Andreas Undisz

The electrochemical characteristics of native Nitinol surfaces.

The present study explored the avenues for the improvement of native Nitinol surfaces for implantation obtained using traditional procedures such as mechanical polishing, chemical etching, electropolishing and heat treatments for a better understanding of their electrochemical behavior and associated surface stability, conductivity, reactivity and biological responses. The corrosion resistance (cyclic potential polarization, open circuit potential and polarization resistance) of Nitinol disc and wire samples were evaluated for various surface states in strain-free and strained wire conditions. The surface response to tension strain was studied in situ. Surface chemistry and structure were explored using XPS and Auger spectroscopy and photoelectrochemical methods, respectively. It was found that the polarization resistance of the Nitinol surfaces varied in a range from 100 kOmega to 10 MOmega cm(2) and the open circuit potentials from -440 mV to -55 mV. The surfaces prepared in chemical solutions showed consistent corrosion resistance in strain-free and strained states, but mechanically polished and heat treated samples were prone to pitting. Nitinol surface oxides are semiconductors with the band gaps of either 3.0 eV (rutile) or 3.4 eV (amorphous). The conductivity of semiconducting Nitinol surfaces relevant to their biological performances is discussed in terms of oxide stoichiometry and variable Ni content. Such biological characteristics of Nitinol surfaces as Ni release, fibrinogen adsorption and platelets behavior are re-examined based on the analysis of the results of the present study.

Effect of thermomechanical pre-treatment on short- and long-term Ni release from biomedical NiTi.

The effect of annealing and deformation on short-term (21days) and long-term (8months) Ni release from biomedical NiTi wires is studied. The deformation of annealed NiTi wires causes cracking and flaking of the surface oxide layer. Flaking of oxide particles does not uncover the Ni-rich layer underneath the surface oxide layer, since at sites where flaking occurs, a thin (∼25nm) layer of oxide remains on top of this Ni-rich layer. The number of cracks in the oxide and Ni-rich layer, respectively, increases with deformation, and intercrystalline crack propagation into the Ni-rich layer and the NiTi bulk is observed. In plastically deformed wires, the cracks may remain opened, providing access of immersion liquid to these zones. Characteristics and quantity of short-term Ni release are significantly affected by the pre-deformation, resulting in an up to 2 times higher total Ni release within the first 21days of deformed compared to annealed wires. Pre-deformation does not significantly influence long-term Ni release; all annealed and deformed samples exhibit similar long-term Ni release rates. The source of Ni during short-term release is the Ni contained in the surface zone of the oxide layer. For high pre-deformation, the Ni-rich layer is a second source for Ni. This second source is also the cause for Ni release in long-term immersion experiments.

Corrosion resistance, chemistry, and mechanical aspects of Nitinol surfaces formed in hydrogen peroxide solutions.

Ti oxides formed naturally on Nitinol surfaces are only a few nanometers thick. To increase their thickness, heat treatments are explored. The resulting surfaces exhibit poor resistance to pitting corrosion. As an alternative approach to accelerate surface oxidation and grow thicker oxides, the exposure of Nitinol to strong oxidizing H(2)O(2) aqueous solutions (3 and 30%) for various periods of time was used. Using X-Ray Photoelectron Spectroscopy (XPS) and Auger spectroscopy, it was found that the surface layers with variable Ti (6-15 at %) and Ni (5-13 at %) contents and the thickness up to 100 nm without Ni-enriched interfaces could be formed. The response of the surface oxides to stress in superelastic regime of deformations depended on oxide thickness. In the corrosion studies performed in both strained and strain-free states using potentiodynamic and potentiostatic polarizations, the surfaces treated in H(2)O(2) showed no pitting in corrosive solution that was assigned to higher chemical homogeneity of the surfaces free of secondary phases and inclusions that assist better biocompatibility of Nitinol medical devices.

The effect of heating rate on the surface chemistry of NiTi

The impact of the heating rate on the Ni content at the surface of the oxide layer of biomedical NiTi is explored. Heat treatment emulating common shape-setting procedures was performed by means of conventional and inductive heating for similar annealing time and temperature, applying various heating rates from ~0.25 K s(-1) to 250 K s(-1). A glow discharge optical emission spectroscopy method was established and employed to evaluate concentration profiles of Ni, Ti and O in the near-surface region at high resolution. The Ni content at the surface of the differently treated samples varies significantly, with maximum surface Ni concentrations of ~20 at.% at the lowest and ~1.5 at.% at the highest heating rate, i.e. the total amount of Ni contained in the surface region of the oxide layer decreases by >15 times. Consequently, the heating rate is a determinant for the biomedical characteristics of NiTi, especially since Ni available at the surface of the oxide layer may affect the hemocompatibility and be released promptly after surgical application of a respective implant. Furthermore, apparently contradictory results presented in the literature reporting surface Ni concentrations of ~3 at.% to >20 at.% after heat treatment are consistently explained considering the ascertained effect of the heating rate.

FUNCTIONALITY OF BARE NITINOL SURFACES

The results of pilot in situ studies of the responses of Nitinol surfaces to deformation are presented. It is shown that the mechanical behavior of Nitinol surfaces differs, depending on oxide thickness and its chemical composition. The corrosion resistance of the surfaces evaluated in strain-free and strained states using potentiodynamic and potentiostatic cyclic polarization at the body potentials demonstrated quite stable behavior.

Microstructure Preparation Using Glow Discharge Plasma Taking the Examples of Ni-Ti, Cu-Zn and a Ni-Based Alloy

Abstract The present work investigates the universal applicability of glow discharge plasmas for the microstructure representation of different materials taking the example of Ni-Ti alloys, Cu-Zn alloys, and the Ni based alloy “Hastelloy C 276”. Results are compared with the results provided by classical etching methods. Microstructures became visible for the previously mechanically polished materials within a few seconds, even without detailed optimization of the excitation conditions of the glow discharge plasma. The results partially significantly outperfomed the results of the classical preparation techniques with respect to the detectability of structural details such as grain and phase boundaries. Due to the demonstrated wide and relatively uncomplicated applicability, the per se established glow discharge technology is expected to have a huge potential for application for a rapid and high-contrast microstructure representation.

Optical Assets of In situ Electro-assembled Platinum Black Nanolayers

Optoelectronic technology has been increasingly driven towards miniaturization. In this regard, maintaining the optical properties of the bulk materials while reducing their size is a critical need. How thin must the film be to preserve the bulk material´s optical absorbance and reflectance characteristics? This is the central question for our study of the in situ electro-assembly broad band optical absorber films of platinum in non-aqueous solution of PtCl4. By reducing the in situ constructed film to sub-visible-wavelength thicknesses, the measured reflectance in the region from the ultraviolet to the infrared remained close to that exhibited by the micrometre-width films. These platinum black films broadly absorb electromagnetic waves at a sub-incident-wavelength thickness owing to their plasmonically increased absorbance cross-section. Simulation of various incident energy electron trajectories gives insights into the electron depth through the porous platinum black of ρ = 1.6 g/cm3 and previews the optical behaviour close to the atomic thickness.

The Copper of the Kyffhäuser Monument

Abstract The connection between copper and art goes way back. For thousands of years, the ductile metal has been worked in cold state via hammer and punch to make jewelry, vessels or monuments. More recent examples are the Statue of Liberty in New York, the Quadriga in Berlin and the equestrian statue of Emperor William I at the Kyffhäuser. During the recently completed renovation of the Kyffhäuser monument it was possible to perform a scientific examination on the copper of the equestrian statue. The examinations showed that the material is multiphase due to the content of oxygen and lead. With regard to the mechanical properties, the impurity phases are only of little importance. Details of the microstructure with a spatially coherent order of impurity phases, however, have never been observed in this way. The formation of the microstructure is discussed taking into account the particular circumstances of the artistic shaping via repoussé and chasing.

Surface Preserving Targeted Preparation using Focused Ion Beam Demonstrated by the Example of Oxide layers on Ni-Ti Alloys

Abstract The use of focused ion beams, whilst permitting the targetted preparation of thin specimens for Transmission Electron Microscopy, also results in modification of the material to be investigated as a result of energy being transferred into the material. This undesirable effect is normally limited to the surface of the material, which is particularly unfavourably orientated towards the impinging ion beam. If the crystal structure and composition of areas close to the surface of such specimens need to be characterised, protective layers may be used. However, those layers, depending on the applied deposition technique, may interact with the sample surface as well thus affecting the results of the analysis. In the work presented here, the possible interactions which might occur between the various protective coatings of ion-beam deposited Platinum, electron beam deposited Platinum, Silicon Oxide or adhesively bonded Gold foil and the subsequent FIB-preparation of the oxide layers on Ni-Ti alloys are investigated, with respect to and how these might affect the TEM-images obtained of areas close to the surface of such specimens. It is shown that the use of adhesively bonded Gold foil as a protective coating, in particular, permits comprehensive characterisation of the surface, including the use of high-resolution TEM, to be carried out, up to the surface of the Oxide layer itself.

Aqueous Black Colloids of Reticular Nanostructured Gold

Since ancient times, noble gold has continuously contributed to several aspects of life from medicine to electronics. It perpetually reveals its new features. We report the finding of a unique form of gold, reticular nanostructured gold (RNG), as an aqueous black colloid, for which we present a one-step synthesis. The reticules consist of gold crystals that interconnect to form compact strands. RNG exhibits high conductivity and low reflection, and these features, coupled with the high specific surface area of the material, could prove valuable for applications in electronics and catalysis. Due to high absorption throughout the visible and infrared domain, RNG has the potential to be applied in the construction of sensitive solar cells or as a substrate for Raman spectroscopy.