Refine
Document Type
- Doctoral thesis (7)
Has Fulltext
- yes (7)
Is part of the Bibliography
- no (7) (remove)
Keywords
- Titanaluminide (3)
- Titanlegierung (3)
- Carbide (2)
- Creep (2)
- Kriechen (2)
- Metal injection moulding (2)
- Metallpulver (2)
- Metallspritzguss (2)
- Nioblegierung (2)
- Spritzgießen (2)
Institute
The main subject of this work was the investigation of sintering behavior, microstructure, mechanical properties and biocompatibility of metal injection moulded (MIM) Ti-Nb alloys for biomedical applications. Commercially pure titanium (CP-Ti) samples were also fabricated by MIM as a reference. The sintering behavior of MIM Ti-Nb alloys was studied at first, in order to roughly determine the sintering parameters in the following investigations. Dilatometry was applied to investigate the linear shrinkage of MIM Ti-Nb samples from room temperature to 1500 °C at a heating rate of 3 °C/min under argon atmosphere. Various sintering parameters and Nb contents were used to investigate their influences on microstructure and mechanical properties of MIM Ti-Nb alloys by means of density measurements, optical microscopy (OM), X-ray diffraction (XRD), scanning electron microscopy (SEM) and mechanical testing. Transmission electron microscopy (TEM) and high energy X-ray diffraction (HEXRD) measurement were applied to investigate the nature and precipitation of the unexpected titanium carbide precipitates in MIM Ti-Nb alloys. Initial cell adhesion and cell proliferation assays of human umbilical cord perivascular cells (HUCPV) on MIM Ti-Nb alloys were performed for biocompatibility characterization. The results of this work show that MIM Ti-Nb and MIM CP-Ti samples have been successfully fabricated and the as-sintered samples show good shape retention without distortion compared to the green sample. The sintering process of MIM Ti-Nb alloys consists of three main steps – Ti-diffusion step, Ti-Nb-diffusion step and Matrix-diffusion step. With increasing sintering temperatures and time, MIM Ti-Nb alloys exhibit lower porosity and higher Young’s modulus. A higher Nb content in MIM Ti-Nb alloys leads to an increase of carbide area fraction and porosity. The three factors – Nb content, carbide area fraction and porosity – determine the mechanical properties of MIM Ti-Nb alloys. An increase of Nb content and amount of carbides as well as a lowered porosity lead to a higher tensile strength. A decrease of Young’s modulus can be expected with higher Nb content and porosity. A high amount of titanium carbides can result in very poor ductility, but annealing and quenching process can significantly improve the elongation by dissolving the carbides. MIM Ti-Nb alloys exhibit good biocompatibility, indicating their potential for implant applications.
The increasing demand for competitive, whilst also environment-friendly airplane travel, compels the design of highly efficient engines in the aeronautical field. A potential for improvement of traditional polycrystalline Ni-based superalloys, aiming higher creep resistance, was investigated. The approach adopted the concept of metal matrix composites (MMCs) to incorporate a rigid discontinuous phase, in the form of particles, to a γ’-strengthened Ni-based superalloy. In order to make the concept feasible, different microstructures resulting from diverse manufacturing techniques were investigated. By using distinct mixing and sintering methods, powders of Inconel X-750 and TiC were combined to form composites containing 15 vol.% of reinforcing particles. Powders were prepared with low and high energy milling processes, and formed by uniaxial pressure sintering and spark plasma sintering methods. Non-reinforced variants and composites had microstructures thoroughly examined at their initial state and after long isothermal aging treatments. Selected variants were further submitted to tensile and compression creep tests at temperatures between 700 and 800 °C, in the stress range of 200 to 500 MPa.
A comprehensive analysis was conducted using techniques such as EBSD, XRD Rietveld refinement, EDS and TEM to evaluate the development of γ’, η and TiC phases, determining the achievable microstructures with each fabrication method and establishing their evolution after aging treatments over times up to 1000 h. Likewise, creep properties were analyzed by obtaining parameters such as creep exponents, threshold stresses and activation energies. A creep life estimation was conducted with the use of a Monkman-Grant relationship and a Larson-Miller parametrization. Lastly, the potential for a reduction in creep strain rates in a working turbine blade, considering the density of investigated materials as a parameter, was evaluated.
All produced composites presented power law creep, with dislocations surpassing γ’ particles by climb. The variant produced by high energy ball milling and spark plasma sintering exhibited the highest creep rates, resulting from intense diffusion through grain boundaries. It also presented η phase after long isothermal aging, which affects negatively the creep resistance. Contrastingly, in the variant produced by low mixing combined with pressure sintering the lowest creep rates were observed. It was proposed that reinforcing TiC particles effectively acted as a load bearing phase, counterbalancing the adverse effects of the intergranular diffusion in the refined microstructure. Furthermore, a higher microstructural stability was observed in this variant, resulting from limited interaction between TiC particles and the matrix during fabrication.
The powder metallurgically produced beta titanium alloys (traditional PM beta Ti-alloys) have long been plagued by high impurities contamination. For binder-based powder technologies, they originate from the sintering atmosphere, the debinding processes and the starting powders. In general, a normal carbon residual of binder-based powder technologies is capable of incurring the formation of aligned TiCx particles along beta grain boundaries (GB-TiCx) in most classes of beta Ti-alloys. Whereas, oxygen atoms are likely to deteriorate the ductility of PM Ti alloys by promoting the formation of diverse brittle phases and/or altering the deformation modes. Such materials exhibiting rather low toughness to strain ratios are not an option for critical structural applications, where catastrophic damage is completely unacceptable.
In this study, biotolerant metastable beta Ti-20Nb-10Zr alloys, containing a certain amount of carbon, oxygen residuals originated from materials processing and consequently 0.5 vol.% in situ synthesized TiCx particles, were fabricated via metal-injection-molding (MIM). With varying yttrium (Y) addition, the effects of Y-induced oxygen scavenging, beta-grain refinement and porosity increment on tensile properties were systematically investigated. To scavenge oxygen from the beta Ti-matrix, the Y elemental powder with a maximum particle size of 15 µm (e.g. <12 µm or 1200 mesh) is more appropriate than the commonly used <45 µm (i.e. 325 mesh) sized powder or larger ones and without significant detrimental effect on the as-sintered density of beta Ti-alloys.
A novel toughening strategy was proposed by regulating TiCx precipitation evolution and resultantly adjusting particles distribution pattern. Synchrotron radiation identified that two separate TiCx precipitation-type reactions occurred at the beta phase region and the alpha/beta region. In a narrow temperature range between these two precipitation reactions, dissolution of carbides was observed just below alpha/beta transus. Y addition can postpone TiCx precipitation. On the basis of those mechanisms, adjusting TiCx particle distribution was proposed for the first time, specifically a combination of yttrium addition (Y) and carbide spheroidization reprecipitation annealing (CSRA). As a result, aligned GB-TiCx particles were adjusted to dispersed intragranular TiCx particles. An apparent toughening effect (≈ 113% increment reaching elongation = 8.3%) was achieved after TiCx redistribution, while non-optimally aligned TiCx pattern seriously limited tensile toughness of materials. Here, the mechanisms of TiCx redistribution behavior and its toughening are elucidated systematically.
Titanium and its alloys have been widely used as implant biomaterials due to their suitable combination of mechanical properties and biological compatibilities. At present, about 70-80% of implants are made of metallic biomaterials. Compared with magnesium alloys, stainless steel and cobalt alloys, titanium alloys have a higher specific strength, high corrosion resistance, and excellent biocompatibility. With research, Ti-Nb biomedical titanium alloys have been constantly developed. In the Ti-Nb alloy, the amount of Nb is usually from 16% to 42% (wt.%) which is about 10% to 30% (at.%). As reported, Mn as a trace element to the human body has the potential to be used in bio-materials. Therefore, this study aims at the partial replacement of Nb by Mn to reduce the costs, without deteriorating the mechanical properties. Moreover, it must be ensured good biocompatibility and corrosion resistance. This is the first investigated on Ti-Mn-Nb ternary alloys.
In this work, According to β single-phase field, Ti-xMn-yNb (x=4, 10, 16; y=2, 8, 14, at.%) alloys (arc-melted) have been fabricated. The Ti-Mn-Nb alloys are investigated by optical microscopy (OM), X-ray diffraction (XRD), hardness test, transmission electron microscopy (TEM) and mechanical testing. By screening study on alloy, Ti-10Mn-14Nb (at.%) (Ti-10Mn-23.7Nb (wt.%)) is the optimal alloy with tensile strength (760 MPa) and elongation (10.5%). After that, the Metal Injection Moulding (MIM) is used to prepare Ti-Mn-Nb alloys. The MIM method can greatly reduce the processing cost. MIM Ti-xMn-yNb (x=3, 4, 6; y=1, 2, 4, at.%), Ti-4Mn-14Nb and Ti-10Mn-14Nb alloys are fabricated. Among them, a very good combination of mechanical properties is achieved for MIM processed Ti-4Mn-2Nb (at.%) (Ti-4.5Mn-3.8Nb (wt.%)), namely a YS of 642 MPa, UTS of 725 MPa and high ductility of 16% elongation to fracture. With further investigations, when the yttrium content is 0.1% (at.%), the tensile strength of Ti-4Mn-2Nb-0.1Y (at.%) (Ti-4.5Mn-3.8Nb-0.18Y (wt.%)) is increased to 785 MPa while elongation of 12.9%. These mechanical properties already exceed Ti-6Al-4V (ASTM F2885 Grade 5 undensified).
In the in vitro evaluation, in comparison with MIM pure titanium, human osteoblasts MG63 adhered as well and proliferated on the surface of MIM Ti-Mn-Nb specimens. In the supernatant after cell culture, the Ti-Mn-Nb alloy shows similar osmolality and pH value results as MIM pure titanium. By LDH assay and DNA isolation, the MIM Ti-Mn-Nb alloys are not found to be toxic to MG63 cells.
In the study of corrosion resistance in Hanks’ balanced salt solution (HBSS) at 37 °C, the corrosion current densities as well as the impedance of MIM Ti-Mn-Nb alloys are all better than those of MIM pure titanium and even better than those of MIM Ti-6Al-4V alloy.
TiAl alloys with a high addition of Nb have recently been applied in the aerospace and automotive fields due to their excellent high-temperature properties. The C additions to TiAl alloys have been reported to improve their strength and creep resistance through solid-solution hardening and / or precipitation hardening. In this work powder metallurgy (PM) based Ti-45Al-5Nb-xC (x=0, 0.5 0.75 and 1.0 at. %) alloys were systematically investigated after different heat treatments. The research is mainly concerned with the temperature range from 800 to 1000ºC which is interesting for processing as well as applications. The results show that the addition of C influences the phase transformations in Ti-45Al-5Nb and that the addition of Nb may influence the carbon solubility in TiAl alloys at high temperatures. The carbon solubility in Ti-45Al-5Nb is > 1.0 at. % at 1400°C, but between 0.5 and 0.75 at. % at 1000°C, and less than 0.5 at. % at 800°C. The carbide precipitation and development of carbide morphology are discussed in great detail. The thermal stability of P-Ti3AlC carbides in Ti-45Al-5Nb-xC alloys is increased, which might be attributed to the addition of high amounts of Nb, or the high amount of carbon, or a combination of both. In heat-treated Ti-45Al-5Nb-0.5C and Ti-45Al-5Nb-0.75C, H-type carbides are not detected to form during annealing. The addition of Nb may increase the formation temperature of the H-Ti2AlC precipitate phase.
Development of creep resistant titanium aluminide alloys for the Metal Injection Moulding process
(2014)
Titanium aluminides show great technological potential due to their light weight and excellent creep resistance. Their utilisation thus offers a potential to decrease fuel consumption and simultaneously improve the performance of components subjected to stress at high temperatures. However, shaping of titanium aluminides is still a very challenging and costly task considering their brittleness and the sensitivity on chemical composition. Therefore powder metallurgy near-net shape manufacturing techniques are very attractive to decrease material waste and reduce overall processing costs.
This research work was focused on the preparation, characterisation and optimisation of creep resistant titanium aluminides for the Metal Injection Moulding (MIM) process. Considering the little information available regarding processing of titanium aluminides by MIM, this work had firstly the goal of assessing the creep behaviour of a reference titanium aluminide alloy. Secondly, alloy variations with compositions based on the reference material were designed with the objective of improving the creep resistance, especially concerning primary creep. The basic strengthening mechanisms applied involved the addition of slow diffusing elements and elements that cause precipitation of hard particles.
The specimens were prepared by using pre-alloyed powder and mixtures of a master alloy (pre-alloyed) and elemental powders. Consequently, a great deal of effort was spent in the characterisation of the sintering behaviour in order to achieve reliable test pieces. Even though both methods can deliver sound specimens, the pre-alloyed powder approach led to the best results in terms of residual porosity and microstructural homogeneity.
The mechanical testing results indicate that processing of titanium aluminides by MIM is feasible and acceptable creep properties can be achieved with the proper sintering parameters. Even though the ductility at room temperature was considerably limited due to the residual porosity and high amounts of impurities intrinsic to the MIM process, alloys developed within this study showed improved primary creep resistance in the high stress – high temperature regime. In particular alloy variations containing additions of Mo, Si and Gd led to a considerable improvement of the primary creep resistance in comparison to the reference material at 800°C – 350 MPa loading.
Um das volle Eigenschaftspotential von Titanaluminiden auszuschöpfen, ist eine homogene und feinkörnige Mikrostruktur notwendig. Um diese zu erreichen, erweist sich Schmieden als ideal, da so eine Rekristallisation und damit Kornfeinung mit einer Formgebung kombiniert werden kann. Die aktuelle Legierungsentwicklung zielt mit β-stabilisierten Legierungen darauf ab, konventionelle Umformverfahren für die sonst schwer umformbaren γ-TiAl-Legierungen zu erschließen. Dadurch ließe sich eine für den industriellen Einsatz notwendige Kostenreduktion in der Herstellung von geschmiedeten Bauteilen auf Basis von Titanaluminiden erreichen. Aus diesem Grund wurden drei β-stabilsierte Legierungsvarianten gewählt und hinsichtlich ihrer mechanischen Eigenschaften und Umformbarkeit mit TNB-V2, einer der Legierungen, die den Stand der Technik zu Beginn dieser Arbeit darstellt, verglichen. Als optimal, hinsichtlich der geforderten Eigenschaften, erwies sich die Legierung Ti-44,5Al-6,25Nb-0,8Mo-0,1B, welche im weiteren Verlauf des Projektes als TNB-V4 bezeichnet wird.
Da die notwendigen Prozessparameter für die Umformung der jeweiligen Legierung angepasst werden müssen, wurde in der vorliegenden Arbeit ein entsprechendes Prozessfenster für TNB-V4 entwickelt. Die optimalen Parameter für eine Umformung sind eine Umformtemperatur im Bereich von 1210 - 1290 °C, eine Umformgeschwindigkeit von < 5∙10^(-3) s^(-1) und ein Umformgrad von φ>65 %. Die sehr hohen Umformtemperaturen und die Affinität zu Sauerstoff machen eine Schutzgasatmosphäre bzw. Vakuum während der Umformung unabdingbar. Aufbauend auf dem feinkörnigen Gefüge nach Umformung lässt sich das Gefüge durch gezieltes Wärmebehandeln hinsichtlich Phasenaufteilung und Gefügeaufbau in gewissen Grenzen den Erfordernissen anpassen. Als ideale Wärmebehandlungsparameter erwiesen sich ein Lösungsglühen bei 1270 °C für eine Stunde mit Luftabkühlung und anschließendes Auslagern bei 800 °C für sechs Stunden mit Ofenabkühlung.
Anhand einer Bauteilschmiedung wurde gezeigt, dass das im Labormaßstab entwickelte Prozessfenster auch auf große Bauteile übertragen werden kann. Dies gilt allerdings nicht für die Wärmebehandlung, da die chemische Zusammensetzung der geschmiedeten Bauteile zu stark von den zuvor untersuchten Proben abwich. Um über mehrere Chargen hinweg die gleichen Eigenschaften gewährleisten zu können, müssen daher die Parameter individuell angepasst werden.