Design, physico-chemical characterization and bioactivity studies of hybrid nanostructured titanium surfaces for enhanced osseointegration

170 p.

Ordered mesoporous titanium oxide for thin film microbatteries with enhanced lithium storage

A 3D mesoporous TiO2 material with well-developed mesostructure is prepared in the form of a binder-free thin (100 nm) film and studied as potential candidate for the negative electrode in lithium microbatteries. By appropriate thermal treatments, the selected crystal structure (anatase, rutile, or amorphous), and micro-/mesostructure of the materials was obtained. The effects of voltage window and prelithiation treatment improved first cycle reversibility up to 86% and capacity retention of 90% over 100 cycles. After a prolonged intercalation of lithium ions in ordered mesoporous TiO2 appeared small particles assigned to Li2Ti2O4 with cubic structure as observed from ex-situ TEM micrographs. This study highlights the flexibility of the potential window to which the electrode can operate. Maximum capacity values over 100 cycles of 470 μA h cm−2 μm−1 and 177 μA h cm−2 μm−1 are obtained for voltage ranges of 0.1–2.6 V and 1.0–2.6 V, respectively. The observed values are between 6 and 2 times higher than those obtained for films with 600 nm (80 μA h cm−2 μm−1) and 900 nm (92 μA h cm−2 μm−1) lengths. This indicates that 100 nm thin TiO2 films with high accessibility show finite-length type diffusion which is interesting for this particular application.

Accelerated growth of preosteoblastic cells on ultrafine grained titanium

This work is part of a general effort to demonstrate the effect of the bulk microstructure of titanium as a model bone implant material on viability of osteoblasts (bone-forming cells). The objective of this work was to study the proliferation of preosteoblastic MC3T3-E1 cells extracted from mice embryos on commercial purity titanium substrates. Two distinct states of titanium were considered: as-received material with an average grain size of 4.5 microm and that processed by equal channel angular pressing (ECAP), with an average grain size of 200 nm. We report the first results of an in vitro study into the effect of this extreme grain refinement on viability and proliferation of MC3T3-E1 cells. By means of MTT assays it was demonstrated that ECAP processing of titanium enhances MC3T3-E1 culture proliferation in a spectacular way. This finding suggests that bone implants made from ECAP processed titanium may promote bone tissue growth.

Effects of combined silicon and molybdenum alloying on the size and evolution of microalloy precipitates in HSLA steels containing niobium and titanium

The effects of combined silicon and molybdenum alloying additions on microalloy precipitate formation in austenite after single- and double-step deformations below the austenite no-recrystallization temperature were examined in high-strength low-alloy (HSLA) steels microalloyed with titanium and niobium. The precipitation sequence in austenite was evaluated following an interrupted thermomechanical processing simulation using transmission electron microscopy. Large (~ 105 nm), cuboidal titanium-rich nitride precipitates showed no evolution in size during reheating and simulated thermomechanical processing. The average size and size distribution of these precipitates were also not affected by the combined silicon and molybdenum additions or by deformation. Relatively fine (< 20 nm), irregular-shaped niobium-rich carbonitride precipitates formed in austenite during isothermal holding at 1173 K. Based upon analysis that incorporated precipitate growth and coarsening models, the combined silicon and molybdenum additions were considered to increase the diffusivity of niobium in austenite by over 30% and result in coarser precipitates at 1173 K compared to the lower alloyed steel. Deformation decreased the size of the niobium-rich carbonitride precipitates that formed in austenite.

Effect of bulk microstructure of commercially pure titanium on surface characteristics and fatigue properties after surface modification by sand blasting and acid-etching

Surface modification techniques are widely used to enhance the biological response to the implant materials. These techniques generally create a roughened surface, effectively increasing the surface area thus promoting cell adhesion. However, a negative side effect is a higher susceptibility of a roughened surface to failure due to the presence of multiple stress concentrators. The purpose of the study reported here was to examine the effects of surface modification by sand blasting and acid-etching (SLA) on the microstructure and fatigue performance of coarse-grained and ultrafine-grained (UFG) commercially pure titanium. Finer grain sizes, produced by equal channel angular pressing, resulted in lower values of surface roughness in SLA-processed material. This effect was associated with greater resistance of the UFG structure to plastic deformation. The fatigue properties of UFG Ti were found to be superior to those of coarse-grained Ti and conventional Ti-6Al-4V, both before and after SLA-treatment.

Processing and characterization of srTiO₃-TiO₂ nanoparticle-nanotube heterostructures on titanium for biomedical applications

Surface properties such as physicochemical characteristics and topographical parameters of biomaterials, essentially determining the interaction between the biological cells and the biomaterial, are important considerations in the design of implant materials. In this study, a layer of SrTiO3-TiO2 nanoparticle-nanotube heterostructures on titanium has been fabricated via anodization combined with a hydrothermal process. Titanium was anodized to create a layer of titania (TiO2) nanotubes (TNTs), which was then decorated with a layer of SrTiO3 nanoparticles via hydrothermal processing. SrTiO3-TiO2 heterostructures with high and low volume fraction of SrTiO3 nanoparticle (denoted by 6.3-Sr/TNTs and 1.4-Sr/TNTs) were achieved by using a hydrothermal processing time of 12 and 3 h, respectively. The in vitro biocompatibility of the SrTiO3-TiO2 heterostructures was assessed by using osteoblast cells (SaOS2). Our results indicated that the SrTiO3-TiO2 heterostructures with different volume fractions of SrTiO3 nanoparticles exhibited different Sr ion release in cell culture media and different surface energies. An appropriate volume fraction of SrTiO3 in the heterostructures stimulated the secretion of cell filopodia, leading to enhanced biocompatibility in terms of cell attachment, anchoring, and proliferation on the heterostructure surface.

Formation of nanoscale titanium carbides in ferrite: an atomic study

The formation and evolution of nanoscale titanium carbide in ferrite during the early isothermal annealing process were investigated via molecular dynamics simulation. The atomic interactions of titanium and carbon atoms during the initial formation process explained the atoms aggregation and carbides formation. It was found that the aggregation and dissociation of titanium carbide occurred simultaneously, and the composition of carbide clusters varied in a wide range. A mechanism for the formation of titanium carbide clusters in ferrite was disclosed.

Prediction of ductile failure in CP-Titanium as criterion of SPD process design

Application of damage model in combination with finite element analysis to design and optimization of equal channel angular pressing - conform of commercially pure titanium against ductile failure is demonstrated. The properties required for precise simulation of the process and prediction of damage accumulation (equivalent stress as function of equivalent strain and temperature and low bound ductility function) are obtained in the temperature interval 20-400 °C and described in details.

Machining of coarse grained and ultra fine grained titanium

Machining of titanium is quite difficult and expensive. Heat generated in the process of cutting does not dissipate quickly, which affects tool life. In the last decade ultra fine grained (UFG) titanium has emerged as an option for substitution for more expensive titanium alloys. Extreme grain refinement can be readily performed by severe plastic deformation techniques. Grain refinement of a material achieved in this way was shown to change its mechanical and physical properties. In the present study, the microstructure evolution and the shear band formation in chips of coarse grained and UFG titanium machined to three different depths and three different feeding rates was investigated. A change in thermal characteristics of commercial purity Ti with grain refinement was studied by comparing heating/cooling measurements with an analytical solution of the heat transfer boundary problem. It was demonstrated that an improvement in the machinability can be expected for UFG titanium. © 2012 Springer Science+Business Media, LLC.

Asymmetric accumulative roll bonding of aluminium-titanium composite sheets

Aluminium-titanium (Al/Ti) composite sheets were fabricated via asymmetric accumulative roll bonding (AARB), which capitalises on additional shear to enhance plastic deformation. Multi-layers of Al alloy (AA1050) and commercially-pure Ti sheets were alternatively stacked and rolled-bonded with varied roll diameter ratios (dr) ranging from 1 to 2, for up to four passes. Annealing of selected composite sheets was subsequently carried out at 600°C for 24h to compare the rates of solid-state diffusion reactions between Al and Ti components. Mechanical tests revealed that both tensile strength and ductility of the sheets increase systematically with dr. The microstructures and the Al/Ti interfaces of the sheets were analysed in detail using TEM, SEM and FIB techniques. It is shown that not only does AARB lead to a more refined grain size of the Al matrix but also it promotes the development of a nanostructured surface layer on Ti that comprises crystallites of 50-100nm in size, which is otherwise absent in the case of symmetric ARB (i.e. dr=1). The AARB-processed sheets exhibit a larger thickness of the interdiffusion layer at the Al/Ti interfaces than the counterparts processed via the symmetric ARB route, the difference being in excess of 15%. The effects and the implications of AARB processing on mechanical behaviour and diffusion kinetics are discussed with respect to the microstructural evolutions.

Bacterial attachment on sub-nanometrically smooth titanium substrata

Despite the volume of work that has been conducted on the topic, the role of surface topography in mediating bacterial cell adhesion is not well understood. The primary reason for this lack of understanding is the relatively limited extent of topographical characterisation employed in many studies. In the present study, the topographies of three sub-nanometrically smooth titanium (Ti) surfaces were comprehensively characterised, using nine individual parameters that together describe the height, shape and distribution of their surface features. This topographical analysis was then correlated with the adhesion behaviour of the pathogenic bacteria Staphylococcus aureus and Pseudomonas aeruginosa, in an effort to understand the role played by each aspect of surface architecture in influencing bacterial attachment. While P. aeruginosa was largely unable to adhere to any of the three sub-nanometrically smooth Ti surfaces, the extent of S. aureus cell attachment was found to be greater on surfaces with higher average, RMS and maximum roughness and higher surface areas. The cells also attached in greater numbers to surfaces that had shorter autocorrelation lengths and skewness values that approached zero, indicating a preference for less ordered surfaces with peak heights and valley depths evenly distributed around the mean plane. Across the sub-nanometrically smooth range of surfaces tested, it was shown that S. aureus more easily attached to surfaces with larger features that were evenly distributed between peaks and valleys, with higher levels of randomness. This study demonstrated that the traditionally employed amplitudinal roughness parameters are not the only determinants of bacterial adhesion, and that spatial parameters can also be used to predict the extent of attachment.

The photostability of wool doped with photocatalytic titanium dioxide nanoparticles

Photoyellowing of wool is a serious problem for the wool industry. This study assessed the role of photocatalytic nanocrystalline titanium dioxide (P-25) as a potential antagonist or catalyst in the photoyellowing of wool. Untreated, bleached and bleached and fluorescent-whitened wool slivers were processed into fine wool powders for the purpose of even and intimate mixing with the TiO2 nanoparticles in the solid state. Pure wool and wool/TiO2 mixtures were then compressed into solid discs for a photoyellowing study under simulated sunlight and under UVB and UVC radiations. Yellowness and photo-induced chemiluminescence (PICL) measurements showed that nanocrystalline TiO2 could effectively reduce the rate of photoyellowing by inhibiting free radical generation in doped wool, and that a higher concentration of TiO2 contributed to a lower rate of photooxidation and reduced photoyellowing. Hence nanocrystalline TiO2 acts primarily as a UV absorber on wool in dry conditions and not as a photocatalyst.

Accelerated stem cell attachment to ultrafine grained titanium

Commercial purity titanium with an average grain size in the low sub-micron range was produced by equal channel angular pressing (ECAP). Attachment of human bone marrow-derived mesenchymal stem cells (hMSCs) to the surface of conventional coarse grained and ECAP-modified titanium was studied. It was demonstrated that the attachment and spreading of hMSCs in the initial stages (up to 24h) of culture was enhanced by grain refinement. Surface characterization by a range of techniques showed that the main factor responsible for the observed acceleration of hMSC attachment and spreading on titanium due to grain refinement in the bulk is the attendant changes in surface topography on the nanoscale. These results indicate that, in addition to its superior mechanical properties, ECAP-modified titanium possesses improved biocompatibility, which makes it to a potent candidate for applications in medical implants.

The influence of temporary hydrogenation on ECAP formability and low cycle fatigue life of CP titanium

It is generally believed that thermo-hydrogen processing has a beneficial effect on tensile ductility and fatigue properties of titanium. This study was concerned with investigating whether this also applies to titanium of commercial purity (CP) with an ultrafine-grained structure obtained by equal-channel angular pressing (ECAP). It was shown that despite the possibility to manipulate the microstructure of titanium the thermo-hydrogen processing offers, temporary hydrogenation was not able to improve ductility and low cycle fatigue life of CP titanium over the levels achievable by straight ECAP.

Constitutive modelling of high strength titanium alloy Ti-6Al-4 V for sheet forming applications at room temperature

To enable the design and optimisation of forming processes at room temperature the material behaviour of Ti-6Al-4 V needs to be accurately represented in numerical analysis and this requires an advanced material model. In particular, an accurate representation of the shape and size of the yield locus as well as its evolution during forming is important. In this study a rigorous set of experiments on the quasi-static deformation behaviour of a Ti-6Al-4 V alloy sheet sample at room temperature was conducted for various loading conditions and a constitutive material model developed. To quantify the anisotropy and asymmetry properties, tensile and compression tests were carried out for different specimen orientations. To examine the Bauschinger effect and the transient hardening behaviour in - plane tensile - compression and compression - tensile tests were performed. Balanced biaxial and plane strain tension tests were conducted to construct and validate the yield surface of the Ti-6Al-4 V alloy sheet sample at room temperature. A recently proposed anisotropic elastic-plastic constitutive material model, so-called HAH, was employed to describe the behaviour, in particular for load reversals. The HAH yield surface is composed of a stable component, which includes plastic anisotropy and is distorted by a fluctuating component. The key of the formulation is the use of a suitable yield function that reproduces the experimental observations well for the stable component. Meanwhile, the rapid evolution of the material structure must be captured at the macro - scale level by the fluctuating component embedded in the HAH model. Compared to conventional hardening equations, the proposed model leads to higher accuracy in predicting the Bauschinger effect and the transient hardening behaviour for the Ti-6Al-4 V sheet sample tested at room temperature.