Influence of Low Temperature Plasma Oxidizing on the Bioactivity of NiTi Shape Memory Alloy for Medical Applications.

The present study elucidates the impact of glow discharge oxidation within a low-temperature plasma environment on the bioactivity characteristics of an NiTi shape memory alloy. The properties of the produced surface layers, such as structure (TEM observations), surface morphology (SEM observations), chemical and phase composition (EDS and XRD measurements), wettability (optical gonimeter), and the biological response of osteoblasts and platelets to the oxidized surface compared with the NiTi alloy without a surface layer are presented. The presented surface modification of the NiTi shape memory alloy, achieved through oxidizing in a low-temperature plasma environment, led to the creation of a continuous surface layer composed of nanocrystalline titanium oxide TiO2 (rutile). The findings obtained from this study provide evidence that the oxidized layer augments the bioactivity of the shape memory alloy. This augmentation was substantiated through the spontaneous biomimetic deposition of apatite from a simulated body fluid (SBF) solution. Furthermore, the modified surface exhibited improved osteoblast proliferation, and enhanced platelet adhesion and activation. This proposed surface modification strategy holds promise as a prospective solution to enhance the biocompatibility and bioactivity of NiTi shape memory alloy intended for prolonged use in bone implant applications.

NiTi Shape Memory Clamps with Modified Surface for Bone Fracture Treatment.

Using NiTi alloys with shape memory for long-term medical implants requires modification of their surface due to the possible occurrence of corrosion. Hence, the surface of the staples used to join fractured bone within the craniofacial region was modified by applying a titanium oxy-nitrogen layer and a hydroxyapatite coating. Surface-modified clamps were tested in vivo using New Zealand white rabbits. After determining the mechanical characteristics of the bone and considering the initial state and surface modification, the diameter of the wire (used to make the clamps with the appropriate compression force) was selected. Implantation was performed on two groups of rabbits: experimental and control. In the experimental group, an intentionally induced bone fracture was treated in one tibia. On the second tibia, two additional clamps were applied to increase the possibility of a negative impact of the NiTi alloy on a living organism. After 6 weeks of application, a proper joining of the broken bone fragments was stated. Whereas after twelve weeks, no negative impact of the clamp material on a living organism, i.e., a rabbit, was found. Hence, the clamp with the modified surface can connect bone fragments in humans as well as small and medium-sized animals, with an extended range of use up to 12 weeks.

Improving the Properties of Composite Titanium Nitride Layers on the AZ91D Magnesium Alloy Using Hydrothermal Treatment.

Coating magnesium alloys with nitride surface layers is a prospective way of improving their intrinsically poor surface properties; in particular, their tribological and corrosion resistance. These layers are usually produced using PVD methods using magnetron sputtering or arc evaporation. Even though the thus-produced layers significantly increase the wear resistance of the alloys, their effects on corrosion resistance are unsatisfactory because of the poor tightness, characteristic of PVD-produced products. Tightness acquires crucial significance when the substrate is a highly-active magnesium alloy, hence our idea to tighten the layers by subjecting them to a post-deposition chemical-hydrothermal-type treatment. This paper presents the results of our experiments with a new hybrid surface engineering method, using a final tightening pressure hydrothermal gas treatment in overheated steam of the composite titanium nitride layers PVD, produced on AZ91D magnesium alloy. The proposed method resulted in an outstanding improvement of the performance properties, in particular resistance to corrosion and wear, yielding values that exceed those exhibited by commercially anodized alloys and austenitic stainless 316L steel. The developed hybrid method produces new, high-performance corrosion and wear resistant, lightweight magnesium base materials, suitable for heavy duty applications.

Plasma Modification of Carbon Coating Produced by RF CVD on Oxidized NiTi Shape Memory Alloy under Glow-Discharge Conditions.

Our previous work has shown that for cardiac applications, combining low-temperature plasma oxidation with an amorphous carbon coating (a-C:N:H type) constitutes a prospective solution. In this study, a short-term modification by low-temperature oxygen plasma is proposed as an example and a method for shaping the topography and surface energy of the outer amorphous carbon coating, produced via the Radio-Frequency Chemical Vapour Deposition (RFCVD) method on NiTi alloy oxidized under glow-discharge conditions. This treatment alters the chemical composition of the outer zone of the surface layer. A slight increase is also noted in the surface roughness at the nanoscale. The contact angles were shown to increase by about 20% for water and 30% for diiodomethane, while the surface free energy decreased by ca. 11%. The obtained results indicate that even short-term contact with low-temperature plasma can shape the surface properties of the carbon coating, an outcome which shows potential in terms of its use in medical applications.

Formation of Nitrogen Doped Titanium Dioxide Surface Layer on NiTi Shape Memory Alloy.

NiTi shape memory alloys are increasingly being used as bone and cardiac implants. The oxide layer of nanometric thickness spontaneously formed on their surface does not sufficiently protect from nickel transition into surrounding tissues, and its presence, even in a small amount, can be harmful to the human organism. In order to limit this disadvantageous phenomenon, there are several surface engineering techniques used, including oxidation methods. Due to the usually complex shapes of implants, one of the most prospective methods is low-temperature plasma oxidation. This article presents the role of cathode sputtering in the formation of a titanium dioxide surface layer, specifically rutile. The surface of the NiTi shape memory alloy was modified using low-temperature glow discharge plasma oxidation processes, which were carried out in two variants: oxidation using an argon + oxygen (80% vol.) reactive atmosphere and the less chemically active argon + air (80% vol.), but with a preliminary cathode sputtering process in the Ar + N2 (1:1) plasma. This paper presents the structure (STEM), chemical composition (EDS, SIMS), surface topography (optical profilometer, Atomic Force Microscopy-AFM) and antibacterial properties of nanocrystalline TiO2 diffusive surface layers. It is shown that prior cathodic sputtering in argon-nitrogen plasma almost doubled the thickness of the produced nitrogen-doped titanium dioxide layers despite using air instead of oxygen. The (TiOxNy)2 diffusive surface layer showed a high level of resistance to E. coli colonization in comparison with NiTi, which indicates the possibility of using this surface layer in the modification of NiTi implants' properties.

Multi-scale characterization and biological evaluation of composite surface layers produced under glow discharge conditions on NiTi shape memory alloy for potential cardiological application.

NiTi shape memory alloys are characterized by relatively good biocompatibility primarily thanks to their ability to self-passivate. However, before they can be used as medical implants for long term use, they need to undergo treatment aimed at producing layers on their surface that are superior to spontaneously formed oxide layers and that would increase their resistance to corrosion, limit nickel ion release from the surface (metallosis) and have the capability to shape their biological properties depending on the application. Furthermore, cardiac implants require addressing the issue of blood clotting on the surface. Treatment in glow-discharge low temperature plasma makes it possible to produce titanium layers with a structure and properties that are controlled via process parameters. In addition, antithrombogenic properties can be improved by depositing a carbon coating via the RFCVD process. The aim of the study was to investigate the structure, surface topography, adhesive properties, wettability, surface free energy and evaluate metallosis after producing TiO2 and a-C:N:H + TiO2 composite layers on NiTi alloy. The capabilities of AFM microscopes in studying the adhesive properties of a surface were also highlighted in the study. The study shows that the produced surface layers are capable of significantly reducing metallosis. Furthermore, in contrast to NiTi in its initial state, layers of nanocrystalline TiO2 titanium oxide (rutile) with a homogeneous structure demonstrate greater adhesion strength and more developed surface in the microscale, which facilitates the formation of an a-C:N:H coating. Therefore the formation of a coating of a-C:N:H amorphous carbon on NiTi alloy that has previously been oxidised in low-temperature plasma may prove to be a favourable solution in terms of using NiTi alloy to produce cardiac implants.

Structure and properties of composite surface layers produced on NiTi shape memory alloy by a hybrid method.

A hybrid process that combines oxidation under glow-discharge conditions with ion beam-assisted deposition (IBAD) has been applied to mechanically polished NiTi shape memory alloy in order to produce composite surface layers consisting of a TiO2 layer and an external carbon coating with an addition of silver. The produced surface layers a-C(Ag) + TiO2 type have shown increased surface roughness, improved corrosion resistance, altered wettability, and surface free energy, as well as reduced platelet adhesion, aggregation, and activation in comparison to NiTi alloy in initial state. Such characteristics can be of great benefit for cardiac applications.

Structure and physico-mechanical properties of low temperature plasma treated electrospun nanofibrous scaffolds examined with atomic force microscopy.

Electrospun nanofibrous scaffolds are willingly used in tissue engineering applications due to their tunable mechanical, chemical and physical properties. Additionally, their complex openworked architecture is similar to the native extracellular matrix of living tissue. After implantation such scaffolds should provide sufficient mechanical support for cells. Moreover, it is of crucial importance to ensure sterility and hydrophilicity of the scaffold. For this purpose, a low temperature surface plasma treatment can be applied. In this paper, we report physico-mechanical evaluation of stiffness and adhesive properties of electrospun mats after their exposition to low temperature plasma. Complex morphological and mechanical studies performed with an atomic force microscope were followed by scanning electron microscope imaging and a wettability assessment. The results suggest that plasma treatment can be a useful method for the modification of the surface of polymeric scaffolds in a desirable manner. Plasma treatment improves wettability of the polymeric mats without changing their morphology.

Hybrid a-CNH+TiO2+TiN-type surface layers produced on NiTi shape memory alloy for cardiovascular applications.

AIM: The goal was to improve the properties of NiTi shape memory alloy to make it suitable for cardiac applications. For this purpose, a hybrid a-CNH+TiO2+TiN-type surface layer was produced on NiTi alloy and characterized. MATERIALS & METHODS: The NiTi alloy subjected to hybrid process combining low-temperature oxynitriding under glow discharge conditions and radio frequency chemical vapor deposition process was examined for microstructure, surface topography, corrosion resistance, wettability and surface-free energy, Ni ion release and platelets adhesion, aggregation and activation. RESULTS: The hybrid surface layers showed slightly increased surface roughness, better corrosion resistance, a more hydrophobic nature, decreased surface free energy, smaller release of nickel ions and reduced platelets activation. CONCLUSION: The produced layers could expand the range of NiTi medical applications.

Properties of Ti-6Al-7Nb titanium alloy nitrocarburized under glow discharge conditions.

PURPOSE: The paper presents the results of physicochemical and mechanical properties of the Ti-6Al-7Nb alloy with surface modified by formation of a diffusive nitrocarburized layer deposited in a low-temperature plasma process. The main aim of the study was to evaluate the influence of steam sterilization and exposure to Ringer's solution on the utility properties of the alloy. METHODS: Based on the study of the microstructure, roughness, wettability, resistance to pitting corrosion, ion infiltration and mechanical properties, the usefulness of the proposed method of surface treatment for clinical application was proven. RESULTS: Deposition of the nitrocarburized layer increased the surface roughness and surface hardness, but also reduced the contact angle, and corrosion resistance with respect to the polished surfaces. The nitrocarburized layer is a barrier against the infiltration of ions to the solution and sterilization and exposure to Ringer solution have greater effect on the physicochemical properties rather than on the mechanical ones. CONCLUSION: It was found that sterilization, and exposure to Ringer's solution greatly affect the change of physicochemical properties rather than mechanical properties for both nitrocarburized layers and the Ti-6Al-7Nb alloy of mechanically polished surface.

Thrombocompatibility of thin dielectric carbon film dependence on electron work function of metallic substrate material.

We demonstrate here for the first time the relationship between electron work function of metallic substrate material, used for coating with thin dielectric carbon (DC) film, and surface thrombocompatybility of this structure. Thin dielectric layers of DC, with thickness below 1 microm, were deposited on medical steel 316L, titanium alloy Ti6Al4V and titanium nitride (TiN) using the RFCVD method. The values of the DC coated metallic electrode potential in water and in serum and the number of adhered blood platelets to the DC coated metals depended on the electron work function (phiM) of the metallic substrate. As the phiM increased, the electrode potentials increased, whereas the number of adhered blood platelets decreased. This effect permits controlling the interaction between blood and the thin DC films by selecting an appropriate metallic substrate.