Effects of oxygen adsorption on the corrosion behavior of the Ti(0001) surface: a DFT investigation.

The electrochemical corrosion of Ti surfaces is significantly affected by O adsorption, yet the underlying mechanisms remain unexplored. Herein, density functional theory calculations are employed to examine the adsorption energies, structural properties, electronic structures, and thermodynamic stability of atomic O on Ti(0001) surfaces during initial oxidation. Additionally, the impact of O adsorption on Ti dissolution is assessed by introducing a Ti vacancy on the Ti(0001) surface. The passivation of the Ti(0001) surface is predominantly ascribed to the robust adsorption of O atoms. The thermodynamic results reveal that bulk TiO2 easily forms at 300 K, which explains the spontaneous passivation of the Ti(0001) surface. The formation of an O monolayer on the Ti(0001) surface increases the work function (Φ), positively shifting the equilibrium potential and reducing the corrosion rate. The surface vacancy formation energy of Ti on the Ti(0001)/O surface surpasses that on the clean surface. The electrode potential shift for a Ti atom dissolving from the Ti(0001)/O surface is positive, indicating that oxidation impedes the formation of Ti vacancies, rendering Ti atoms less soluble. This study enhances our comprehension of the corrosion mechanism in Ti metal.

Dealloyed nano-porous TiCu coatings with controlled copper release for cardiovascular devices.

TiCu coatings with controlled copper release and nano-porous structures were fabricated as biocompatible, blood-contacting interfaces through a two-step process. Initially, coatings with 58 % Cu were created using HiPIMS/DC magnetron co-sputtering, followed by immersion in a dilute HF solution for varying durations to achieve dealloying. The presence of Ti elements in the as-deposited TiCu coatings facilitated their dissolution upon exposure to the dilute HF solution, resulting in the formation of nanopores and increased nano-roughness. Dealloying treatment time correlated with higher Cu/(Ti + Cu) values, nanopore size, and nano-roughness in the dealloyed samples. The dealloyed TiCu coatings with 87 % Cu exhibited a controlled release of copper ions and displayed nanopores (approximately 80 nm in length and 31.0 nm in width) and nano-roughness (Ra roughness: 82 nm). These coatings demonstrated inhibited platelet adhesion and suppressed smooth muscle cell behavior, while supporting favorable endothelial cell viability and proliferation, attributed to the controlled release of copper ions and the extent of nanostructures. In contrast, the as-deposited TiCu coatings with 85 % Cu showed high copper ion release, leading to decreased viability and proliferation of endothelial cells and smooth muscle cells, as well as suppressed platelet adhesion. The TiCu coatings met medical safety standards, exhibiting hemolysis rates of <5 %. The technology presented here paves the way for the simple, controllable, and cost-effective fabrication of TiCu coatings, opening new possibilities for surface modification of cardiovascular devices such as vascular stents and inferior vena cava filters.

Diamond-like carbon films prepared by a low temperature periodic process for application in ventricular assist devices.

Due to the poor tribological properties of titanium (Ti) and its alloy Ti6Al4V (commonly used for ventricular assist devices manufacturing), diamond-like carbon (DLC) films with excellent anti-wear properties are pursued to improve the wear resistance of Ti and its alloys. Considering the effect of temperature on magnets inside pump impellers and workpiece deformation, DLC films are preferred to be prepared under low temperature. In this study, DLC films were prepared on Ti6Al4V alloys by periodic and continuous processes, and the corresponding maximum deposition temperature was 85 and 154°C, respectively. The periodic DLC films exhibited the feature of columnar structure, and the surface hillocks were less uniform than that of continuous DLC films. The periodic DLC films possessed more sp3 -bonded structures, and the accessorial sp3 -bonding mainly existed in the form of CH. Compared to continuous DLC films, the periodic DLC films had lower residual stress and better adhesion with Ti6Al4V substrates. Both DLC films could effectively reduce the friction coefficient and wear rate of Ti6Al4V alloys both in air and fetal bovine serum (FBS), and the periodic DLC films exhibited superior anti-wear properties to that of continuous DLC films in FBS. Haemocompatibility evaluation revealed that both DLC films presented similar levels of more human platelet adhesion and activation as compared with that of bare Ti6Al4V. However, both DLC films significantly prolonged plasma clotting time in comparison to bare Ti6Al4V. This study demonstrates the potential of low-temperature DLC films as wear-resistant surface modification for VADs.

Antibacterial Ti-Cu implants: A critical review on mechanisms of action.

Titanium (Ti) has been widely used for manufacturing of bone implants because of its mechanical properties, biological compatibility, and favorable corrosion resistance in biological environments. However, Ti implants are prone to infection (peri-implantitis) by bacteria which in extreme cases necessitate painful and costly revision surgeries. An emerging, viable solution for this problem is to use copper (Cu) as an antibacterial agent in the alloying system of Ti. The addition of copper provides excellent antibacterial activities, but the underpinning mechanisms are still obscure. This review sheds light on such mechanisms and reviews how incorporation of Cu can render Ti-Cu implants with antibacterial activity. The review first discusses the fundamentals of interactions between bacteria and implanted surfaces followed by an overview of the most common engineering strategies utilized to endow an implant with antibacterial activity. The underlying mechanisms for antibacterial activity of Ti-Cu implants are then discussed in detail. Special attention is paid to contact killing mechanisms because the misinterpretation of this mechanism is the root of discrepancies in the literature.

Reactive magnetron co-sputtering of Ti-xCuO coatings: Multifunctional interfaces for blood-contacting devices.

Multifunctional interfaces that promote endothelialisation, suppress the viability of smooth muscle cells (SMCs), prevent the adhesion and activation of platelets, while demonstrating antibacterial activity are of great interest for surface engineering of blood-contacting devices. Here, we report for the first time the high-power pulsed magnetron sputtering (HPPMS)/DC magnetron sputtering (DCMS) co-sputtering of Ti-xCuO coatings that demonstrate this required multifunctionality. The Cu contents and surface chemistry of the coatings are optimized, and the critical role of copper release on the viability of endothelial cells (ECs) and SMCs, platelet adhesion, and antibacterial activities is elucidated. Rutile phase is formed for Ti-xCuO coatings with Cu atomic concentrations in the range of 1.9 to 13.7 at.%. Rutile and nanocrystalline/amorphous structures were determined for the coatings with 16.8 at.% Cu, while an amorphous phase was observed for the coating with 33.9 at.% Cu. The Ti-xCuO coatings with higher Cu contents were more susceptible to corrosion, and the release rates of Cu ions increased with increasing the Cu contents, maintaining a stable releasing state for up to 28 days. The Ti-xCuO coatings with optimum microstructure and Cu contents of 3.1 and 4.2 at.% promoted the viability and proliferation of ECs, suppressed the viability of smooth muscle cells, inhibited the platelet adhesion and activation, and showed excellent antibacterial activities. Such multifunctionality was achieved in one-pot through controlled copper ions release in the presence of titanium oxides such as TiO2 and Ti2O3 on the surface. The Ti-xCuO coatings developed through HPPMS/DCMS co-sputtering are attractive for surface modification of blood-contacting materials such as implantable cardiovascular devices.

Transparent Conductive Dielectric-Metal-Dielectric Structures for Electrochromic Applications Fabricated by High-Power Impulse Magnetron Sputtering.

The growing applications of electrochromic (EC) devices have generated great interest in bifunctional materials that can serve as both transparent conductive (TC) and EC coatings. WO3/Ag/WO3 (WAW) heterostructures, in principle, facilitate this extension of EC technology without reliance on an indium tin oxide (ITO) substrate. However, these structures synthesized using traditional methods have shown significant performance deficiencies. Thermally evaporated WAW structures show weak adhesion to the substrate with rapid degradation of coloration efficiency. Improved EC durability can be obtained using magnetron sputtering deposition, but this requires the insertion of an extra tungsten (W) sacrificial layer beneath the external WO3 layer to prevent oxidation and associated loss of conductivity of the silver film. Here, we demonstrate for the first time that a new method, known as high-power impulse magnetron sputtering (HiPIMS), can produce trilayer bifunctional EC and TC devices, eliminating the need for the additional protective layer. X-ray photoelectron spectroscopy and X-ray diffraction data provided evidence that oxidation of the silver layer can be avoided, whilst stoichiometric WO3 structures are achieved. To achieve optimum WAW structures, we tuned the partial pressure of oxygen in the HiPIMS atmosphere applied for the deposition of WO3 layers. Our optimized WO3 (30 nm)/Ag (10 nm)/WO3 (50 nm) structure had a sheet resistance of 23.0 ± 0.4 Ω/□ and a luminous transmittance of 80.33 ± 0.07%. The HiPIMS coatings exhibited excellent long-term cycling stability for at least 2500 cycles, decent switching times (bleaching: 22.4 s, coloring: 15 s), and luminescence transmittance modulation (Δ T) of 34.5%. The HiPIMS strategy for the fabrication of ITO-free EC coatings for smart windows holds great promise to be extended to producing other metal-dielectric composite coatings for modern applications such as organic light-emitting diodes (OLEDs), liquid crystals, and wearable displays.

Multifunctional Ti-xCu coatings for cardiovascular interfaces: Control of microstructure and surface chemistry.

Ti-xCu coatings with varied Cu contents were deposited by hybrid HiPIMS/DC magnetron co-sputtering to achieve optimum microstructures and surface chemistries for applications as multi-functional, blood-contacting interfaces. We have demonstrated that control over the chemistry and microstructure of the coatings provides interfaces that simultaneously exhibit antibacterial properties, show endothelial cell (EC) compatibility, and prevent smooth muscle cell (SMC) proliferation. Using XRD and HRTEM analyses, we identified distinct microstructures for coatings with various Cu/(Cu + Ti) atomic concentrations. The corrosion resistance was controlled by the microstructure of the Ti-xCu coatings and decreased with increases in the Cu atomic concentration. XPS and ICP-MS results provided evidence that copper ions are released from the coatings upon immersion in PBS solution. We have demonstrated that the Cu-containing phases are weak points that are attacked and corroded easily, resulting in the release of Cu ions from the coatings. The coatings with Cu/(Ti + Cu) ratios ranging from 3 to 65 at.% inhibited the viability of SMCs significantly. The optimized coating with Ti and Cu/CuTix crystals and Cu/(Ti + Cu) ratio of 16 at.% showed significant improvements in EC compatibility as well as reduced viability of SMCs, holding great promise for the surface modification of cardiovascular devices such as stents and coronary implants. The coatings with amorphous phases and Cu/(Ti + Cu) ratios of 55 and 65 at.% showed excellent antibacterial properties against Staphylococcus aureus bacteria. The coating with 55.0 at.% Cu is an encouraging material for the surface engineering of blood-contacting implant surfaces that have antibacterial properties but are not cytotoxic to SMCs.

[Study on a novel vascular stent material (titanium oxide, Ti-O) coated with albumin and heparin: is it hemocompatible with fibrinogen].

The functional hemocompatibility between fibrinogen (FIG) and a novel vascular stent material (Ti-O film fixed with albumin and heparin) was investigated as follows: (1) Preparing the new biologic material (Ti-O) film; (2) Coating albumin and heparin on the Ti-O film; (3) Testing platelets (PL) adsorption; (4) Determining FIG adhesion number by use of enzyme linked immunoassay (ELISA); (5) Implanting the films from the test group of Ti-O film and from the comparison group of stainless steel (SS) film into the left and right femoral arteries respectively in 4 dogs. It was proved that albumin and heparin were fixed on Ti-O film. After 6 months, the femoral arteries of the dogs were resected. In the test group of Ti-O film coated with albumin and heparin, few PL adhered to the coat, their form did not change, and no thrombus was found by scanning electron microscopy; the result was better than that of plain Ti-O film, and was much better than that of SS film. Ti-O maintained normal transformation condition of FIG, and no C terminal of gamma chain in FIG was revealed. As it is known whether the hemocompatibility of a biomaterial is good depends upon its adsorption of FIG, and Ti-O has excellent reaction on albumin and heparin by chemical processes. In this study, the Ti-O film coated with albumin and heparin further reduced the absorption of FIG and PL when compared against the plain Ti-O film. So the Ti-O film coated with albumin and heparin has the insistent and permanent anticoagulant character.

Nitric oxide producing coating mimicking endothelium function for multifunctional vascular stents.

The continuous release of nitric oxide (NO) by the native endothelium of blood vessels plays a substantial role in the cardiovascular physiology, as it influences important pathways of cardiovascular homeostasis, inhibits vascular smooth muscle cell (VSMC) proliferation, inhibits platelet activation and aggregation, and prevents atherosclerosis. In this study, a NO-catalytic bioactive coating that mimics this endothelium functionality was presented as a hemocompatible coating with potential to improve the biocompatibility of vascular stents. The NO-catalytic bioactive coating was obtained by covalent conjugation of 3,3-diselenodipropionic acid (SeDPA) with glutathione peroxidase (GPx)-like catalytic activity to generate NO from S-nitrosothiols (RSNOs) via specific catalytic reaction. The SeDPA was immobilized to an amine bearing plasma polymerized allylamine (PPAam) surface (SeDPA-PPAam). It showed long-term and continuous ability to catalytically decompose endogenous RSNO and generate NO. The generated NO remarkably increased the cGMP synthesis both in platelets and human umbilical artery smooth muscle cells (HUASMCs). The surface exhibited a remarkable suppression of collagen-induced platelet activation and aggregation. It suppressed the adhesion, proliferation and migration of HUASMCs. Additionally, it was found that the NO catalytic surface significantly enhanced human umbilical vein endothelial cell (HUVEC) adhesion, proliferation and migration. The in vivo results indicated that the NO catalytic surface created a favorable microenvironment of competitive growth of HUVECs over HUASMCs for promoting re-endothelialization and reducing restenosis of stents in vivo.

The covalent immobilization of heparin to pulsed-plasma polymeric allylamine films on 316L stainless steel and the resulting effects on hemocompatibility.

For an improved hemocompatibility of 316L stainless steel (SS), we develop a facile and effective approach to fabricating a pulsed-plasma polymeric allylamine (P-PPAm) film that possesses a high cross-linking degree and a high density of amine groups, which is used for subsequent bonding of heparin. The P-PPAm film as a stent coating shows good resistance to the deformation behavior of compression and expansion of a stent. Using deionized water as an aging medium, it is demonstrated that the heparin-immobilized P-PPAm (Hep-P-PPAm) surface has a good retention of heparin. The systematic in vitro hemocompatibility evaluation reveals lower platelet adhesion, platelet activation and fibrinogen activation on the Hep-P-PPAm surface, and the activated partial thromboplastin time prolongs for about 15 s compared with 316L SS. The P-PPAm surface significantly promotes adhesion and proliferation of endothelial cells (ECs). For the Hep-P-PPAm, although EC adhesion and proliferation is slightly suppressed initially, after cultivation for 3 days, the growth behavior of ECs is remarkably improved over 316L SS. In vivo results indicate that the Hep-P-PPAm surface successfully restrain thrombus formation by growing a homogeneous and intact shuttle-like endothelium on its surface. The Hep-P-PPAm modified 316L SS shows a promising application for vascular devices.