The purpose of this research project was to study the αᵧ phase in Alnico 6. Other phases were studies for comparison. Also the effect of an applied magnetic field on the formation of the αᵧ phase was investigated. Three single crystals of Alnico 6 were heat treated for one hour—one at 1250°C, one at 1000°C, and one at 800°C—and water-quenched. The microstructure of each sample was observed with the optical microscope, and X-ray diffraction patterns were taken to determine the crystal structure of the phases present. Several single crystal samples of Alnico 6 were heat treated at 1000°C and furnace-cooled. Some of the samples were heat treated and furnace-cooled in the presence of an applied magnetic field of about 5000Oe, and the others were heat treated and furnace-cooled without an applied magnetic field. Each set of samples were electrothinned, and the microstructure of the αᵧ and α₁ ₊ α₂ phases was studied using the electron microscope. Electron diffraction patterns and electron micrographs were taken from αᵧ regions and α₁ ₊ α₂ regions of each sample. By a combination of X-ray and electron diffraction, it was determined that the crystal structure of the α, α₁, α₂ and αᵧ phases is body-centered cubic, with a lattice parameter of 2.87 Å. Electron diffraction showed that the crystal structure of the combined α₁ ₊ α₂ phases is ordered body-centered cubic, and that the lattices of these two phases are coherent. Other investigators have found that only the α₁ phase is ordered in Alnico 5 and Alnico 8 and thus is believed be the case in Alnico 6 also. Electron diffraction showed the αᵧ phase to be ordered, with the degree of ordering less than that in the α₁ phase. Some difference was noted between the αᵧ phase formed with a magnetic field and that formed without a magnetic field. The αᵧ formed with a magnetic field showed twinning and some small lattice rotations, while stat formed without a field did not. The reason for this is not known.

M. Tech. (Department of Metallurgical Engineering, Faculty of Engineering and Technology), Vaal University of Technology. / Pure Ti, Nb, Zr, Al and V powders were used as starting materials. Ti, Ti-6Al-4V and Ti-34Nb-25Zr materials produced by SPS were compared on the basis of density, microstructure, biocompatibility, tensile strength and corrosion resistance. In this study, powder metallurgy (PM) processing route was used to fabricate the alloys. The processing route was mechanical alloying (MA) and spark plasma sintering (SPS). Commercially pure metallic powders (Ti, Nb, Zr, V and Al) of different morphological features and different formulations were prepared. Powder mixing for ternary alloys with Ti as the matrix were conducted in a turbula mixer at a speed of 49 rpm. Followed by mechanical alloying of Ti, Ti-6Al-4V and Ti-34Nb-25Zr in a high energy ball mill for 5h at 500rpm, with a ball to powder ratio of 10:1. Spark plasma sintering of Ti, Ti-6Al-4V and Ti-34Nb-25Zr biomedical alloys was conducted using a hybrid spark plasma sintering furnace at a sintering temperature, heating rate, holding time and pressure of 1200°C, 100°C/min, 10min and 50MPa, respectively. Ti-34Nb-25Zr was fabricated in two ways, fully densified and porous samples. The fully densified sample was fabricated at a sintering temperature, heating rate and holding time and pressure of 1200°C, 100°C/min, 10min and 50MPa, respectively. Whereas, porous Ti-34Nb-25Zr was fabricated using NaCl space holder at a sintering temperature, heating rate, holding time and pressure of 750°C, 50°C/min, 5min and 50MPa, respectively. This was done to compare the solid and porous alloy biocompatibility behaviour. Microstructures, elemental compositions. Phase constitution of the sintered specimens were examined using a field emission scanning electron microscope (FE-SEM) equipped with energy dispersive x-ray spectrometer (EDS) and an x-ray diffractometer (XRD). The microstructure of Ti-34Nb-25Zr had pores and precipitates of niobium. Relative density, micro-hardness, biocompatibility and corrosion test was also conducted on the metallographically polished cross sections of sintered specimens. Ti, Ti-6Al-4V and Ti-34Nb-25Zr alloys made from the irregularly shaped Ti powders and sintered on the hybrid sintering machine yielded higher densifications reaching up to 100 % relative densities. Hardness values ranging from 300-600Hv at a load of 0.5kg. The corrosion resistance of the alloys was higher in the range of 2-4 nA/cm2 exhibiting a passive behaviour in simulated body fluids, such as Hank’s, 0.9wt.% NaCl and eagles minimum essential + 10% fetal bovine serum (E-MEM+ 10% FBS). Biocompatibility tests were conducted (cytotoxicity by WST-1 with SaOS-2 human osteosarcoma cells, protein adsorption and surface wettability). Fibronectin adsorption was less for solid Ti and Ti-34Nb-25Zr (<2ng/mm) compared to Ti-34Nb-25Zr porous and Ti-6Al-4V (4 ng/mm). Albumin adsorption was the highest on Ti substrate (3 ng/mm) than on the fully densified and porous Ti-34Nb-25Zr surfaces followed by less adsorption on Ti-6Al-4V. Surface wettability of Ti and Ti-6Al-4V showed a high contact angle of between 93-98° compared to 86° for the Ti-34Nb-25Zr solid alloy, indicating that Ti-34Nb-Zr alloys exhibited hydrophilic behaviour. The surface wettability results correlated well to less fibronectin adsorption on Ti-34Nb-25Zr solid alloy and excellent adsorption for Ti-6Al-4V. Solid and porous Ti-34Nb-25Zr showed less cell proliferation (0.06 and 0.02% cell viability) which was possibly linked to fibronectin adsorption results. Biocompatibility behaviour of Ti-34Nb-25Zr solid and porous alloys was poorer than Ti (0.20% cell viability) and Ti-6Al-4V (0.23% cell viability). There was poor protein adsorption and cell proliferation on all the alloy substrates.

No description available.

No description available.

Selective laser melting (SLM) has been shown to be an attractive manufacturing route for the production of ??/?? titanium alloys, and in particular Ti-6Al-4V. A thorough understanding of the relationship between the process, microstructure and mechanical properties of the components produced by this technology is however crucial for the establishment of SLM as an alternative manufacturing route. The purpose of the present study is thus to determine the microstructure evolution, crystallographic texture and the mechanical properties of SLM Ti-6Al-4V. The effect of several processing parameters on the density and the microstructure of the SLM samples were initially investigated. It was found that different sets of process parameters can be used to fabricate near fully dense components. It was found that the samples built using the optimised process window consist exclusively of ????? martensitic phase precipitated from prior ?? columnar grains. It was observed that the ?? grain solidification is influenced by the laser scan strategy and that the ?? phase has a strong <001> texture along its grain growth direction. The ????? martensitic laths that originate from the parent ?? grains precipitate according to the Burgers orientation relationship. It was found that ????? laths clusters from the same ?? grain have a specific misorientation that minimise the local shape strain. Texture inheritance across successive deposited layers was also observed and discussed in relation to various variant selection mechanisms. The mechanical properties of as-built and stress relieved SLM Ti-6Al-4V built using the same optimised process parameters were then investigated. It was found that the build orientation affects the tensile properties, and in particular the ductility of the samples. Samples built perpendicularly to the building direction showed higher ductility than those built in the vertical orientation. It was also observed that a stress relief heat treatment was beneficial to the mechanical properties of SLM Ti-6Al-4V. The ductility of the stress relieved samples was indeed higher than those found in the as-built condition. It was found that the predominant fracture mode during tensile testing is inter-granular. In terms of high-cycle fatigue, it was found that SLM Ti-6Al-4V is comparable to HIPed cast Ti-6Al-4V but it has a significantly lower fatigue resistance than that of wrought and annealed alloys. It was observed that porosity and the elongated prior ?? grain boundaries decrease substantially the fatigue life of the components. Cracks propagate either by fatigue striation or ductile tearing mechanisms. Using alternative laser scan strategies it was possible to control the microstructure of the as-built samples. It was observed that the laser scan vector length influences several microstructural features, such as the width of the prior ?? grains and the thickness of the ????? laths. It was found that re-melting the same layer has instead little effect on the microstructure. A novel laser scan strategy characterised by much lower laser power and scan speed than those typically used in SLM enabled finally to fabricate SLM Ti-6Al-4V with a microstructure close to that of conventionally manufactured Ti-6Al-4V. This study investigates for the first time the crystallographic texture evolution in Ti-6Al-4V manufactured by SLM. Further, this research presents for the first time the effect of the characteristic microstructure and crystallographic texture on the mechanical properties and fracture of SLM Ti-6Al-4V. Lastly, for the first time this research shows examples of microstructural control during the SLM fabrication of the same alloy using long laser dwell times.

La diffraction des rayons X à haute énergie est une technique puissante pour caractériser les transformations de phases dans les matériaux métalliques. Cette technique nous a permis d'étudier quantitativement le changement de phases ß ? a + ß dans les alliages de titane au cours de traitements thermiques. Nous avons pu caractériser les différentes phases en présence, déterminer en temps réel les cinétiques de transformation et suivre l'évolution des paramètres de maille de chacune des phases. Dans un premier temps, nous avons étudié le changement de phases a + ß ? ß des alliages Ti17, Ti64 et Ti6242, au cours du chauffage en utilisant des vitesses lentes. Les évolutions des paramètres de maille ont été corrélées aux variations de composition chimique des phases (déterminées par ThermoCalc). Les cinétiques de transformation ont ensuite été comparées à celles calculées par l'intermédiaire d'un modèle par champ de phases. Dans le cas de l'alliage Ti17, la transformation de phases ß ? a + ß a également été étudiée au refroidissement. Différentes conditions de refroidissement ont été étudiées : en condition anisotherme au cours de refroidissements continus et en condition isotherme, au cours de maintiens à différentes températures. L'influence du chemin thermique a également été étudié, en réalisant des revenus à partir d'un état [bêta]-métastable à température ambiante. Les cinétiques de transformation obtenues ont été comparées à celles déterminées par résistivité électrique. L'évolution des paramètres de maille des phases et de la largeur à mi hauteur (FWHM) des pics de la phase [bêta] ont permis de mettre en évidence les variations de composition chimique de cette phase et les changements d'état de contrainte engendrés lors des transformations / The high energy X-rays diffraction is a powerful tool to characterize the phase transformation in metallic materials. Its use in the case of titanium alloys has allowed to study the phase transformation during heat treatments. We were able to characterize the different phases involved, to determine in situ the evolution of the mass fraction and the cell parameters of each phase. In the first time, we have studied the phase transformation a + ß ? ß during heating of Ti17, Ti64 and Ti6242 titanium alloys. The cell parameters evolutions have been compared to the chemical composition variations (determined by Thermocalc). Then, the transformation kinetics have been compared to calculated results obtained by a phase field approach. For the Ti17 alloy, we have characterized the phase transformation ß ? a + ß during the cooling. Different conditions were used: the anisothermal condition (during continuous cooling) and the isothermal condition (during dwells at different temperatures). The influence of the thermal path have been considered by means of tempering from a [bêta]-metastable state at room temperature. The evolution of the phase fraction has been compared to kinetics measured by electrical resistivity. The cell parameter and full width at half maximum (FWHM) variations and of each phase have allowed to highlight the changes of the chemical composition and the elastic strain during phase transformation

Orientador: Ana Paula Rosifini Alves Claro / Resumo: Titânio e suas ligas têm sido amplamente aplicados em materiais biomédicos devido as suas excelentes propriedades de volume (relação massa específica e resistência mecânica), biocompatibilidade e resistência à corrosão. As ligas de titânio utilizadas comercialmente são a Ti CP (comercialmente puro) e Ti6Al4V e apesar de muito utilizadas apresentam problemas de citotoxicidade e dessa maneira se faz importante o desenvolvimento de novas ligas que levem a substituição das mesmas. Ligas de titânio do tipo beta têm sido amplamente exploradas devido a sua excelente relação baixo peso específico e módulo de elasticidade, fator que reduz o efeito de Stress Shielding. O objetivo deste trabalho foi processar e caracterizar uma liga de titânio do tipo beta com composição Ti10Mo8Nb6Zr (%m) visando aplicações biomédicas. Os lingotes da liga foram obtidos em um forno de fusão a arco voltaico com atmosfera inerte de gás argônio. A liga foi tratada em um forno tubular a vácuo a 1000ºC por 24 horas para garantir a homogeneidade química, forjada a frio em barras de 9,60 mm de diâmetro e tratadas termicamente novamente a 950°C por 2 horas, seguido de resfriamento em água. A microestrutura e as fases presentes de cada etapa do processamento da liga foram investigadas por Microscopia Óptica (MO), Difração de Raios X (DRX) e Calorimetria Exploratória Diferencial (DSC). Sendo possível constatar a presença da fase beta e a presença de uma possível fase metaestável a ω, comprovando o diagrama de prev... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Titanium and its alloys have been widely applied in biomedical materials because of their excellent volume properties (specific mass ratio and strength), biocompatibility and corrosion resistance. The titanium alloys used commercially are Ti CP (commercially pure) and Ti6Al4V, although they are widely used they present problems of cytotoxicity (Ti6Al4V) and high Young's modulus (Ti CP) and in this way it is important to develop new alloys that lead to their replacement. Beta-type titanium alloys have been extensively explored because of their excellent low specific weight ratio and low modulus of elasticity, which reduces the effect of Stress Shielding, besides absence of problems with citotoxicity. The purpose of this study was processing and characterization of the new beta-titanium alloy Ti10Mo8Nb6Zr (%wt) for biomedical applications. The ingots were obtained in an eletric arc furnace with an inert atmosphere of argon gas. They were heat treated in a tubular vacuum furnace at 1000°C for 24 hours to ensure chemical homogeneity, cold worked in rods with 9.60 mm diameter, and solubilized in tubular furnace under vacuum at 950°C for 2 hours followed by cooling in water. The microstructure and the phases present in each step of the alloy processing were investigated by The microstructure and the phases present at each step of the processing of the alloy were investigated by optical microscopy, X-ray Diffraction (XRD) and Differential Scanning Calorimetry (DSC). It was possible ... (Complete abstract click electronic access below) / Mestre

This work describes advanced fabrication of custom orthopaedic implants using unconventional additive manufacturing technology - Selective Laser Melting (SLM). There was a main focus on custom knee replacement and certainly on its femoral component. The study investigated three general issues within the domain of the usage of additive manufacturing technology in medical application. First, there was an evaluation of process parameters influences of SLM fabrication method on surface and mechanical properties of titanium Ti6Al4V ELI specimens. This material was used because of its biocompatibility and its wide use within implant fabrication. Then, a proposal of the manufacturing strategy was carried out and the fabrication of customized knee femoral component prototype by SLM technology was done. The elaboration of the numerical chain prior the SLM implant fabrication, from patient's CT knee scan to final femoral replacement model, was also done. Then, a proposal of different 3-axis and 5-axis strategies of machining of the fitting femoral surface of bone prototype (3D printed from the powder) using CNC machines FV 25 CNC and TAJMAC ZPS MCV 1210 was projected and also, the 3-axis spiral machining was realised. The individual machining tool paths were generated by software Power Mill from Delcam group. Finally, these machining strategies were generated as a prior step before a machining of real patient’s bone, therefore the machining tests of cartilage and bone were done.

Orientador: Miguel Angel Ramirez Gil / Resumo: O titânio e as suas ligas são utilizados em aplicações biomédicas devido às suas excelentes propriedades, tais como resistência mecânica e biocompatibilidade. As técnicas de modificação de superfície são utilizadas nestas ligas para alterar as propriedades de superfície, aumentar a osseointegração e evitar falhas em implantes. Além destas técnicas, a incorporação de nanopartículas na superfície do implante têm sido grande aliada dos biomateriais, em especial às do óxido de ferro, devido às suas propriedades físico-químicas, sua biocompatibilidade e biodegradabilidade. O objetivo dessa dissertação foi propor método de incorporação de óxido de ferro na superfície nanoporosa da liga experimental Ti10Mo8Nb modificada por oxidação anódica, visando aplicações biomédicas. Os lingotes da liga experimental Ti10Mo8Nb foram obtidos a partir da fusão dos metais puros em forno a arco voltaico. A anodização foi realizada para obtenção das nanoestruturas de TiO2 (tensão de 20 V por 3 h), resultando em diâmetro interno dos nanoporos igual a aproximadamente 24 nm. A síntese do óxido de ferro foi realizada usando o método dos precursores poliméricos, sendo avaliado o comportamento reológico (viscosidade de 22,65 mPa.s) e a temperatura de cristalização para formação de nanopartículas de óxido de ferro. A partir da difratometria de raios X e da microscopia eletrônica de varredura, a temperatura de calcinação mais adequada para a formação da fase pura de hematita foi 600°C. A incorporação do óxid... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Titanium and its alloys are used in biomedical applications because of their excellent properties, such as mechanical resistance and biocompatibility. Surface modification techniques are used to alter the surface properties, increase osseointegration and avoid implant failure. Beside these techniques, nanoparticles incorporation on implant surface are great biomaterials allies, specially iron oxides, due to their physicochemical properties, biocompatibility and biodegradability. The objective of this dissertation was to propose a method of iron oxide incorporation on the surface of experimental alloy Ti10Mo8Nb modified by anodization. The ingots of experimental alloy Ti10Mo8Nb were obtained from melting pure metals in an arc furnace. Anodization process was performed to obtain the TiO2 nanostructures, with internal diameter 24 nm. Iron oxide synthesis was carried out using the method of the polymeric precursors, assessing rheological behavior (22,65 mPa.s viscosity) and crystallization temperature ideal to produce iron oxide nanoparticles. Results from X Ray Diffratogram and Scanning Electron Microscopy presented that the most adequated annealing temperature to pure phase hematite was 600°C. Iron oxide incorporation on alloy surface was performed by immersion and spin coating, and in the second method the deposition was uniform and widespread. Spin coating was performed with 3 and 5 layers of iron oxide deposition, implying that with 5 layers is most appropriate because it do... (Complete abstract click electronic access below) / Mestre

Les implants de corps humain biocompatibles à base de Ti de faible module de Young et sans élèments toxiques sont développés dans deux régimes de matériaux, les alliags cristallins à base de Ti-Nb(-Sn) et les alliages amorphes à base de Ti -Fe -Si. Une série d'alliages à base de Ti-Nb(-Sn) a été synthétisée par une aspiration coulée par la moule de cuivre et soumis à différents traitements thermiques (refroidissement du four ou trempe à l'eau). La microstructure, les propriétés thermiques et mécaniques des échantillons traités telles que la coulée et la chaleur ont été étudiées. On montre que l'addition de Sn augmente la stabilité de la phase β. Les modules de Young de ces alliages ont été également mesurés avec des mesures par ultrasons. Les alliages Ti74Nb26 trempés à l'eau avaient le plus faible module de Young. L'addition de Sn a peu d'impact sur le module de Young des alliages Ti-Nb. Les alliages amorphes à base de Ti- Fe-Si ont été synthétisés par filage à l'état fondu. La capacité de formation des verres, les propriétés thermiques et les propriétés de corrosion des alliages à base de Ti- Fe-Si ont été étudiées. La composition vitreuse a été conçue en fonction de la règle de l'eutectique profond. On a constaté que la région la plus proche du point eutectique ternaire(Ti65Fe30Si5) est une région quasi-cristalline icosaédrique, tandis que le côté plus raide (Si côté riche) de ce point eutectique ternaire est la région de formation de verre. L'effet de L'addition élémentaire mineur (Ge, Pd, Zr) sur la capacité de formation de verre des alliages à base de Ti- Fe-Si a été également étudié. L'observation in situ d'amorphisation des alliages vitreux Ti40Zr10Cu34Pd14Sn2 en faisceau synchrotron a été effectuée. L'alliage a été vitrifié avec succès dans un appareil à sustentation aérodynamique. / The Ti-based biocompatible human body implants of low Young's modulus and without toxic elements are developed in two regime of materials, crystalline Ti-Nb(-Sn) based alloys and amorphous Ti-Fe-Si based alloys. A series of Ti-Nb(-Sn) alloys were synthesized by copper mould suction casting and subjected to different heat treatments (furnace cooling or water quenching). The microstructure, thermal and mechanical properties of the as-cast and heat treated samples were investigated. It is shown that the addition of Sn increases the stability of the β phase. The Young's moduli of these alloys were also measured by ultrasonic measurements. Water-quenched Ti74Nb26 alloy was found to exhibits the lowest Young's modulus. Sn addition has little impact on the Young's moduli of the TiNb alloys. The Ti-Fe-Si based amorphous alloys were synthesized by melt spinning. The glass forming ability, thermal properties and corrosion properties of Ti-Fe-Si based alloys were investigated. The glassy compositions were designed according to the deep eutectic rule. It was found that the region near ternary eutectic point (Ti65Fe30Si5) is an icosahedral quasicrystal forming region, whereas the steeper side (Si rich side) of this ternary eutectic point is the glass forming region. Effect of minor elemental addition (Ge, Pd, Zr) on glass forming ability of the Ti-Fe-Si based alloys was also studied. The in situ observation of amorphization of Ti40Zr10Cu34Pd14Sn2 glassy alloy in synchrotron beam was conducted. The alloy was successfully vitrified in an aerodynamic levitation apparatus.