The objective of this study is to investigate the feasibility of depositing 1.5 mm thick titanium coatings, as a repair method for aerospace Ti-6Al-4V substrates, using two new commercially available processes: Low Pressure Cold Spray (LPCS) and Pulsed Gas Dynamic Spray (PGDS). The coatings produced were examined and characterized by their porosity level, microhardness, adhesion strength, particle flattening ratio, wipe tests, fracture surface type and wear tests. Phases and chemical composition were determined using X-Ray diffraction analysis and energy dispersive spectroscopy, respectively. It was found that both spraying processes are capable of producing dense, hard and oxide-free coatings using specific parameters. Finally, as a first step towards repair implementation of these processes, damages were simulated on Ti-6Al-4V samples, which were successfully repaired with low porosity and high hardness levels. The feasibility of repairs was confirmed, the next step will consist in qualification testing to assess coating performances under real life application.

Esta dissertação, investiga o comportamento em fadiga da liga Ti-6Al-4V após o tratamento superficial denominado oxidação térmica, para aplicação em pinos fusíveis mecânicos. A oxidação térmica controlada do titânio e suas ligas apresenta propriedades interessantes na resistência à corrosão-desgaste, devido a sua alta estabilidade e dureza, contudo, há lacunas na literatura se esse benefício é recíproco nas propriedades da vida em fadiga. Corpos-de-prova foram tratados termicamente em atmosfera de ar ambiente e após foram submetidos a ensaios de rugosidade, metalografia, dureza, tração, fadiga e análise fractográfica. Os resultados obtidos em fadiga foram comparados com a mesma liga não oxidada, mostrando que as propriedades em fadiga não são recíprocas às propriedades de corrosão-desgaste da liga Ti- 6Al-4V, após o tratamento superficial de oxidação térmica. Enquanto para uma determinada condição de tratamento superficial, houve melhora de até 30x na resistência à corrosãodesgaste (redução de 97% na taxa de desgaste), nas propriedades mecânicas houve redução de 18% no limite de resistência à fadiga. / This dissertation investigates the fatigue behavior of thermally oxidized Ti-6Al-4V alloy, applied to break bolts. The controlled thermal oxidation of titanium and its alloys presents interesting properties in fretting-corrosion resistance, especially to the high stability and hardness. However, there are gaps in the literature regarding the effect of this oxide layer on fatigue properties. Thermally Oxidized specimens were tested for roughness, metallography, hardness, tensile strength, fatigue and fractographic analysis. The results were compared with the fatigue results of the same alloy when untreated, showing that the fatigue properties and the fretting-corrosion properties of thermally oxidized Ti-6Al-4V are not reciprocal. While with a given condition for the thermal oxidation, an improvement up to 30x occurred on fretting-corrosion resistance (97% reduction in the rate of wear), the endurance decreased 18%.

Made available in DSpace on 2016-12-08T17:19:32Z (GMT). No. of bitstreams: 1 PRE-TEXTUAL.pdf: 61510 bytes, checksum: de42e44f3e60516728ad63e4d079e03e (MD5) Previous issue date: 2008-10-31 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Titanium and its alloys are widely used in biomedical area. Although these materials have a good biocompatibility in nature , a surface treatment is generally required to prevent ionic dissolution and improve surface properties for use as implants and proteases. In this study we performed a thermal oxidation in order to thicker the oxide film aiming to prevent ionic dissolution and improve the surface properties. Thermal oxidation was carried out in air between 300 °C and 700 oC for 5 and 24 hours. Evidences from X-ray diffraction and differential thermal analyses showed that the passive film is converted into crystalline anatase at approximately 280 oC on titanium and Ti-6Al-4V alloy. At approximately 450 oC occurs the nucleation and growth of rutile. Between 450 °C and 700 oC the film is constituted of anatase and rutile on both materials. Surface roughness, micro and nanoindentation, wearcorrosion and Rokwell C adhesion tests were used to evaluate the surface properties of the oxide films. A significant increase on surface roughness was observed on the samples oxidized between 500 °C and 700 oC. The surface roughness increased steeply with temperature and oxidation time. A significant increase in the microhardness was observed on the samples treated over 500 °C. The highest values were found at 650 °C on both materials, measuring about 12,000 MPa and 10,000 MPa on Ti and Ti-6Al-4V, respectively. However, at 700 °C lower values were obtained due to the formation of a porous and fragile oxide film, composed essentially of rutile. Bellow 500 °C the oxide films are thin and the microhardness is somewhat the same of that of the substrate. The thin oxide films were evaluated by nanoindentation in terms of harness and elastic modulus. The hardness (H) and the modulus (E) found on the titanium and Ti-6Al-4V were of about H = 10-12 GPa and E = 180-250 GPa, and H = 10-18 GPa and E = 180-250 GPa, respectively. The specific wear-corrosion rate measured on the oxide films showed that the samples oxidized at 600 °C - 650 °C presented the lowest values. Rockwell-C adhesion tests reveled that the oxide films formed between 600 °C - 650 oC have good adhesion. / O titânio é considerado um metal apropriado para aplicações in vivo por causa de sua boa biocompatibilidade e excelente resistência à corrosão. Por isso, o titânio e suas ligas têm sido amplamente utilizados por várias décadas como materiais para implantes, próteses e dispositivos médicos. No entanto, o titânio comercialmente puro (Ti_cp) apresenta baixa dureza superficial e resistência ao desgaste, limitando sua aplicação em próteses articuladas, pois a articulação sofre impactos e atrito constantes. A liga Ti-6Al-4V ainda é a principal liga de titânio usada como biomaterial, mas existe a preocupação sobre a toxicidade do alumínio e do vanádio. Os íons de titânio são considerados agentes químicos cancerígenos, os íons alumínio causam desordem neurológica e os íons vanádio estão associados com distúrbios enzimáticos, entre outros problemas. Sabe-se que a camada passiva formada naturalmente é muito fina e permite uma certa dissolução iônica. Para limitar a dissolução iônica optou-se pela formação de um filme de óxido bem mais espesso do que ao filme passivo pelo processo de oxidação térmica. Este tratamento superficial também tem por finalidade aumentar a rugosidade superficial (de modo a otimizar a osseointegração), a dureza e a resistência à corrosão-desgaste (em próteses sujeitas a impactos e atrito constantes). Portanto, esse estudo consistiu em analisar a influência da oxidação térmica sobre as propriedades de superfície do Ti_cp e da liga Ti-6Al-4V para aplicações biomédicas e odontológicas. Os ensaios de oxidação térmica foram realizados entre 300 °C e 700 °C em atmosfera de ar ambiente durante 5 e 24 horas. Os filmes de óxido formados foram avaliados por ensaios de difração de raios-x, análise térmica, rugosidade superficial, micro e nanodureza, corrosão-desgaste e aderência Rockwell C. As análises por difração de raios-x e análise térmica mostraram que os óxidos são formados de rutilo e anatásia. Os filmes de óxidos formados entre 600 °C e 650 oC, tanto para o Ti_cp como para a liga Ti-6Al-4V apresentaram os melhores resultados quanto a resistência à corrosão-desgaste, rugosidade superficial e aderência. A dureza do filme de óxido aumentou expressivamente com a temperatura e tempo de oxidação térmica a partir de 500 °C. Os valores mais altos de dureza ocorreram para a temperatura de 650 °C, em ambas as amostras e tempos de oxidação térmica, correspondendo à aproximadamente 12.000 MPa e 10.000 MPa, para o Ti_cp e a liga Ti-6Al-4V, respectivamente. Porém a 700 °C, quando os filmes de óxido apresentaram fase predominante de rutilo, a dureza superficial diminuiu devido a maior porosidade e fragilidade do filme de óxido formado, para ambas as amostras e tempos de oxidação térmica. Quanto à propriedade de resistência à corrosão desgaste, o Ti_cp apresentou os melhores resultados para as amostras oxidadas a 650 °C por 5 horas e 600 °C por 24 horas, enquanto a liga Ti-6Al-4V apresentou os melhores resultados, para ambos os tempos de oxidação (5 e 24 horas), à temperatura de 600 °C.

Esta dissertação, investiga o comportamento em fadiga da liga Ti-6Al-4V após o tratamento superficial denominado oxidação térmica, para aplicação em pinos fusíveis mecânicos. A oxidação térmica controlada do titânio e suas ligas apresenta propriedades interessantes na resistência à corrosão-desgaste, devido a sua alta estabilidade e dureza, contudo, há lacunas na literatura se esse benefício é recíproco nas propriedades da vida em fadiga. Corpos-de-prova foram tratados termicamente em atmosfera de ar ambiente e após foram submetidos a ensaios de rugosidade, metalografia, dureza, tração, fadiga e análise fractográfica. Os resultados obtidos em fadiga foram comparados com a mesma liga não oxidada, mostrando que as propriedades em fadiga não são recíprocas às propriedades de corrosão-desgaste da liga Ti- 6Al-4V, após o tratamento superficial de oxidação térmica. Enquanto para uma determinada condição de tratamento superficial, houve melhora de até 30x na resistência à corrosãodesgaste (redução de 97% na taxa de desgaste), nas propriedades mecânicas houve redução de 18% no limite de resistência à fadiga. / This dissertation investigates the fatigue behavior of thermally oxidized Ti-6Al-4V alloy, applied to break bolts. The controlled thermal oxidation of titanium and its alloys presents interesting properties in fretting-corrosion resistance, especially to the high stability and hardness. However, there are gaps in the literature regarding the effect of this oxide layer on fatigue properties. Thermally Oxidized specimens were tested for roughness, metallography, hardness, tensile strength, fatigue and fractographic analysis. The results were compared with the fatigue results of the same alloy when untreated, showing that the fatigue properties and the fretting-corrosion properties of thermally oxidized Ti-6Al-4V are not reciprocal. While with a given condition for the thermal oxidation, an improvement up to 30x occurred on fretting-corrosion resistance (97% reduction in the rate of wear), the endurance decreased 18%.

Esta dissertação, investiga o comportamento em fadiga da liga Ti-6Al-4V após o tratamento superficial denominado oxidação térmica, para aplicação em pinos fusíveis mecânicos. A oxidação térmica controlada do titânio e suas ligas apresenta propriedades interessantes na resistência à corrosão-desgaste, devido a sua alta estabilidade e dureza, contudo, há lacunas na literatura se esse benefício é recíproco nas propriedades da vida em fadiga. Corpos-de-prova foram tratados termicamente em atmosfera de ar ambiente e após foram submetidos a ensaios de rugosidade, metalografia, dureza, tração, fadiga e análise fractográfica. Os resultados obtidos em fadiga foram comparados com a mesma liga não oxidada, mostrando que as propriedades em fadiga não são recíprocas às propriedades de corrosão-desgaste da liga Ti- 6Al-4V, após o tratamento superficial de oxidação térmica. Enquanto para uma determinada condição de tratamento superficial, houve melhora de até 30x na resistência à corrosãodesgaste (redução de 97% na taxa de desgaste), nas propriedades mecânicas houve redução de 18% no limite de resistência à fadiga. / This dissertation investigates the fatigue behavior of thermally oxidized Ti-6Al-4V alloy, applied to break bolts. The controlled thermal oxidation of titanium and its alloys presents interesting properties in fretting-corrosion resistance, especially to the high stability and hardness. However, there are gaps in the literature regarding the effect of this oxide layer on fatigue properties. Thermally Oxidized specimens were tested for roughness, metallography, hardness, tensile strength, fatigue and fractographic analysis. The results were compared with the fatigue results of the same alloy when untreated, showing that the fatigue properties and the fretting-corrosion properties of thermally oxidized Ti-6Al-4V are not reciprocal. While with a given condition for the thermal oxidation, an improvement up to 30x occurred on fretting-corrosion resistance (97% reduction in the rate of wear), the endurance decreased 18%.

Le procédé de fabrication directe par projection laser (FDPL), est un procédé de fabrication additive qui permet de fabriquer des pièces de forme complexe directement à partir d'un fichier CAO, sans outil et sans moule. L'un de ses inconvénients majeurs est la mauvaise qualité des états de surface obtenus (Ra supérieur à 15 μm) qui nécessite systématiquement des étapes de ré-usinage. Dans ce contexte, et dans le cadre du projet ANR « ASPECT », cette thèse a pour double objectif une meilleure compréhension de l'origine des états de surface dégradés, et le développement de différentes solutions expérimentales innovantes permettant d'améliorer les états de surface.Dans un premier temps, en considérant des géométries simples (murs) en alliage de titane Ti-6Al-4V, nous avons étudié l'interaction faisceau laser / jet de poudre / bain liquide métallique par différents diagnostics (caméra rapide, caméra thermique, pyrométrie…) pour comprendre l'évolution de la géométrie, la thermique et l'hydrodynamique de la zone fondue (ZF). Ces analyses nous ont permis de corréler les évolutions des ZF à celles des états de surface, et de mettre en évidence, sur le Ti-6Al-4V la prépondérance des effets de tension superficielle sur les effets de gravité, dans l'équilibre des ZF, et l'effet bénéfique de zones fondues larges et profondes combinées à de faibles hauteurs par couche, dans la réduction des micro et macro-rugosités. La réduction du débit massique local Dm* en vis-à-vis des parois latérales et l'augmentation du rayon de courbure des ZF avec l'élargissement des ZF (donc avec des rapports El= P/V (J/m) élevés) sont à l'origine des effets bénéfiques obtenus. Différents modèles analytiques et numériques ont également été utilisés ou développés, en complément des résultats expérimentaux, pour décrire le procédé (modèle d'interaction laser-poudre, modèle numérique thermique 3D du procédé, modèle de calcul des ondulations périodiques).En utilisant un large spectre de conditions expérimentales, et une caractérisation rigoureuse des conditions de fabrication (analyses de faisceau, de jet de poudre …) nous avons également apporté des améliorations notables à la qualité des états de surface obtenus. Ainsi, l'utilisation d'un éclairement laser uniforme plutôt que quasi-Gaussien, ou l'utilisation d'un régime quasi-pulsé plutôt que continu ont permis, sur le Ti-6Al-4V de réduire significativement les gradients thermiques en ZF et les mouvements de convection de Marangoni associés, et d'obtenir des qualités d'états de surface fortement améliorées (Ra< 3 µm) par rapport aux études antérieures sur le sujet.Pour finir, une partie de l'étude s'est concentrée sur l'utilisation d'un autre matériau: l'acier inoxydable 316L, afin d'analyser l'influence de la nature chimique et des propriétés thermo-physiques de la poudre projetée sur la qualité des états de surface. Les résultats ont montré que, contrairement à l'alliage de titane, les meilleures rugosités étaient obtenues pour les énergies linéiques El (J/m) les plus faibles, en raison de la formation, à El élevé, de macro-agglomérats de poudre sur les parois des murs. Ce résultat confirme la difficulté d'une approche prédictive globale des états de surface à partir des paramètres thermo-physiques des matériaux projetés. / The process of direct manufacturing by projection laser ( FDPL), is a process of additive manufacturing which allows to make rooms(parts,plays) of complex shape directly from a file CAD, without tool and without mold(mussel). One of its major inconveniences is the bad quality of the states of surface obtained (Ra upper to 15 µm) which requires systematically stages of remanufacturing. In this context, and within the framework of the project ANR " aspect ", this thesis(theory) has for double objective a better understanding of the origin of the degraded states of surface, and the development of various innovative experimental solutions allowing to improve the states of surface. At first, by considering simple geometries (walls) in alloy of titanium Ti-6Al-4V, we studied the interaction

The recent breakthroughs of Additive Manufacturing (AM) have shed light on the ever more versatile technologies this term encompasses. AM, popularly known as 3D printing, offers distinct benefits compared to traditional manufacturing, such as reduced design constraints, “complexity for free” and waste reduction. This “bottom-up” strategy differs from the more constraining “top-down” approach used in traditional manufacturing. Among the many AM processes developed for metals, Electron Beam Melting (EBM) and Selective Laser Melting (SLM) are powder-bed fusion processes allowing complex three-dimensional geometries to be produced from the selective melting of successive layers of metal powder. EBM and SLM are the two most widely used AM processes for the production of critical Ti-6Al-4V parts, particularly for the biomedical and aeronautic industries. Despite their many advantages, these technologies present severe limitations that remain to be addressed. These include the presence of build defects in the material and a high surface roughness, which is inherent to powder-bed fusion processes.Moreover, the microstructure of as-built EBM or SLM Ti-6Al-4V is far from being optimized. In order to improve the material properties of additively manufactured Ti-6Al-4V parts, postprocess treatments can be considered. This thesis aims at investigating the impact of such treatments on the microstructure and mechanical properties of Ti-6Al-4V produced by EBM. After characterizing the microstructure, texture, and tensile properties of as-built Ti-6Al-4V, the effect of standard post-treatments, such as Hot Isostatic Pressing (HIP) and surface machining, are quantified on simple geometries. The interest of HIP is clearly demonstrated, especially when combined to improvement of the surface finish via machining. The removal of critical defects from both the bulk and the surface results in a substantial increase in ductility. Removal of the rough surface via machining also increases the mechanical efficiency of the parts. Regarding microstructural optimization, considering the impossibility of applying hot working on near-net shape parts as a major limitation, innovative heat treatments have to be specifically developed for additively manufactured Ti-6Al-4V. In this thesis, dual-phase alpha+alpha’ microstructures are generated, by performing subtransus annealing followed by water quenching. Depending on the annealing temperature, a broad range of mechanical properties are obtained. For annealing temperatures of 900 to 920°C, a simultaneous increase in ultimate tensile strength and ductility is achieved. The existence of a mechanical contrast between the soft alpha’ martensite and the harder alpha phase is clearly demonstrated and partly explains the remarkable work-hardening behaviour of this heterogeneous material. Further annealing of this out-of equilibrium alpha+alpha’ microstructure generates various microstructures. In the continuous process of martensite decomposition, precipitation hardening strengthens the alpha’ phase. Eventually, bimodal microstructures consisting in coarse primary alpha and fine secondary alpha+alpha' can be engineered, without involving any hot working in the process. Post-processing is also performed on more complex structures, namely additively manufactured lattices. Since machining cannot be performed on such intricate geometries, a chemical etching procedure inducing a substantial and homogeneous decrease in surface roughness is developed. Dissolution of surface defects results in an improvement of the mechanical efficiency of the structure. As a result, when chemical etching is performed, the relative stiffness approaches that of an ideal structure. Performing subtransus annealing and water quenching in order to induce a dual-phase alpha+alpha’ microstructure substantially increases the ability of these structures to absorb energy during compression. This thesis demonstrates the interest of developing post-process treatments specifically for near-net shape additively manufactured parts. Such treatments partially address critical issues of powder bed AM, expanding the range of possible applications of additively manufactured Ti-6Al-4V. / Doctorat en Sciences de l'ingénieur et technologie / info:eu-repo/semantics/nonPublished

To ensure the widespread adoption of metal Additive Manufacturing (AM) processes, a complete understanding of the interactions between process variables is necessary. The process variables of beam power, beam velocity, deposition geometry, and beam diameter have been shown in prior works to have major effects on resultant melt pool and solidification characteristics, but this list is incomplete. Without accounting for part temperatures prior to deposition, unintended outcomes may result. In the current work, Ti-6Al-4V is studied in the Powder Bed Fusion (PBF) processes to gain an in-depth understanding of how part temperature interactions with other process variables affect physical properties of the process such as melt pool size and variability, part distortion, porosity, and microstructural characteristics. This research is performed through a combination of finite element modelling, single melt track experiments, full part production, and in-situ monitoring in order to gain a full understanding of the underlying relationships between part temperature and part outcomes. In the Arcam Electron Beam Melting (EBM®) process, this knowledge is used to generate a feedback control strategy to constrain prior beta grain width to remain constant while part surface temperatures are allowed to vary. In the Laser Powder Bed Fusion (LPBF) process, deposition is investigated at elevated substrate temperatures and several findings show that unintended part temperature increases can lead to undesirable consequences while prescribed part temperature changes can increase the available processing window and allow for more uniform deposition. This work also shows that both global temperature changes due to substrate heating and local temperature changes due to the choice of scan strategy can be combined into one metric: the temperature encountered by the melt pool during deposition. A combination of destructive and non-destructive characterization methods are utilized to understand and measure the changes to the melt pool and microstructural development that are seen during deposition. The feasibility of using a commercial high speed camera as a tool for thermography is characterized and the ability to discern cooling rates and thermal gradients within and surrounding the melt pool provide validation for trends in melt pool properties generated from simulations. This work provides a greater understanding of the role of part temperature during deposition and presents methodologies to account for the changes to the melt pool and resultant part due to both prescribed and unintended temperature changes during deposition.

The selective laser sintering (SLS) process or the additive manufacturing (AM) enables the construction of a three-dimensional object through melting and solidification of metal powder. The primary advantage of AM over the conventional process is providing the manufacturing flexibility, especially for highly complicated products. The quality of AM products depends upon various processing parameters such as laser power, laser scanning velocity, laser scanning pattern, layer thickness, and hatch spacing. The improper selection of these parameters would lead to parts with defects, severe distortion, and even cracking. I herein perform the numerical and experimental analysis to investigate the interplay between processing parameters and the defect generation. The analysis aims to resolve issues at two different scales, micro-scale and product-scale. At the micro-scale, while the numerical model is developed to investigate the interaction of the laser and materials in the AM process, its advantages and disadvantages compared to an analytical approach (Rosenthal’s equation), which provides a quicker thermal solution, are thoroughly studied. Additionally, numerical results have been verified by series of experiments. Based on the analysis, it is found that the simultaneous consideration of multiple processing parameters could be achieved using the energy density. Moreover, together with existing criteria, a processing window is numerically developed as a guideline for AM users to avoid common defects at this scale including the lack of fusion, balling effect, and over-melting. Thermal results at a micro-scale are extended as an input to determine the residual stress initiation in AM products. The effect of energy density and substrate temperature on a residual stress magnitude is explored. Results show that the stress magnitude within a layer is a strong function of the substrate temperature, where a higher substrate temperature results in a lower stress. Moreover, the stress formation due to a layer’s addition is studied, in which the stress relaxation at locations away from a top surface is observed. Nevertheless, even though the micro-scale analysis can resolve some common defects in AM, it is not capable of predicting product-scale responses such as residual stress development and entire product’s distortion. As a result, the multiscale modeling platform is developed for the numerical investigation at the product level. Three thermal models at various scales are interactively used to yield an effective thermal development calculation at a product-scale. In addition, the influence of the multiple layers, energy densities and scanning patterns on the residual stress formation has been addressed, which leads to the prediction of the residual stress development during the fabrication. The distortion of products due to the residual stress can be described by the product-scale model. Furthermore, among many processing parameters, the energy input and the scanning length are found to be important factors, which could be controlled to achieve the residual stress reduction in AM products. An optimal choice of a scanning length and energy input can reduce an as-built residual stress magnitude by almost half of typically encountered values. Ultimately, the present work aims to illustrate the integration of the computational method as tools to provide manufacturing qualification for part production by the AM process.

With an increasingly aging population, a significant challenge in implantology is the creation of biomaterials that actively promote and accelerate tissue integration while offering excellent mechanical properties. Engineered surfaces with superimposed micro and nanoscale topographies showed great potential to control and direct biomaterial-host tissue interactions. However, these modified surfaces require a careful assessment to prevent potential adverse effects on the fatigue resistance, a factor which may ultimately cause premature failure of biomedical implants. In this context, the surfaces of two widely used biocompatible metals, namely CP Ti and Ti-6Al-4V, were engineered through simple yet efficient chemical treatments which demonstrated the ability to confer exciting new bioactive capacities. The qualitative and quantitative assessments of the fatigue resistance of polished and treated metals were carried out. Results from this study highlight the importance of mechanical considerations in the development and evaluation of nanoscale surface treatments for metallic biomedical implants.