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Couplages entre précipitation et plasticité dans un alliage d'aluminium 7xxx : application à des traitements thermomécaniques de réduction des distorsions dans des composants aéronautiquesFribourg, Guillaume 20 May 2009 (has links) (PDF)
Les alliages d'aluminium de la série 7xxx sont des alliages à durcissement structural, principalement utilisés dans des applications aéronautiques en raison de leurs propriétés mécaniques spécifiques élevées. Le composant principal de leur résistance mécanique est leur microstructure de précipitation, obtenue par le biais de traitements thermomécaniques complexes. Ceux-ci induisent cependant des contraintes internes à longue distance, susceptibles de générer des distorsions sévères dans les pièces aéronautiques. Certains traitements thermomécaniques comme le grenaillage (shot peening), le formage laser (laser forming) et le formage revenu (age-forming), des procédés respectivement purement mécanique, purement thermique et thermomécanique, permettent de réduire les distorsions de pièces usinées. Ils modifient cependant la microstructure, et, par conséquent, les propriétés mécaniques. La présente étude, portant sur les couplages entre ces traitements thermomécaniques, la microstructure et les propriétés mécaniques d'un alliage 7xxx, comprend un travail de caractérisation expérimentale et de modélisation à base physique. L'effet de la précipitation sur l'écrouissage du matériau est ainsi examiné, et un modèle d'écrouissage destiné à être implémenté dans un modèle éléments finis de simulation du grenaillage est proposé. L'étude du formage laser aboutit quant à elle à un modèle prédictif de l'état de précipitation et des propriétés mécaniques locales induits par ce procédé. La dernière partie est consacrée à l'étude de l'effet du formage revenu – procédé combinant déformation plastique et traitement thermique simultanés – sur la précipitation.
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The Influence of Adjacent Segment on the Reliability of Cu Dual Damascene InterconnectsChang, Choon Wai, Choi, Z.-S., Thompson, Carl V., Gan, C.L., Pey, Kin Leong, Choi, Wee Kiong, Hwang, N. 01 1900 (has links)
Three terminal âdotted-I’ interconnect structures, with vias at both ends and an additional via in the middle, were tested under various test conditions. Mortalities (failures) were found in right segments with jL value as low as 1250 A/cm, and the mortality of a dotted-I segment is dependent on the direction and magnitude of the current in the adjacent segment. Some mortalities were also found in the right segments under a test condition where no failure was expected. Cu extrusion along the delaminated Cu/Si₃N₄ interface near the central via region was believed to cause the unexpected failures. From the time-to-failure (TTF), it is possible to quantify the Cu/Si₃N₄ interfacial strength and bonding energy. Hence, the demonstrated test methodology can be used to investigate the integrity of the Cu dual damascene processes. As conventionally determined critical jL values in two-terminal via-terminated lines cannot be directly applied to interconnects with branched segments, this also serves as a good methodology to identify the critical effective jL values for immortality. / Singapore-MIT Alliance (SMA)
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Fate of Cu, Cr, As and some other trace elements during combustion of recovered waste fuelsLundholm, Karin January 2007 (has links)
The increased use of biomass and recovered waste fuels in favor of fossil fuels for heat and power production is an important step towards a sustainable future. Combustion of waste fuels also offers several advantages over traditional landfilling, such as substantial volume reduction, detoxification of pathological wastes, and reduction of toxic leaches and greenhouse gas (methane) formation from landfills. However, combustion of recovered waste fuels emits more harmful trace elements than combustion of other fuels. These elements are distributed between bottom ash, fly ash and flue gas, depending on the elements partitioning and enrichment behavior. Volatilized harmful trace elements are mainly enriched in the submicron fly ash fraction. If emitted to the atmosphere, submicron particles can penetrate deep into the alveoli of the lungs, causing severe impacts on human health. Consequently, to reduce ash related problems and to control the emissions to the atmosphere, there is an increased need for understanding the physicochemical processes involved in ash transformation, including particle formation. The objective of this thesis was to carefully and systematically study the fate of trace elements during combustion, i.e. the chemical form of the elements and the partitioning behavior, by means of chemical equilibrium model calculations, X-ray diffraction, microscopy techniques and various spectroscopy methods. The influence of some fuel additives was also analyzed. Primarily, the elements copper, chromium and arsenic were studied. An initial review and evaluation of the content of thermodynamical data in commercial thermochemical databases used for chemical equilibrium model calculations showed that there was a significant difference in number of included phases and species between databases. Thermodynamical data also differed between databases, although in general less for condensed phases than for gaseous species. A state-of-the-art database for Cu, Cr and As was compiled and used for further chemical equilibrium model calculations. The fate of Cu, Cr and As was determined in combustion experiments on wood impregnated with copper, chromium and arsenic (CCA) in a bench scale reactor (15 kW). The results showed that global chemical equilibrium model calculations predicted the overall fate of Cu, Cr and As in bottom ash and ash particles quite well. However, compared to the experimental results the global model overpredicted the formation of refractory calcium arsenates, thus the arsenic volatilization was found to be higher then the predicted volatilization. In terms of chromium volatility, copper was found to be an important refractory element forming stable CuCrO2(s) and CuCr2O4(s) that suppressed the formation of CrO2(OH)2(g). The retention and speciation of Cu, Cr and As in bottom ash was further determined from combustion experiments of CCA wood fuel particles in a single particle reactor. Local chemical equilibrium model calculations were performed to simulate the combustion stages of a burning CCA treated wood fuel particle: drying, devolatilization, char burning and post-combustion. The results from the work showed that a mix of global and local chemical equilibrium model calculations is needed to describe the reality and that the combustion stages are partially overlapping. The fate of harmful trace elements, including Cu, Cr and As, was finally studied in full scale (65 MW) combustion experiments. Particles from the raw flue gas emissions were sampled and analyzed. The comparison with chemical equilibrium model calculations showed that the model explained the results well, but due to lack of thermodynamic data for K2ZnCl4(s), the formation of this phase could not be predicted.
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Environmental assessment of incinerator residue utilisationToller, Susanna January 2008 (has links)
In Sweden, utilisation of incinerator residues outside disposal areas is restricted by environmental concerns, as such residues commonly contain greater amounts of potentially toxic trace elements than the natural materials they replace. On the other hand, utilisation can also provide environmental benefits by decreasing the need for landfill and reducing raw material extraction. This thesis provides increased knowledge and proposes better approaches for environmental assessment of incinerator residue utilisation, particularly bottom ash from municipal solid waste incineration (MSWI).A life cycle assessment (LCA) based approach was outlined for environmental assessment of incinerator residue utilisation, in which leaching of trace elements as well as other emissions to air and water and the use of resources were regarded as constituting the potential environmental impact from the system studied. Case studies were performed for i) road construction with or without MSWI bottom ash, ii) three management scenarios for MSWI bottom ash and iii) three management scenarios for wood ash. Different types of potential environmental impact predominated in the activities of the system and the scenarios differed in use of resources and energy. Utilising MSWI bottom ash in road construction and recycling of wood ash on forest land saved more natural resources and energy than when these materials were managed according to the other scenarios investigated, including dumping in landfill. There is a potential for trace element leaching regardless of how the ash is managed.Trace element leaching, particularly of copper (Cu), was identified as being relatively important for environmental assessment of MSWI bottom ash utilisation. CuO is suggested as the most important type of Cu-containing mineral in weathered MSWI bottom ash, whereas in the leachate Cu is mainly present in complexes with dissolved organic matter (DOM). The hydrophilic components of the DOM were more important for Cu binding than previously understood. Differences were also observed between MSWI bottom ash DOM and the natural DOM for which the geochemical speciation models SHM and NICA-Donnan are calibrated. Revised parameter values for speciation modelling are therefore suggested. Additions of salt or natural DOM in the influent did not change the leachate concentration of Cu. Thus, although Cl and natural DOM might be present in the influent in the field due to road salting or infiltration of soil water, this is of minor importance for the potential environmental impact from MSWI bottom ash.This thesis allows estimates of long-term leaching and toxicity to be improved and demonstrates the need for broadening the system boundaries in order to highlight the trade-offs between different types of impact. For decisions on whether incinerator residues should be utilised or landfilled, the use of a life cycle perspective in combination with more detailed assessments is recommended. / QC 20100914
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Characterization of High-PGE Low-Sulphur Mineralization at the Marathon PGE-Cu Deposit, OntarioRuthart, Ryan January 2013 (has links)
The Marathon PGM-Cu deposit is hosted by the Coldwell alkaline complex, which consists predominantly of gabbro and syenite and was emplaced at 1108 Ma as part of the Mid-Continent Rift System. Mineralization at the Marathon PGM-Cu deposit is hosted by the Two Duck Lake Gabbro (TDLG), a fresh olivine-bearing gabbro. The Marathon deposit contains several zones of mineralization including the Basal Zone, the Main Zone and the W-Horizon. The W-Horizon is a high-grade PGE zone characterized by low S, low Cu/Pd and high Cu/Ni. The sulphide mineral assemblage is predominantly chalcopyrite and bornite. This contrasts with the Main Zone where the dominant sulphide mineral assemblage is chalcopyrite and pyrrhotite. The Main Zone contains higher S, higher Cu/Pd and shows a decrease in Cu/Pd and pyrrhotite/chalcopyrite from base to top.
Four drill holes were selected for detailed analysis to characterize the W-Horizon style of mineralization. Detailed petrographic study of the pristine and largely unaltered TDLG shows that wide spread hydrothermal alteration is not responsible for the mineralization. Detailed outcrop mapping shows that the TDLG intruded as a series of multiple intrusions in a dynamic magmatic system. Geochemical studies through the W-Horizon show that the mineralization is not the result of crystallization in a layered intrusion. The results of geochemical assays and electron microprobe analysis of olivine grains show that the chemistry through the TDLG hosting the W-Horizon is erratic. This data supports the TDLG intruding as a series of sills in a dynamic conduit environment.
The calculated sulphide metal tenors for the W-Horizon are higher than can be explained by closed system R Factor models. Multistage dissolution upgrading in an open system is examined as the process forming the W-Horizon. This model is able to produce the sulphide metal tenors observed in the W-Horizon. Sulphur loss also affects grades and tenors and was examined through geochemical and petrological data. The change in sulphide mineral assemblage from a pyrrhotite and chalcopyrite (S-rich) to chalcopyrite and bornite (S-poor) supports S-loss. Whole rock S and Se contents are also analyzed to investigate S loss, a lower S/Se indicates that sulphur has been removed from the system. Average S/Se values are ~800 for the W-Horizon, ~1980 for the Main Zone and ~1700 in unmineralized samples. The very low S/Se observed within the W-Horizon supports S-loss.
Sulphur loss in a dynamic magmatic conduit system is proposed for the formation of the W-Horizon mineralization. In this model sulphur undersaturated basaltic magma interacted with an immiscible sulphide liquid in a magma conduit, resulting in the dissolution of sulphide into the basaltic melt and PGE enrichment.
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Origine de l'émission des électrons Auger lors du bombardement ionique des solidesViaris de Lesegno, Patrick 27 November 1981 (has links) (PDF)
Les premières observations de l'émission d'électrons Auger au cours du bombardement ionique d'une cible solide remontent à 1965 (Snoek et al. 11) dans le cas d'électrons caractéristiques des particules projectiles, et à 1967 (Hennequin et al. 12) dans le cas d'électrons caractéristiques des atomes cibles. Il existe actuellement une soixantaine de publications sur le sujet, mais les publications étrangères n'apparaissent qu'à partir de 1974, certains auteurs semblant même avoir incidenment redécouvert le phénomène. L'émission Auger lors de collisions en phase gazeuse a fait aussi l'objet de nombreuses études durant la même période. La connaissance précise des conditions mécaniques de la collision et l'existence d'états électroniques bien définis, tant avant qu'après la désexcitation par effet Auger, facilitent considérablement l'interprétation des expériences. La théorie de Fano et Lichten 1960 est maintenant bien établie : certaines des orbitales moléculaires formées lors de la collision de deux particules sont promues vers des niveaux moins liés et, après interaction avec une orbitale incomplète, peuvent conduire à la formation d'un trou électronique interne dans l'un ou l'autre des partenaires. Plus généralement, ce sont les progrès récents de la physique des collisions qui permettent maintenant de comprendre l'ensemble du mécanisme de l'émission Auger à partir des solides. Il existe naturellement un lien entre -l'émission d'électrons Auger et l'émission d'ions secondaires durant le bombardement ionique d'un solide. Ce lien est même direct dans le cas des ions rapides ou multichargés qui sont formés par désexcitation Auger, à l'extérieur de la cible, d'atomes éjectés ayant conservé un trou électronique interne : c'est le modèle de l'émission cinétique de Joyes 1975. C'est d'ailleurs à la suite d'une suggestion de Castaing, et pour interpréter l'émission d'ions secondaires, que l'étude de ce lien a été entreprise tant sur le plan expérimental que théorique. L'émission Auger permet en outre d'atteindre une meilleure connaissance des collisions les plus violentes à l'intérieur d'un solide, et c'est dans cet esprit que le présent travail a été réalisé. Plus précisément, nous avons cherché à mieux déterminer dans quelle mesure les conclusions théoriques de la physique des collisions peuvent être utilisées pour rendre compte des résultats expérimentaux relatifs à l'émission Auger des solides et prévoir l'influence de la nature de la cible et du projectile sur les caractéristiques de cette émission. D'abord un rappel théorique nécessaire à l'interprétation des résultats expérimentaux, nous suivrons les étapes conduisant à l'émission d'un électron Auger à la suite de l'impact de l'ion primaire sur les atomes de la cible : la création d'une cascade de collisions dans le solide, l'excitation d'un niveau électronique interne au cours d'une collision violente, la désexcitation par effet Auger au cours de la migration de la particule excitée et enfin la sortie de l'électron à l'extérieur de la cible. Puis la description des propriétés des dispositifs expérimentaux que nous avons réalisés pour cette étude. Ensuite, dans les deux chapitres suivants, nous étudierons les collisions responsables de l'émission des électrons Auger caractéristiques soit du projectile, soit de la cible. Dans le premier cas (chapitre III), nous nous intéresserons essentiellement à l'émission des électrons Auger de l'argon lors du bombardement de diverses cibles par des ions Ar d'énergie comprise entre 2 et 16 keV et pourrons montrer ainsi le bon accord entre les expériences sur les solides et les interprétations théoriques fondées sur les collisions atomiques et la promotion des orbitales moléculaires. Une fois établi cet accord, il nous sera possible (chapitre IV) d'étendre cette interprétation à l'émission des électrons Auger caractéristiques de la cible, pour lesquels la situation est compliquée par le fait que l'énergie de collision est mal connue et qu'un doute peut subsister sur la nature de la collision responsable de l'excitation : collision symétrique entre deux atomes identiques de la cible ou collision asymétrique entre l'ion incident et l'un des atomes de la cible. Dans le cas des métaux légers, magnésium et aluminium, nous montrerons que la proportion des collisions asymétriques est une fonction croissante de l'énergie des ions incidents, mais reste faible dans notre domaine d'énergie (2 - 16 keV). Les résultats que nous présentons ont pour la plupart fait l'objet de publications antérieures.
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Estudio molecular y citogenético del carcinoma urotelial: Detección temprana de la enfermedad y de su diseminaciónMarín Aguilera, Mercedes 09 December 2008 (has links)
En España se diagnostican cada año unos 12.000 nuevos casos de carcinoma urotelial (CU). Más concretamente, en Cataluña este tumor representa entre un 9,9 y un 11,7% del total de tumores malignos, dando lugar a una mortalidad cáncer específica del 5,2% en el sexo masculino. Aunque en la mayoría de casos la enfermedad se acaba detectando en su fase más inicial, la alta frecuencia de recidivas y la posibilidad de progresión y diseminación debido a la agresividad de algunas formas limitarán la supervivencia del paciente.El método estándar para la detección y seguimiento del CU se basa en la combinación de la citología urinaria y la cistoscopia. Sin embargo, la primera de estas técnicas presenta baja sensibilidad en la detección de tumores de estadio inical y bajo grado, mientras que la segunda es una técnica invasiva que además no es lo suficientemente sensible para detectar todas las lesiones de crecimiento plano.Por otro lado, las técnicas histológicas convencionales para el diagnóstico de la diseminación linfática del CU no son lo suficientemente sensibles ya que alrededor del 50% de pacientes sometidos a cirugía radical con linfadenectomía N0, fallecen antes de los 5 años post-cirugía. Estos datos sugieren que existe una diseminación tumoral antes de la cirugía que no es detectada mediante estas técnicas histológicas.Debido a la elevada prevalencia y gravedad de la enfermedad, a la invasividad de las pautas utilizadas en su diagnóstico y a la falta de métodos de estadiaje refinados, el desarrollo de nuevos sistemas diagnósticos que permitan una detección temprana tanto del CU inicial como de sus recidivas y de su diseminación es esencial para mejorar la calidad de vida y el pronóstico de los pacientes con esta enfermedad.En el presente trabajo se ha evaluado la utilidad de la técnica "fluorescence in situ hibridization" (FISH) en el diagnóstico no invasivo del Cu de bajo estadio, en el diagnóstico no invasivo del CU localizado en el tracto urnario superior (TUS) y en el pronóstico de pacientes con CU de alto riesgo de recurrencia y progresión, tratados mediante inmunoterapia con el bacilo de Calmette Guérin (BCG). Por otro lado se ha intentado detectar la presencia de micrometástasis linfáticas así como de diseminación sanguínea del CU, mediante marcadores moleculares en pacientes sometidos a cistectomía y linfadenectomía radical.Los resultados obtenidos indican que la técnica FISH basada en los cromosomas 3, 7, 9 y 17 presenta mayor sensibilidad que la citología urinaria, y una similar especificidad equivalente en la detección del CU no músculo-infiltrante, así como en la detección del CU localizado en el TUS. La naturaleza no invasiva de este ensayo así como su elevada sensibilidad y especificidad podrían contribuir a mejorar el actual diagnóstico/seguimiento del CU en estas localizaciones. Otro resultado interesante fue que los pacientes con un resultado positivo de FISH tras la terapia BCG tienen mayor probabilidad de presentar una recurrencia del tumor. Así, la técnica FISH parece ser útil en el seguimiento de los pacientes con un tumor no músculo-infiltrante de alto riesgo de recurrencia y progresión sometidos a terapia BCG. Finalmente, se observó que la utilización de marcadores moleculares permite mejorar la sensibilidad del análisis histopatológico en la detección de la diseminación linfática tumoral y que la linfadenectomía juega un importante papel curativo eliminando la enfermedad microdiseminada. Sin embargo, el análisis de la expresión génica en muestras de sangre periférica no es adecuado para seleccionar a aquellos pacientes que desarrollarán metástasis detectables clínicamente, aunque sí permite distinguir entre pacientes con CU de controles sanos. / Cystoscopy and cytology are the standard methods to detect and monitor urothelial carcinoma (UC). Cystoscopy is an invasive technique (especially to visualize the upper urinary tract or UUT) that has a high sensitivity, except in flat malignancies. Cytology has the advantage of being non-invasive with a high specificity, but it lacks sensitivity and produces high rates of suspicious cases, especially for low-stage and low-grade tumors. Another weak point in the clinical management of UC is the fact that current methodologies to detect disseminated UC lack sensitivity.The aims of this study were: (1) to evaluate the performance of a multiprobe FISH (fluorescence in situ hybridization) assay for non-invasive detection of superficial UC in the bladder, in comparison to urinary cytology, (2) to assess the clinical utility of FISH as a non-invasive method for diagnosing and monitoring UC in UUT, (3) to evaluate the use of FISH for determining the response of patients with high-risk superficial bladder tumour (HRSBT) to bacillus Calmette-Guérin (BCG) therapy, (4) to identify and test potential mRNA markers of UC dissemination in lymph nodes, and to compare the performance of selected markers with patients' clinical outcome, and (5) to test the efficiency of such mRNA markers in detecting and monitoring UC haematogenous dissemination.According to our results, FISH assay for chromosomes 3, 7, 9, and 17 has higher sensitivity than cytology and a similar specificity in the detection of superficial UC and UC at UUT, which could be useful for reducing some cystoscopies in the follow-up of these patients. Moreover, a high percentage of positive pre-BCG FISH results were obtained, suggesting the need for adjuvant therapy in patients with HRSBT after the transurethral resection. In addition, patients with a positive post-BCG FISH result were more likely to relapse after therapy. Thus, FISH appears to be useful for the surveillance of patients with HRSBT following BCG therapy.Finally, using molecular markers it was possible to improve the sensitivity of LN histologic analysis. Also this methodology allowed distinguishing between UC patients and controls. However, despite its high sensitivity, it was not possible to monitor UC haematogenous dissemination.
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Effect of BaZrO3 Addition and Film Growth on Superconducting Properties of (Nd,Eu,Gd)Ba2Cu3Oy Thin FilmsIchino, Yusuke, Yoshida, Yutaka, Inoue, Kouichi, Ozaki, Toshinori, Takai, Yoshiaki, Matsumoto, Kaname, Mukaida, Masashi, Kita, Ryusuke, Ichinose, Ataru, Horii, Shigeru 06 1900 (has links)
No description available.
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Process Kinetics of Transient Liquid PhaseTurriff, Dennis Michael Ryan 09 1900 (has links)
The problem of inadequate measurement techniques for quantifying the isothermal solidification process during transient liquid phase sintering (TLPS) in binary isomorphous systems such as Ni-Cu, and the resulting uncertainty regarding the solidification mechanism and its sensitivity to important process parameters, has been investigated. A unique combination of differential scanning calorimetry (DSC), neutron diffraction (ND), and metallographic techniques has enabled the quantitative characterization of important TLPS stages (i.e., solid-state sintering, melting and dissolution, isothermal solidification, and homogenization) as well as verifying the re-melt behaviour of post-sintered specimens and measuring variable melting point (VMP) properties. This has resulted in the advancement of the fundamental understanding of liquid formation and its removal mechanism during isothermal, or diffusional, solidification. The Ni-Cu system was chosen for experimentation due to its commercial relevance as a braze filler material and also because it is an ideal model system (due to its isomorphous character) that is not well understood on a quantitative or phenomenological basis. Samples consisted of elemental Ni and Cu powder mixtures of varying particle size and composition.
In DSC experiments, the progress of isothermal solidification was determined by measuring the enthalpy of melting and solidification after isothermal hold periods of varying length and comparing these to the measured enthalpy of pure Cu. The low melting enthalpies measured for all Ni/Cu mixtures heated just past the Cu melting point (1090°C) indicate that solid-state sintering and interdiffusion during heat-up significantly suppress initial liquid formation and densification from the wetting liquid. For samples heated well past the Cu melting point (1140°C), Ni dissolution causes increased initial liquid fractions and densification. It was found that significantly more time was required for complete liquid removal at 1140°C vs. 1090°C. This is attributed to the observed increase in initial liquid fractions formed at higher processing temperatures due to the dissolution of Ni. This effectively counteracts the increased diffusivities at these temperatures, and thus more time is required to completely remove the increased liquid content. TLP mixtures sintered at 1140°C using three different particle sizes revealed that fine base metal Ni particles cause high degrees of solid-state interdiffusion during heat-up, small initial liquid fractions, and accelerated liquid removal rates due to high surface area/volume ratios. A diffusion-based analytical model was developed to account for these effects (i.e., particle size, temperature, solid-state sintering, and dissolution). Comparison with experimental DSC results reveals that this model can accurately predict liquid removal given accurate diffusivities. Metallographic analysis of post-sintered DSC specimens via SEM and EDS indicates that isothermal liquid solidification leaves behind Ni-rich cores surrounded by Cu-rich matrix regions having compositions given by the Ni-Cu phase diagram solidus (CS) at a selected isothermal processing temperature (TP).
ND experiments were used to investigate the melting event and interdiffusion during the isothermal hold segment by analyzing the evolution of the {200} FCC peaks of Ni and Cu. ND patterns were collected in situ at 1 minute intervals during prolonged sintering cycles for larger powder specimens. The Cu melting event was characterized by an abrupt decrease in Cu peak intensity at 1085°C as well as a shift towards higher 2 angles corresponding to lower Cu contents. This shifted residual peak (hereafter referred to as the CS peak) originates from regions of the specimen having compositions near solidus at TP. Immediately following the melting event, the evolution of ND patterns shows that these CS peaks grow rapidly, indicating the isothermal growth of a Cu-rich phase. These in situ findings confirmed the metallographic and DSC data and indicated that isothermal solidification of the liquid phase proceeds via the growth of a solute-rich solid solution layer surrounding the Ni particles. This occurs by the transient progression of the solid/liquid interface at compositions given by the liquidus and solidus (CS/CL). During sintering, diffraction intensities gradually increased at intermediate 2 angles between previous Ni and Cu peaks. ND patterns gradually evolved from initially having a broad double-peak profile to a sharper single-peak profile due to increased Ni-Cu interdiffusion. The 2position and width of the post-sintered peaks indicated very homogeneous sintered alloys. Metallographic analysis of post-sintered specimens having undergone prolonged sintering and homogenization revealed extensive Kirkendall pore formation from unequal diffusivities (DCu > DNi).
In this study, the unique combination of diffusion-based modelling as well as DSC, ND, and supporting metallographic analysis has enabled the identification of characteristic sintering behaviour, important process parameters, and processing windows for TLPS in Ni-Cu systems. Quantitative and in situ information of this nature is absent in the previous TLPS literature.
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Process Kinetics of Transient Liquid PhaseTurriff, Dennis Michael Ryan 09 1900 (has links)
The problem of inadequate measurement techniques for quantifying the isothermal solidification process during transient liquid phase sintering (TLPS) in binary isomorphous systems such as Ni-Cu, and the resulting uncertainty regarding the solidification mechanism and its sensitivity to important process parameters, has been investigated. A unique combination of differential scanning calorimetry (DSC), neutron diffraction (ND), and metallographic techniques has enabled the quantitative characterization of important TLPS stages (i.e., solid-state sintering, melting and dissolution, isothermal solidification, and homogenization) as well as verifying the re-melt behaviour of post-sintered specimens and measuring variable melting point (VMP) properties. This has resulted in the advancement of the fundamental understanding of liquid formation and its removal mechanism during isothermal, or diffusional, solidification. The Ni-Cu system was chosen for experimentation due to its commercial relevance as a braze filler material and also because it is an ideal model system (due to its isomorphous character) that is not well understood on a quantitative or phenomenological basis. Samples consisted of elemental Ni and Cu powder mixtures of varying particle size and composition.
In DSC experiments, the progress of isothermal solidification was determined by measuring the enthalpy of melting and solidification after isothermal hold periods of varying length and comparing these to the measured enthalpy of pure Cu. The low melting enthalpies measured for all Ni/Cu mixtures heated just past the Cu melting point (1090°C) indicate that solid-state sintering and interdiffusion during heat-up significantly suppress initial liquid formation and densification from the wetting liquid. For samples heated well past the Cu melting point (1140°C), Ni dissolution causes increased initial liquid fractions and densification. It was found that significantly more time was required for complete liquid removal at 1140°C vs. 1090°C. This is attributed to the observed increase in initial liquid fractions formed at higher processing temperatures due to the dissolution of Ni. This effectively counteracts the increased diffusivities at these temperatures, and thus more time is required to completely remove the increased liquid content. TLP mixtures sintered at 1140°C using three different particle sizes revealed that fine base metal Ni particles cause high degrees of solid-state interdiffusion during heat-up, small initial liquid fractions, and accelerated liquid removal rates due to high surface area/volume ratios. A diffusion-based analytical model was developed to account for these effects (i.e., particle size, temperature, solid-state sintering, and dissolution). Comparison with experimental DSC results reveals that this model can accurately predict liquid removal given accurate diffusivities. Metallographic analysis of post-sintered DSC specimens via SEM and EDS indicates that isothermal liquid solidification leaves behind Ni-rich cores surrounded by Cu-rich matrix regions having compositions given by the Ni-Cu phase diagram solidus (CS) at a selected isothermal processing temperature (TP).
ND experiments were used to investigate the melting event and interdiffusion during the isothermal hold segment by analyzing the evolution of the {200} FCC peaks of Ni and Cu. ND patterns were collected in situ at 1 minute intervals during prolonged sintering cycles for larger powder specimens. The Cu melting event was characterized by an abrupt decrease in Cu peak intensity at 1085°C as well as a shift towards higher 2 angles corresponding to lower Cu contents. This shifted residual peak (hereafter referred to as the CS peak) originates from regions of the specimen having compositions near solidus at TP. Immediately following the melting event, the evolution of ND patterns shows that these CS peaks grow rapidly, indicating the isothermal growth of a Cu-rich phase. These in situ findings confirmed the metallographic and DSC data and indicated that isothermal solidification of the liquid phase proceeds via the growth of a solute-rich solid solution layer surrounding the Ni particles. This occurs by the transient progression of the solid/liquid interface at compositions given by the liquidus and solidus (CS/CL). During sintering, diffraction intensities gradually increased at intermediate 2 angles between previous Ni and Cu peaks. ND patterns gradually evolved from initially having a broad double-peak profile to a sharper single-peak profile due to increased Ni-Cu interdiffusion. The 2position and width of the post-sintered peaks indicated very homogeneous sintered alloys. Metallographic analysis of post-sintered specimens having undergone prolonged sintering and homogenization revealed extensive Kirkendall pore formation from unequal diffusivities (DCu > DNi).
In this study, the unique combination of diffusion-based modelling as well as DSC, ND, and supporting metallographic analysis has enabled the identification of characteristic sintering behaviour, important process parameters, and processing windows for TLPS in Ni-Cu systems. Quantitative and in situ information of this nature is absent in the previous TLPS literature.
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