 increases with decreasing section thickness while its hardness remains approximately constant. This behaviour is in contrast with that of the gravity cast alloy, whose hardness scales with the yield strength. Vickers hardness measured on the surface of hpdc test bars using increasing loads shows that the subsurface porosity layer usually found in hpdc material may gradually collapse under the indent, lowering the hardness. However, this is insufficient to explain the lack of correlation between hardness and yield strength. It is argued that the low strain-hardening rate of high-pressure diecast material leads to lower than expected hardness values. In addition, it is shown that the plastic zone under a macro indentation is largely contained by the softer core of the castings, rendering hardness insensitive to the casting thickness. It is concluded that macrohardness is too coarse a tool for a meaningful determination of the strength of hpdc material. (c) 2005 Elsevier B.V. All rights reserved.

Structure and thermal properties of yttrium alumino-phosphate glasses

The structure and thermal properties of yttrium alumino-phosphate glasses, of nominal composition (Y2O3)(0.31-z)(Al2O3)(z)(P2O5)(0.69) with 0 less than or similar to z less than or similar to 0.31, were studied by using a combination of neutron diffraction, Al-27 and P-31 magic angle spinning nuclear magnetic resonance, differential scanning calorimetry and thermal gravimetric analysis methods. The Vickers hardness of the glasses was also measured. The data are compared to those obtained for pseudo-binary Al2O3-P2O5 glasses and the structure of all these materials is rationalized in terms of a generic model for vitreous phosphate materials in which Y3+ and Al3+ act as modifying cations that bind only to the terminal (non-bridging) oxygen atoms of PO4 tetrahedra. The results are used to help elucidate the phenomenon of rare-earth clustering in phosphate glasses which can be reduced by substituting Al3+ ions for rare-earth R3+ ions at fixed modifier content.

In vitro effects of erosive challenge on the surface properties of sealants

Aim: To assess in vitro the surface roughness (Ra), Vickers hardness (VHN) and surface morphology of resin and glass ionomer materials used for sealants after dynamic erosive challenge. Methods: Twenty specimens of each material were prepared and divided into experimental (erosive challenge) and control groups (n=10): Protect Riva (SDI), Opallis Flow (3M ESPE), Fluroshield (Dentsply), Filtek Z350 XT Flow (3M ESPE). The erosive challenge was performed 4 times per day (90 s) in cola drink and for 2 h in artificial saliva for 7 days. The control specimens were maintained in artificial saliva. Ra and VHN readings were performed before and after erosion. The percentage of hardness loss (%VHN) was obtained after erosion. The surface morphology was evaluated by scanning electron microscopy (SEM). The data were analyzed by ANOVA, Tukey and paired t tests (α=0.05). Results: After erosion and saliva immersion, there was an increase in Ra values for all groups and Riva group showed the highest Ra values. After erosive challenge, Riva and Filtek groups showed significant decrease in VHN values, but Filtek group showed the greatest %VHN. For all groups there was inorganic particle protrusion and matrix degradation after erosion visualized by SEM images. Conclusions: Erosive challenge affected the surface properties of all materials used as sealants, particularly in the Riva and Filtek groups.

Estudo termo-mecânico de interconector metálico recoberto com filme de La0,8Ca0,2CrO3 e de interconector cerâmico de La0,8Sr0,2Cr0,92Co0,08O3 para PaCOS

Doped lanthanum chromite ( LaCrO3 ) has been the most common material used as interconnect in solid oxide fuel cells for high temperature ( SOFC-HT ) that enabling the stack of SOFCs. The reduction of the operating temperature, to around 800 º C, of solid oxide fuel cells enabled the use of metallic interconnects as an alternative to ceramic LaCrO3, From the practical point of view, to be a strong candidate for interconnect the material must have good physical and mechanical properties such as resistance to oxidizing and reducing environments, easy manufacture and appropriate thermo-mechanical properties. Thus, a study on the physic-mechanical interconnects La0,8Sr0,2Cr0,92Co0,08O3 ceramics for SOFC -AT obtained by the method of combustion , as well as thermo-mechanical properties of metallic interconnects (AISI 444) covered with La0,8Ca0,2CrO3 by deposition technique by spray-pyrolysis fuel cells for intermediate temperature (IT-SOFCs). The La0,8Sr0,2Cr0,92Co0,08O3 was characterized by X -ray diffraction(XRD) , density and porosity , Vickers hardness (HV) , the flexural strength at room temperature and 900 °C and scanning electron microscopy (SEM). The X -ray diffraction confirmed the phase formation and LaCrO3 and CoCr2O4, in order 6 GPa hardness and mechanical strength at room temperature was 62 MPa ceramic Interconnector. The coated metal interconnects La0,8Ca0,2CrO3 passed the identification by XRD after deposition of the film after the oxidation test. The oxidative behavior showed increased resistance to oxidation of the metal substrate covered by La0,8Ca0,2CrO3 In flexural strength of the coated metal substrate, it was noticed only in the increased room temperature. The a SEM analysis proved the formation of Cr2O3 and (Cr,Mn)3O4 layers on metal substrate and confirmed the stability of the ceramic La0,8 Ca0,2CrO3 film after oxidative test

Surface roughness and hardness of a composite resin: influence of finishing and polishing and immersion methods

This study evaluated the finishing and polishing effect on the surface roughness and hardness of the Filtek Supreme XT, in fluoride solutions. Specimens were prepared (n = 140) with half of the samples finished and polished with Super-Snap (R) disks. The experimental groups were divided according to the presence or absence of finishing and polishing and immersion solutions (artificial saliva, sodium fluoride solution at 0.05%-manipulated, Fluordent Reach, Oral B, Fluorgard). The specimens remained immersed in artificial saliva for 24 hours and were then subjected to initial analysis (baseline) of surface roughness and Vickers microhardness. Next, they were immersed in different fluoride solutions for 1 min/day, for 60 days. Afterwards, a new surface roughness and microhardness reading was conducted. The data were submitted to a two-way ANOVA and Tukey's test (5% significance level). For the comparison of mean roughness and hardness at baseline and after 60 days, the paired Student t test was used. The results showed that the surface roughness and microhardness of the Filtek Supreme XT were influenced by the finishing and polishing procedure, independently of the immersion methods.