L'enginyeria de les propietats plasmòniques de les nanoestructures metàl·liques requereix un control acurat de les seves formes i distribució. Això normalment s'aconsegueix amb l'ús de la litografia per feix d'electrons sobre polímers electro-sensibles combinat amb la deposició de capes fines de metall i el lift-off. La deposició directa i localitzada de metalls induïda per un feix d'electrons (FEBID per Focused Electron Beam Induced Deposition) és un mètode alternatiu querecentment ha rebut un interès creixent en microelectrònica però encara no ha despertat massa atenció dins la comunitat d'òptica. L'FEBID és el resultat de la descomposició local, per un feixd'electrons focalitzat, de les molècules d'un precursor adsorbides sobre una superfície. Aquesta s'ha aplicat majoritàriament en la escriptura directa de contactes o per a la reparació de circuits, però amb l'ús de metalls nobles podria aprofitar-se per a l'òptica de plasmons.En aquesta tesi es demostra l'ús de l'FEBID per a fabricar nanoestructures d'or per a aplicacions d'òptica de plasmons. S'investiguen els efectes del material del substrat i dels paràmetres de deposició, com ara el corrent del feix i la pressió de vapor d'aigua, sobre el ritme de creixement i la puresa de l'or. S'ha emprat un recuit ex situ de la mostra com a mètode de millora de la puresa. Les mesures òptiques de dispersió sobre les estructures purificades evidencien que suporten plasmons de superfície localitzats. Aquest mètode de fabricació permet el creixement d'estructures plasmòniques amb una elevada relació d'aspecte i ha de facilitar l'escriptura en superfícies no planes com l'extremitat d'una sonda de rastreig allargada. / La ingeniería de las propiedades plasmónicas de las nanoestructuras metálicas requiere un control preciso de sus formas y distribución. Esto normalmente se consigue con el uso de la litografía por haz de electrones sobre polímeros electro-sensibles combinado con la deposición de capas finas de metal y el lift-off. La deposición directa y localizada de metales inducida por un haz de electrones (FEBID por Focused Electron Beam Induced Deposition) es un método alternativo que recientemente ha despertado un interés creciente en microelectrónica pero todavía no ha recibido demasiada atención dentro de la comunidad de óptica. La FEBID es el resultado de la descomposición local, por un haz de electrones focalizado, de las moléculas de un precursor adsorbidas sobre una superficie. Esta se ha aplicado mayoritariamente en la escritura directa de contactos o para la reparación de circuitos, pero con el uso de metales nobles podría ser aprovechada para la óptica de plasmones.En esta tesis se demuestra el uso de la FEBID para fabricar nanoestructuras de oro para aplicaciones de óptica de plasmones. Se investigan los efectos del material del sustrato y de los parámetros de deposición, como la corriente del haz y la presión de vapor de agua, sobre el ritmo de crecimiento y la pureza del oro. Se ha utilizado un recocido ex situ de la muestracomo método de mejora de la pureza. Las medidas ópticas de dispersión sobre las estructuras purificadas evidencian que soportan plasmones de superficie localizados. Este método de fabricación permite el crecimiento de estructuras plasmónicas con una elevada relación de aspecto y tiene que facilitar la escritura en superficies no planas como la extremidad de una sonda de rastreo alargada. / Engineering the plasmon properties of metal nanostructures requires an accurate control on their shapes and distribution. This is conventionally achieved by using electron-beam lithography on electro-sensitive polymers combined with thin-metal-film deposition and lift-off. Direct local deposition of metals induced by a focused electron beam (FEBID for Focused ElectronBeam Induced Deposition) is an alternative method that has been receiving a growing interest in microelectronics but it has not yet received much attention in the optical community. The FEBID is the result of the local decomposition, by a focused electron beam, of precursor molecules adsorbed on a surface. It has mostly been applied to direct-contact writing or to circuit reparation, but can be applied advantageously to plasmon optics when involving noble metals.In this thesis the use of the FEBID to fabricate gold nanostructures for plasmon optics applications is demonstrated. The effects of the substrate material and the deposition parameters, such as beam current and water vapor pressure, on both the deposition rate and the gold purity are investigated. Ex-situ annealing of the sample is used as a purity improvement method. Scattering optical measurements on the purified structures evidence that they support localized surface plasmon resonances. This fabrication method enables to grow high aspect ratio plasmonic structures and to render much easier nano-patterning on non-flat surfaces such as the extremity of an elongated scanning probe.

<p>Duplex stainless steels are a very attractive alternative to austenitic grades due to their higher strength and good corrosion performance. The austenitic grades can often be welded autogenously, while the duplex grades normally require addition of filler metal. This is to counteract segregation of important alloying elements and to give sufficient austenite formation to prevent precipitation of chromium nitrides that could have a negative effect on impact toughness and pitting resistance. The corrosion performance of the recently-developed lean duplex stainless steel LDX 2101 is higher than that of 304 and can reach the level of 316. This thesis summarises pitting resistance tests performed on laser and gas tungsten arc (GTA) welded LDX 2101. It is shown here that this material can be autogenously welded, but additions of filler metal, nitrogen in the shielding gas and use of hybrid methods increases the austenite formation and the pitting resistance by further suppressing formation of chromium nitride precipitates in the weld metal. If the weld metal austenite formation is sufficient, the chromium nitride precipitates in the heat-affected zone (HAZ) could cause local pitting, however, this was not seen in this work. Instead, pitting occurred 1–3 mm from the fusion line, in the parent metal rather than in the high temperature HAZ (HTHAZ). This is suggested here to be controlled by the heat tint, and the effect of residual weld oxides on the pitting resistance is studied. The composition and the thickness of weld oxide formed on LDX 2101 and 2304 were determined using X-ray photoelectron spectroscopy (XPS). The heat tint on these lean duplex grades proved to contain significantly more manganese than what has been reported for standard austenitic stainless steels in the 300 series. A new approach on heat tint formation is consequently presented. Evaporation of material from the weld metal and subsequent deposition on the weld oxide are suggested to contribute to weld oxide formation. This is supported by element loss in LDX 2101 weld metal, and nitrogen additions to the GTA shielding gas further increase the evaporation.</p><p> </p>

The present dissertation reports the findings of a study of cracking behavior of a newly developed superalloy, Allvac 718Plus during high power beam welding and post-weld heat treatment. Microstructures of the base alloy, heat affected zone (HAZ) and fusion zone (FZ) of welded and post-weld heat treated (PWHT) coupons were examined by the use of standard metallographic techniques involving optical microscopy, analytical scanning electron microscopy (SEM) and analytical transmission electron microscopy. Moreover, grain boundary segregation behavior of boron atoms during pre-weld heat treatments was evaluated using secondary ion mass spectroscopic system. In the first phase of the research, 718Plus was welded using a low and high heat input CO2 laser to assess its weld cracking response. Detailed examination of the welds by analytical electron microscopic technique revealed the occurrence of cracking in the HAZ of low heat input welds, while their FZ was crack free. However, both the FZ and HAZ of high heat input welds were crack-free. Resolidified constituents were observed along the cracked grain boundaries of the lower heat input welds, which indicated that HAZ cracking in this newly developed superalloy was associated with grain boundary liquation. However, despite a more extensive liquation of grain boundaries and grain interior in the HAZ of high heat input welds, no cracking occurred. This was attributed to the combination of lower welding stresses generated during cooling, and relaxation of these stresses by thick intergranular liquid. Although HAZ cracking was prevented by welding with a high heat input laser, it resulted in a significant damage to the parent microstructure through its extensive liquation. Thus, the use of low heat input welding is desirable. However, this resulted in HAZ cracking which needs to be minimized or eliminated. Therefore, during the second phase of this research, the effects of pre-weld thermal processing on the cracking response of 718Plus were investigated. Results from the quantification of the cracking of the alloy showed that HAZ cracking may be significantly reduced or eliminated through an adequate selection of pre-weld thermal cycle. In the third stage of this research, crack-free welds of 718Plus were post-weld heat treated using standard thermal schedules. A significant solid state cracking of the alloy occurred during the PWHT. The cracking was attributed to the presence of embrittling phases on HAZ grain boundaries, coupled with aging contraction stresses that are generated by a considerable precipitation of gamma prime phase during aging.

The present dissertation reports the findings of a study of cracking behavior of a newly developed superalloy, Allvac 718Plus during high power beam welding and post-weld heat treatment. Microstructures of the base alloy, heat affected zone (HAZ) and fusion zone (FZ) of welded and post-weld heat treated (PWHT) coupons were examined by the use of standard metallographic techniques involving optical microscopy, analytical scanning electron microscopy (SEM) and analytical transmission electron microscopy. Moreover, grain boundary segregation behavior of boron atoms during pre-weld heat treatments was evaluated using secondary ion mass spectroscopic system. In the first phase of the research, 718Plus was welded using a low and high heat input CO2 laser to assess its weld cracking response. Detailed examination of the welds by analytical electron microscopic technique revealed the occurrence of cracking in the HAZ of low heat input welds, while their FZ was crack free. However, both the FZ and HAZ of high heat input welds were crack-free. Resolidified constituents were observed along the cracked grain boundaries of the lower heat input welds, which indicated that HAZ cracking in this newly developed superalloy was associated with grain boundary liquation. However, despite a more extensive liquation of grain boundaries and grain interior in the HAZ of high heat input welds, no cracking occurred. This was attributed to the combination of lower welding stresses generated during cooling, and relaxation of these stresses by thick intergranular liquid. Although HAZ cracking was prevented by welding with a high heat input laser, it resulted in a significant damage to the parent microstructure through its extensive liquation. Thus, the use of low heat input welding is desirable. However, this resulted in HAZ cracking which needs to be minimized or eliminated. Therefore, during the second phase of this research, the effects of pre-weld thermal processing on the cracking response of 718Plus were investigated. Results from the quantification of the cracking of the alloy showed that HAZ cracking may be significantly reduced or eliminated through an adequate selection of pre-weld thermal cycle. In the third stage of this research, crack-free welds of 718Plus were post-weld heat treated using standard thermal schedules. A significant solid state cracking of the alloy occurred during the PWHT. The cracking was attributed to the presence of embrittling phases on HAZ grain boundaries, coupled with aging contraction stresses that are generated by a considerable precipitation of gamma prime phase during aging.

Duplex stainless steels are a very attractive alternative to austenitic grades due to their higher strength and good corrosion performance. The austenitic grades can often be welded autogenously, while the duplex grades normally require addition of filler metal. This is to counteract segregation of important alloying elements and to give sufficient austenite formation to prevent precipitation of chromium nitrides that could have a negative effect on impact toughness and pitting resistance. The corrosion performance of the recently-developed lean duplex stainless steel LDX 2101 is higher than that of 304 and can reach the level of 316. This thesis summarises pitting resistance tests performed on laser and gas tungsten arc (GTA) welded LDX 2101. It is shown here that this material can be autogenously welded, but additions of filler metal, nitrogen in the shielding gas and use of hybrid methods increases the austenite formation and the pitting resistance by further suppressing formation of chromium nitride precipitates in the weld metal. If the weld metal austenite formation is sufficient, the chromium nitride precipitates in the heat-affected zone (HAZ) could cause local pitting, however, this was not seen in this work. Instead, pitting occurred 1–3 mm from the fusion line, in the parent metal rather than in the high temperature HAZ (HTHAZ). This is suggested here to be controlled by the heat tint, and the effect of residual weld oxides on the pitting resistance is studied. The composition and the thickness of weld oxide formed on LDX 2101 and 2304 were determined using X-ray photoelectron spectroscopy (XPS). The heat tint on these lean duplex grades proved to contain significantly more manganese than what has been reported for standard austenitic stainless steels in the 300 series. A new approach on heat tint formation is consequently presented. Evaporation of material from the weld metal and subsequent deposition on the weld oxide are suggested to contribute to weld oxide formation. This is supported by element loss in LDX 2101 weld metal, and nitrogen additions to the GTA shielding gas further increase the evaporation. / QC 20101126

An effective procedure and parameter window was developed for underwater friction stir welding (UWFSW) 304L stainless steel with a PCBN tool. UWFSW produced statistically significant: increases in yield strengths, decreases in percent elongation. The ultimate tensile strength was found to be significantly higher at certain parameters. Although sigma was identified in the UWFSWs, a significant reduction of sigma was found in UWFSWs compared to ambient FSWs. The degree of sensitization in UWFSWs was evaluated using double loop EPR testing and oxalic acid electro-etched metallography. Results were compared to base metal, ambient FSW, and arc welds. Upper and lower sensitization localization bands were identified in the UWFSWs. Although higher sensitization levels were present in UWFSWs compared to the arc weld, ambient FSW, and heat treated base metals, the UWFSWs were found less susceptible to corrosion than arc welds due to the subsurface location of the sensitization bands. A SCC analysis of UWFSWs relative to base metal and arc weldments was performed. U-bends were exposed to two 3.5% NaCl cyclic immersion experiments at 21 °C and 63 °C for 1000 hours each. A tertiary test was conducted in a 25% NaCl boiling solution. The UWFSW u-bends were no more susceptible to SCC than base metal in the cyclic immersion tests. In the boiling NaCl test, the SCC of the UWFSWs showed significant improvement over the SCC of arc welds. Arc u-bends cracked entirely within the weld bead and HAZ, while SCC in the UWFSWs showed no cracking localization.