O presente trabalho tem como objetivo principal o processamento da liga Ti-13Nb-13Zr (com porcentagens em peso) pela técnica da metalurgia do pó denominada space-holder, para se obter scaffolds (suportes porosos ou arcabouços) para osseointegração. Assim primeiramente realizou-se moagens da mistura de pós elementares de Ti, Nb e Zr pesados na proporção em peso da liga Ti-13Nb-13Zr, utilizando-se jarros e esferas de carbeto de tungstênio nos moinhos Fritsch Pulverisette e SPEX. Em todas as moagens utilizou-se álcool isopropílico para avaliar e otimizar sua aplicação como agente controlador de processo. Observou-se que o álcool isopropílico foi eficiente como agente controlador de processo, e que a moagem em moinho SPEX por 8 horas foi a que permitiu a obtenção do pó pré-ligado com a composição da liga Ti-13Nb-13Zr em todas as partículas do pó. Os pós produzidos no moinho Fritsch Pulverisette foram prensados, e as peças a verde obtidas foram sinterizadas em várias condições de tempo e temperatura. Todas as amostras sinterizadas no presente trabalho foram caracterizadas via MEV+EDS, DRX, FRX, microscopia óptica, metalografia quantitativa, e ensaio de dureza. Observou-se que as peças sinterizadas a 1000°C por uma hora foram as que apresentaram maior porosidade, cerca de 30% na amostra na condição álcool, de tal forma que a dureza desta amostra foi de 981 MPa, não muito inferior à dos materiais sinterizados nas demais condições. O pó moído no moinho SPEX por 8h, e o pó elementar de Nb, foram misturados ao pó de naftaleno (50% em volume da peça final), prensados e sinterizados nas condições menos agressivas de sinterização. Além das caracterizações já citadas, estas amostras também foram caracterizadas pelo método de Arquimedes e picnometria de He, para avaliação da porosidade. Destes estudos observou-se que o naftaleno, com tamanhos de partículas entre 500 ?m e 1 mm, gerou de 30 a 50% em volume de porosidade, e permitiu a obtenção de uma estrutura de poros grandes e interconectados, ideais para a aplicação pretendida. Por fim, concluiu-se que é possível obter-se scaffolds da liga de Ti-13Nb-13Zr utilizando-se as técnicas desenvolvidas no presente trabalho. / The present study has, as main goal, the processing of the Ti-13Nb-13Zr alloy (percentages in weight) using the space-holder powder metallurgy technique, to obtain scaffolds for osseointegration. Firstly, elementary powders of Ti, Nb, and Zr weighted to obtain the 74wt.%Ti+13wt.%Nb+13wt.%Zr composition were milled in Fritsch Pulverisette and SPEX mills, using grinding media of tungsten carbide. In all millings, isopropyl alcohol was used to evaluate and optimize its application as process controlling agent. It was observed that the isopropyl alcohol was efficient as process controlling agent, and that the milling by 8 hours in a SPEX mill allowed the production of a pre-alloyed powder with the 74wt.%Ti+13wt.%Nb+13wt.%Zr composition in all particles. The powders produced in the Fritsch Pulverisette mill were pressed, and the obtained green bodies were sintered in several time and temperature conditions. All the samples sintered in the present work were characterized using SEM-EDX, XRD, XRF, optical microscopy, quantitative metallography, and microhardness test. It was observed that the samples sintered at 1000°C for one hour presented the highest porosity, around 30% for the alcohol condition, presenting a microhardness of 981 MPa, not so distant of the values found for samples sintered using other conditions. The powder milled in the SPEX mill for 8 hours, and the niobium powder, were mixed with naphtalene powder (50% in volume), pressed and sintered using the less aggressive sintering conditions. Besides the characterization techniques already cited, these samples were also characterized by Archimedes test and He picnometry, to evaluate the porosity. From these studies, it could be observed that the naphtalene, with particle size ranging from 500 ?m to 1 mm, produced samples with 30 to 50% of porosity in volume, and allowed the formation of a structure of large and interconnected pores. It could be concluded that it is possible to obtain scaffolds of the Ti-13Nb-13Zr alloy using the techniques developed in the present work.

In the scope of this study, TiNi foams with porosities in the range of 39-64 vol% were processed from prealloyed powders by Mg space holder technique. Porous TiNi alloys displayed homogeneously distributed spherical pores with interconnections, which is suitable for bone ingrowth. Porous Ti-50.8 at%Ni alloys were processed by sintering at 1200 &deg / C for 2 h to analyze the microstructure as well as mechanical behavior. SEM, TEM and XRD studies were conducted for the characterization of microstructure and phase analyses in addition to the mechanical characterization performed by monotonic and superelasticity compression tests as well as compressive fatigue tests. It was observed that stress required to trigger martensitic transformation was decreased via increasing porosity. The monotonic compression test results also indicated that altering the porosity content of TiNi foams leads to different monotonic compression behaviors. It was observed that the foams display more bulk deformation like behavior as a composite structure composed of TiNi and macropores when the porosity content was low. As the porosity content has increased, the struts became more effective and deformation proceeds by the collapse of favorable struts. On the other hand, cyclic superelasticity tests results indicated that maximum achieved and recovered strain values at the end of fifth cycle increase while the fraction of strain recovered at the end of fifth cycle decreases with decreasing porosity content. Furthermore, the fatigue lives of the processed foams were observed to vary within a band which has a width decreasing with decreasing &sigma / max / &sigma / y yielding an endurance limit ranging in between 26-89 MPa or 0.5-0.6 &sigma / y. Fractography studies on the failed foams after fatigue testing revealed that the failure occurs by the coalescence of micro-cracks initiated from pore walls leading to macro-cracks aligned at 45o with respect to the loading axis. In addition to the mentioned characterization studies, the effects of sintering temperature and time on TiNi foams with 58 vol% porosity as well as heat treatment on the microstructure and the mechanical behavior of TiNi foams with 49 vol% porosity were analyzed with SEM and compression tests. Aging of TiNi foams with 49 vol% porosity at 450 &deg / C for 1.5 h has shown that the presence of Ti3Ni4 precipitates improve the superelastic response.

In the present study, production of titanium and Ti6Al4V alloy foams has been investigated using powder metallurgical space holder technique in which magnesium powder were utilized to generate porosities in the range 30 to 90 vol. %. Also, sintering of titanium and Ti-6Al-4V alloy powders in loose and compacted condition at various temperatures (850-1250oC) and compaction pressures (120-1125 MPa), respectively, were investigated to elucidate the structure and mechanical properties of the porous cell walls present due to partial sintering of powders in the specimens prepared by space holder technique. In addition, microstructure and mechanical response of the porous alloys were compared with the furnace cooled bulk samples of Ti-6Al-4V-ELI alloy subsequent to betatizing. It has been observed that the magnesium also acts as a deoxidizer during foaming experiments, and its content and removal temperature is critical in determining the sample collapse. Stress-strain curves of the foams exhibited a linear elastic region / a long plateau stage / and a densification stage. Whereas, curves of loose powder sintered samples were similar to that of bulk alloy. Shearing failure in foam samples occurred as series of deformation bands formed in the direction normal to the applied load and cell collapsing occured in discrete bands. Average neck size of samples sintered in loose or compacted condition were found to be different even when they had the same porosity, and the strength was observed to change linearly with the square of neck size ratio. The relation between mechanical properties of the foam and its relative density, which is calculated considering the micro porous cell wall, was observed to obey power law. The proportionality constant and the exponent reflect the structure and properties of cell walls and edges and macro pore character.

Porous TiNi alloys (Ti-50.4 at. %Ni and Ti-50.6 at. %Ni) with porosities in the range 21%-81% were prepared successfully applying a new powder metallurgy fabrication route in which magnesium was used as space holder resulting in either single austenite phase or a mixture of austenite and martensite phases dictated by the composition of the starting prealloyed powders but entirely free from secondary brittle intermetallics, oxides, nitrides and carbonitrides. Magnesium vapor do not only prevents secondary phase formation and contamination but also provides higher temperature sintering opportunity preventing liquid phase formation at the eutectic temperature, 1118 &deg / C resulting from Ni enrichment due to oxidation. By two step sintering processing (holding the sample at 1100 &deg / C for 30 minutes and subsequently sintering at temperatures higher than the eutectic temperature, 1118 &deg / C) magnesium may allow sintering probably up to the melting point of TiNi. The processed alloys exhibited interconnected (partially or completely depending on porosity content) open macro-pores spherical in shape and irregular micro-pores in the cell walls resulting from incomplete sintering. It has been found that porosity content of the foams have no influence on the phase transformation temperatures while deformation and oxidation are severely influential. Porous TiNi alloys displayed excellent superelasticity and shape memory behavior. Space holder technique seems to be a promising method for production of porous TiNi alloys. Desired porosity level, pore shape and accordingly mechanical properties were found to be easily adjustable.

Porous Ti-6Al-4V alloys are widely used in the biomedical applications for hard tissue implantation due to its biocompatibility and elastic modulus being close to that of bone. In this study, porous Ti-6Al-4V alloys were produced with a powder metallurgical process, space holder technique, where magnesium powders were utilized in order to generate porosities in the range of 50 to 70 vol. %. In the productions of Ti-6Al-4V foams, first, the spherical Ti-6Al-4V powders with an average size of 55 &mu / m were mixed with spherical magnesium powders sieved to an average size of 375 &mu / m, and then the mixtures were compacted with a hydraulic press under 500 MPa pressure by using a double-ended steel die and finaly, the green compacts were sintered at 1200

O presente trabalho tem como objetivo principal o processamento da liga Ti-13Nb-13Zr (com porcentagens em peso) pela técnica da metalurgia do pó denominada space-holder, para se obter scaffolds (suportes porosos ou arcabouços) para osseointegração. Assim primeiramente realizou-se moagens da mistura de pós elementares de Ti, Nb e Zr pesados na proporção em peso da liga Ti-13Nb-13Zr, utilizando-se jarros e esferas de carbeto de tungstênio nos moinhos Fritsch Pulverisette e SPEX. Em todas as moagens utilizou-se álcool isopropílico para avaliar e otimizar sua aplicação como agente controlador de processo. Observou-se que o álcool isopropílico foi eficiente como agente controlador de processo, e que a moagem em moinho SPEX por 8 horas foi a que permitiu a obtenção do pó pré-ligado com a composição da liga Ti-13Nb-13Zr em todas as partículas do pó. Os pós produzidos no moinho Fritsch Pulverisette foram prensados, e as peças a verde obtidas foram sinterizadas em várias condições de tempo e temperatura. Todas as amostras sinterizadas no presente trabalho foram caracterizadas via MEV+EDS, DRX, FRX, microscopia óptica, metalografia quantitativa, e ensaio de dureza. Observou-se que as peças sinterizadas a 1000°C por uma hora foram as que apresentaram maior porosidade, cerca de 30% na amostra na condição álcool, de tal forma que a dureza desta amostra foi de 981 MPa, não muito inferior à dos materiais sinterizados nas demais condições. O pó moído no moinho SPEX por 8h, e o pó elementar de Nb, foram misturados ao pó de naftaleno (50% em volume da peça final), prensados e sinterizados nas condições menos agressivas de sinterização. Além das caracterizações já citadas, estas amostras também foram caracterizadas pelo método de Arquimedes e picnometria de He, para avaliação da porosidade. Destes estudos observou-se que o naftaleno, com tamanhos de partículas entre 500 ?m e 1 mm, gerou de 30 a 50% em volume de porosidade, e permitiu a obtenção de uma estrutura de poros grandes e interconectados, ideais para a aplicação pretendida. Por fim, concluiu-se que é possível obter-se scaffolds da liga de Ti-13Nb-13Zr utilizando-se as técnicas desenvolvidas no presente trabalho. / The present study has, as main goal, the processing of the Ti-13Nb-13Zr alloy (percentages in weight) using the space-holder powder metallurgy technique, to obtain scaffolds for osseointegration. Firstly, elementary powders of Ti, Nb, and Zr weighted to obtain the 74wt.%Ti+13wt.%Nb+13wt.%Zr composition were milled in Fritsch Pulverisette and SPEX mills, using grinding media of tungsten carbide. In all millings, isopropyl alcohol was used to evaluate and optimize its application as process controlling agent. It was observed that the isopropyl alcohol was efficient as process controlling agent, and that the milling by 8 hours in a SPEX mill allowed the production of a pre-alloyed powder with the 74wt.%Ti+13wt.%Nb+13wt.%Zr composition in all particles. The powders produced in the Fritsch Pulverisette mill were pressed, and the obtained green bodies were sintered in several time and temperature conditions. All the samples sintered in the present work were characterized using SEM-EDX, XRD, XRF, optical microscopy, quantitative metallography, and microhardness test. It was observed that the samples sintered at 1000°C for one hour presented the highest porosity, around 30% for the alcohol condition, presenting a microhardness of 981 MPa, not so distant of the values found for samples sintered using other conditions. The powder milled in the SPEX mill for 8 hours, and the niobium powder, were mixed with naphtalene powder (50% in volume), pressed and sintered using the less aggressive sintering conditions. Besides the characterization techniques already cited, these samples were also characterized by Archimedes test and He picnometry, to evaluate the porosity. From these studies, it could be observed that the naphtalene, with particle size ranging from 500 ?m to 1 mm, produced samples with 30 to 50% of porosity in volume, and allowed the formation of a structure of large and interconnected pores. It could be concluded that it is possible to obtain scaffolds of the Ti-13Nb-13Zr alloy using the techniques developed in the present work.

Thesis (MScEng) -- Stellenbosch University, 2014. / ENGLISH ABSTRACT: In this study, commercially pure titanium foam was produced using space holder powder metallurgy techniques. Titanium foam is attractive as a scaffolding material for bone replacement and implants in the body. The porous morphology of the foam promotes osteogenesis, while the mechanical behaviour of the foam is closer to that of bone, which has an elastic moduli range of 5 - 40 GPa. Titanium foam was manufactured from powder mixtures of commercially pure titanium (CPTi) powder mixed with 41.4 wt% ammonium bicarbonate (ABC) powder and 1.45 wt% polyethyl glycol (PEG) powder. In this study, two CPTi powders with different particle size distributions, < 75 μm (-200 mesh, designated TiAA) and < 200 μm (-100 mesh, designated TiG), were mixed with the space holder ABC powder, that had been sieved into specified particle size ranges. The size ranges of space holder material studied were: 0 - 710, 250 - 425, 425 - 560, and 560 - 710 μm. This allowed foams with different large or macropore distributions to be produced from the different mixtures. The mixtures were uniaxially compacted at 100 MPa into transverse rupture bars. The ABC and PEG was then removed by thermal debinding in air for 5 hours at 100 °C and 1 hour at 330 °C each, consecutively. The debound samples are then sintered under high (10-6 mbar) vacuum on yttria-stabilised zirconia substrates, heating at 5 °C/min to 1200 °C, with a 2 hour hold at temperature. The microstructures of the different foams were evaluated by examining the polished samples using light optical microscopy. Three point bend tests were conducted on the sintered bars in order to determine the flexural strength and flexural modulus of the different foams. The produced foams had a relative density range between 37.5 - 62.5 % and average macro pore size range between 300 - 500 μm. The foams were found to have an elastic modulus similar to that of bone, 2 - 7 GPa. Finally, the mechanical properties of the foams were compared to known open foam mechanical models and other research projects. It was found that: (i) changes in either metal or space holder powder influences the sintering behaviour of metal foams, (ii) sintered titanium foams with similar densities but different macro/micropore size distributions have different mechanical responses to stress and (iii) the Ashby-Gibson model, based on foam density alone, gives a rough estimate of mechanical properties for the titanium foams studied, but does not capture variations due to pore size distribution. / AFRIKAANSE OPSOMMING: In hierdie studie is kommersiële suiwer titaanskuim geproduseer met behulp van ruimtehouer poeier metallurgie tegnieke. Titaanskuim is aantreklik as 'n raamwerkmateriaal vir beenvervanging en -inplantings in die liggaam. Die poreuse morfologie van die skuim bevorder osteogenese, terwyl die meganiese gedrag van die skuim naby aan dié van been is, met ‘n elasticiteitsmodulus tussen 5 - 40 GPa. Titaanskuim is vervaardig van ‘n poeier mengsel van kommersiële suiwer titaan (CPTi) poeier gemeng met 41,4 gew% ammonium bikarbonaat (ABC) poeier en 1.45 gew% poli-etileenglikol (PEG) poeier. In hierdie studie is twee tipes CPTi poeiers met verskillende deeltjiegrootteverspreiding, < 75 μm (-200 stofdigtheid, TiAA genoem) en <200 μm (-100 stofdigtheid, TiG genoem), met die ruimtehouer ABC-poeier, wat in bepaalde deeltjiegroottereekse gesif is, gemeng. Die wisselende groottes van ruimtehouer wat bestudeer is, was: 0 - 710, 250 - 425, 425 - 560, 560 - 710 μm. Dit het die vervaardiging van skuim met verskillende groot of macroporeuse vanaf die verskillende mengsels toegelaat. Die mengsel is teen 100 MPa in een rigting gekompakteer. Die ABC en PEG is dan verwyder word deur termiese ontbinding in lug vir 5 uur by 100 °C en 1 uur by 330 °C elk, onderskeidelik. Die ontbinde monsters is dan onder hoë (10-6 mbar) leemte op yttrium-gestabiliseer zirconia-substraat, met verwarming teen 5 °C/min tot 1200 °C met 'n verdere 2 uur by 1200 °C, gesinterd. Die mikrostrukture van die verskillende skuim is geëvalueer deur gepoleerde monsters met behulp van ‘n ligmikroskopie te ondersoek . Driepunt draaitoetse is op die gesinterd stawe uitgevoer om die buigsterkte en buigmodulus van die verskillende skuime te bepaal. Die vervaardigde skuime se relatiewe digtheid het tussen 37,5 - 62,5 % gewissel en die gemiddelde makroporiegrootte tussen 300 - 500 μm gewissel. Die skuim het 'n elastisiteitsmodulus soortgelyk aan dié van been getoon, 2 – 7 GPa. Ten slotte is die meganiese eienskappe van die skuim met bekende oop skuim meganiese modelle en ander navorsingsprojekte vergelyk. Daar is bevind dat: (i) veranderinge in óf metaal of ruimtehouer poeier beïnvloed die sinteringgedrag van metaalskuime, (ii) gesinterd titaniumskuim met soortgelyke digthede, maar verskillende makro / mikroporeuse verdelings, toon verskillende meganiese reaksies op stres en die Ashby-Gibson model, gebaseer op die skuimdigtheid alleen, (iii) wat 'n rowwe skatting van die meganiese eienskappe vir die bestudeerde titaniumskuime gee, maar nie die variasies ingrootteverspreiding van porieë ondervang nie.

Ziel der Arbeit war es in einem pulvermetallurgischen Ansatz gasverdüste Ti-45Nb-Pulver mittels Heißpressen zunächst zu kompakten Formkörpern zu verpressen und über geeignete Gefügeeinstellung und bestmöglicher Partikelverzahnung maximale Druckfestigkeiten bei gleichzeitig niedrigem E-Modul zu erhalten. In einem nächsten Schritt wurden mittels Heißpressen mit Platzhalterphase definierte Porenanteile in die Formkörper eingebracht und der Einfluss dieser auf die mechanischen Eigenschaften untersucht. Die porösen Strukturen sollen als Knochenersatzmaterial in einem osteoporotischen Knochendefekt dienen. In einem solchen Defekt stellen Druckkräfte den dominierenden Belastungsfall dar. Die mechanische Charakterisierung der im Rahmen der Arbeit erzeugten porösen Formkörper erfolgte daher im Druckversuch. Die Oberfläche eines metallischen Knochenersatzmaterials muss chemisch und topografisch modifiziert werden, um damit Einfluss auf das Gleichgewicht zwischen zellbiologischen Prozessen zum Knochenauf- und -abbau an der Grenzfläche zwischen Implantat und Knochengewebe zu nehmen. Im speziellen Fall von Osteoporose, wo dieses Gleichgewicht nachweislich gestört ist, spielt die Stimulation des Knochenaufbaus eine besondere Rolle. Für Strontiumspezies konnte eine das Knochenwachstum stimulierende Wirkung und die Inhibierung des Knochenabbaus in mehreren Studien gezeigt werden. Ein weiteres Ziel der Arbeit stellte daher die Erzeugung von strontiumhaltigen Hydroxylapatitschichten mittels Elektrodeposition dar. Die erzeugten Schichten wurden strukturell, morphologisch und chemisch charakterisiert. Weiterhin wurden die Sr-Freisetzung aus den Schichten und die zellbiologische Wirkung untersucht. Konzepte zur Abscheidung auf planaren Legierungsoberflächen konnten in einem nächsten Schritt im Rahmen einer Machbarkeitsstudie auf poröse Ti-45Nb Strukturen übertragen werden. / Aim of the work was the production of dense Ti-45Nb material by hot-pressing of gas-atomized Ti-45Nb powder. Maximum compression strength and low Young’s modulus values were obtained by means of a tailored microstructure and improved interlinking of the powder particles. In a next step defined amounts of porosity were introduced by hot-pressing the alloy powder with a space holder phase. The produced porous structures should be used as bone substitute material in an osteoporotic bone defect. Compression is the dominating load in such a defect. Accordingly, compression tests were conducted to assess the mechanical properties. The surface state of metallic bone replacement materials plays an important role regarding the osseointegration of the material into the surrounding bone tissue. A chemical and topographical modification of the surface is necessary to influence the equilibrium between the formation and resorption of bone on the interphase of implant and bone tissue. Especially in case of osteoporosis the stimulation bone formation is essential. Several studies have shown that strontium species have a positive effect on the formation of bone tissue and the inhibition of bone resorption. Therefore, a further aim of the work was the electrodeposition of Sr-containing hydroxyapatite layers and the structural, morphological and chemical characterization of the deposited layers. Furthermore, the release of Sr-species from the layers and the effect on hMSC (human mesenchymal stroma cells) were examined. Originating from studies on planar alloy surfaces, the transfer of the deposition approaches was shown in a proof of concept on the porous Ti-45Nb scaffolds.