Shaping the Structure and Properties of TiO2-ZnO Oxide Coatings Produced by Plasma Electrolytic Oxidation on Titanium Substrate.

The paper presents the results of preliminary research on the possibility of synthesizing ZnO-TiO2 mixed coatings by plasma electrochemical oxidation (PEO). The aim of the work was to synthesize TiO2-ZnO mixed coatings on a titanium substrate from an electrolyte containing ZnO nanoparticles (NPs) and to assess the parameters of PEO on the structure, chemical composition, and properties of the obtained oxide coatings. The PEO process was carried out under various current-voltage conditions using different signals: DC, DC pulse, and AC. In this work, optimal conditions for the PEO process were determined to obtain well-adhering oxide coatings with the highest possible content of ZnO. The structure and morphology of the resulting oxide coatings were investigated, and their chemical and phase composition was comprehensively examined (EDX, XRD, XPS, and GD-OES). In addition, their basic optical properties were assessed. It has been shown that in the PEO DC pulse process, it is possible to obtain oxide coatings characterized by a high degree of structure order, high ZnO content in the oxide coating (3.6 at.%, XPS), and prospective applications for photocatalytic purposes (3.12 eV).

Nitrilotriacetic Acid Improves Plasma Electrolytic Oxidation of Titanium for Biomedical Applications.

Dental implants have become a routine, affordable, and highly reliable technology to replace tooth loss. In this regard, titanium and its alloys are the metals of choice for the manufacture of dental implants because they are chemically inert and biocompatible. However, for special cohorts of patients, there is still a need for improvements, specifically to increase the ability of implants to integrate into the bone and gum tissues and to prevent bacterial infections that can subsequently lead to peri-implantitis and implant failures. Therefore, titanium implants require sophisticated approaches to improve their postoperative healing and long-term stability. Such treatments range from sandblasting to calcium phosphate coating, fluoride application, ultraviolet irradiation, and anodization to increase the bioactivity of the surface. Plasma electrolytic oxidation (PEO) has gained popularity as a method for modifying metal surfaces and delivering the desired mechanical and chemical properties. The outcome of PEO treatment depends on the electrochemical parameters and composition of the bath electrolyte. In this study, we investigated how complexing agents affect the PEO surfaces and found that nitrilotriacetic acid (NTA) can be used to develop efficient PEO protocols. The PEO surfaces generated with NTA in combination with sources of calcium and phosphorus were shown to increase the corrosion resistance of the titanium substrate. They also support cell proliferation and reduce bacterial colonization and, hence, lead to a reduction in failed implants and repeated surgeries. Moreover, NTA is an ecologically favorable chelating agent. These features are necessary for the biomedical industry to be able to contribute to the sustainability of the public healthcare system. Therefore, NTA is proposed to be used as a component of the PEO bath electrolyte to obtain bioactive surface layers with properties desired for next-generation dental implants.

Corrosion Resistance and Electrical Conductivity of Hybrid Coatings Obtained from Polysiloxane and Carbon Nanotubes by Electrophoretic Co-Deposition.

Nanocomposites developed based on siloxanes modified with carbon nanoforms are materials with great application potential in the electronics industry, medicine and environmental protection. This follows from the fact that such nanocomposites can be endowed with biocompatibility characteristics, electric conductivity and a high mechanical durability. Moreover, their surface, depending on the type and the amount of carbon nanoparticles, may exhibit antifouling properties, as well as those that limit bacterial adhesion. The paper reports on the properties of polysiloxane (PS) and carbon nanotubes (CNT) nanocomposite coatings on metal surfaces produced by the electrophoretic deposition (EPD). A comparison with coatings made of pure PS or pure CNT on the same substrates using the same deposition method (EPD) is provided. The coatings were examined for morphology and elemental composition (SEM, EDS), structural characteristics (confocal Raman spectroscopy), electrical conductivity and were tested for corrosion (electrochemical impedance spectroscopy-EIS, potentiodynamic polarization-PDP). The results obtained in this study clearly evidenced that such hybrid coatings conduct electricity and protect the metal from corrosion. However, their corrosion resistance differs slightly from that of a pure polymeric coating.

Fabrication and Characterization of New Functional Graded Material Based on Ti, Ta, and Zr by Powder Metallurgy Method.

In view of the aging population and various diseases worldwide, the demand for implants has been rapidly increasing. Despite the efforts of doctors, engineers, and medical companies, the fabrication of and procedures associated with implants have not yet been perfected. Therefore, a high percentage of premature implantations has been observed. The main problem with metal implants is the mechanical mismatch between human bone and the implant material. Zirconium/titanium-based materials with graded porosity and composition were prepared by powder metallurgy. The whole samples are comprised of three zones, with a radial gradient in the phase composition, microstructure, and pore structure. The samples were prepared by a three-step powder metallurgy method. The microstructure and properties were observed to change gradually with the distance from the center of the sample. The x-ray diffraction analysis and microstructure observation confirmed the formation of diffusive connections between the particular areas. Additionally, the mechanical properties of the obtained materials were checked, with respect to the distance from the center of the sample. An analysis of the corrosion properties of the obtained materials was also carried out.

Electrodeposition of Copper and Brass Coatings with Olive-Like Structure.

One method of creating a brass coating is through electrodeposition, which is most often completed in cyanide galvanic baths. Due to their toxicity, many investigations focused on the development of more environmentally friendly alternatives. The purpose of the study was to explore a new generation of non-aqueous cyanide-free baths based on 1-ethyl-3-methylimidazolium acetate ionic liquids. The study involved the formation of copper, zinc, and brass coatings. The influence of the bath composition, cathodic current density, and temperature was determined. The obtained coatings were characterized in terms of their morphology, chemical composition, phase composition, roughness, and corrosion resistance. It was found that the structure of the obtained coatings is strongly dependent on the process parameters. The three main structure types observed were as follows: fine-grained, porous, and olive-like. To the best knowledge of the authors, it is the first time the olive-like structure was observed in the case of an electrodeposited coating. The Cu-Zn coatings consisted of 19-96 at. % copper and exhibited relatively good corrosion resistance. A significant improvement of corrosion properties was found in the case of copper and brass coatings with the olive-like structure.

Corrosion Inhibitor-Modified Plasma Electrolytic Oxidation Coatings on 6061 Aluminum Alloy.

There are many methods for incorporating organic corrosion inhibitors to oxide coatings formed on aluminum alloys. However, typically they require relatively concentrated solutions of inhibitors, possibly generating a problematic waste and/or are time-/energy-consuming (elevated temperature is usually needed). The authors propose a three-step method of oxide layer formation on 6061-T651 aluminum alloy (AAs) via alternating current (AC) plasma electrolytic oxidation (PEO), impregnation with an 8-hydroxyquinoline (8-HQ) solution, and final sealing by an additional direct current (DC) polarization in the original PEO electrolyte. The obtained coatings were characterized by scanning electron microscopy, roughness tests, contact angle measurements, X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy. Additionally, corrosion resistance was assessed by potentiodynamic polarization in a NaCl solution. Two types of the coating were formed (A-thicker, more porous at 440 mA cm-2; B-thinner, more compact at 220 mA cm-2) on the AA substrate. The 8-HQ impregnation was successful as evidenced by XPS. It increased the contact angle only for the B coatings and improved the corrosion resistance of both coating systems. Additional DC treatment destroyed superficially adsorbed 8-HQ. However, it served to block the coating pores (contact angle ≈ 80°) which improved the corrosion resistance of the coating systems. DC sealing alone did not bring about the same anti-corrosion properties as the combined 8-HQ impregnation and DC treatment which dispels the notion that the provision of the inhibitor was a needless step in the procedure. The proposed method of AA surface treatment suffered from unsatisfactory uniformity of the sealing for the thicker coatings, which needs to be amended in future efforts for optimization of the procedure.

Effects of the sources of calcium and phosphorus on the structural and functional properties of ceramic coatings on titanium dental implants produced by plasma electrolytic oxidation.

Plasma Electrolytic Oxidation (PEO) is as a promising technique to modify metal surfaces by application of oxide ceramic coatings with appropriate physical, chemical and biological characteristics. Therefore, objective of this research was to find the simplest settings, yet able to produce relevant bioactive implant surfaces layers on Ti implants by means of PEO. We show that an electrolyte containing potassium dihydrogen phosphate as a source of P and either calcium hydroxide or calcium formate as a source of Ca in combination with a chelating agent, ethylenediamine tetraacetic acid (EDTA), is suitable for PEO to deliver coatings with desired properties. We determined surface morphology, roughness, wettability, chemical and phase composition of titanium after the PEO process. To investigate biocompatibility and bacterial properties of the PEO oxide coatings we used microbial and cell culture tests. The electrolyte based on Ca(OH)2 and EDTA promotes active crystallization of apatites after PEO processing of the Ti implants. The PEO layers can increase electrochemical corrosion resistance. The PEO can be potentially used for development of bioactive surfaces with increased support of eukaryotic cells while inhibiting attachment and growth of bacteria without use of antibacterial agents.

Incorporation of Ca ions into anodic oxide coatings on the Ti-13Nb-13Zr alloy by plasma electrolytic oxidation.

The present work concerns the surface modification of The Ti-13Nb-13Zr alloy by electropolishing and plasma electrolytic oxidation (PEO) process in Ca-containing electrolytes: calcium formate and calcium lactate solutions (0.1-1.0 mol dm-3) under voltages of 200 and 400 V. As a result of the PEO process, a porous oxide layer containing incorporated calcium compounds was formed on the Ti-13Nb-13Zr alloy surface. The morphology and chemical composition of the modified Ti-13Nb-13Zr alloy were investigated using scanning electron microscopy (SEM + EDS), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). An increase in the applied voltage caused an increase in the number of pores and an increase in the amount of calcium incorporated in the oxide layer. Analysis showed that all samples were covered by titanium oxide, which was present in the form of anatase and/or rutile. In course of the experiments, it was showed that the proposed procedure has a positive effect on the overall bioactivity of the Ti-13Nb-13Zr alloy. Bioactivity investigations using simulated body fluid (SBF) confirmed the formation of apatite on the anodized surfaces. The cell adhesion results obtained by the use of human bone marrow mesenchymal stem cells (hBMSC) demonstrated that the PEO coatings on the Ti-13Nb-13Zr alloy remarkably enhanced the cytocompatibility of the substrate, indicating a potential application in orthopedic surgeries. The incorporation of Ca into the oxide layer proceeded to a higher extent when the PEO treatment was performed in the calcium lactate bath. The oxide layers formed in the calcium lactate solution exhibited also superior biological behavior towards hBMSC. This can be ascribed to the presence of carboxylic groups onto coatings' surface (as identified by XPS), which facilitated the anchoring of cells and tissues.

Effect of DC Plasma Electrolytic Oxidation on Surface Characteristics and Corrosion Resistance of Zirconium.

Zr is a valve metal, the biocompatibility of which is at least on par with Ti. Recently, numerous attempts of the formation of bioactive coatings on Zr by plasma electrolytic oxidation (PEO) in solutions that were based on calcium acetate and calcium β-glycerophosphate were made. In this study, the direct current (DC) PEO of commercially pure zirconium in the solutions that contained Ca(H2PO2)2, Ca(HCOO)2, and Mg(CH3COO)2 was investigated. The treatment was conducted at 75 mA/cm² up to 200, 300, or 400 V. Five process stages were discerned. The treatment at higher voltages resulted in the formation of oxide layers that had Ca/P or (Mg+Ca)/P ratios that were close to that of hydroxyapatite (Ca/P = 1.67), determined by SEM/EDX. The corrosion resistance studies were performed using electrochemical impedance spectroscopy (EIS) and DC polarization methods. R(Q[R(QR)]) circuit model was used to fit the EIS data. In general, the coatings that were obtained at 200 V were the most corrosion resistant, however, they lacked the porous structure, which is typical for PEO coatings, and is sought after in the biomedical applications. The treatment at 400 V resulted in the formation of the coatings that were more corrosion resistant than those that were obtained at 300 V. This was determined mainly by the prevailing plasma regime at the given process voltage. The pitting resistance of Zr was also improved by the treatment, regardless of the applied process conditions.

Electrochemical Impedance and Polarization Corrosion Studies of Tantalum Surface Modified by DC Plasma Electrolytic Oxidation.

Tantalum has recently become an actively researched biomaterial for the bone reconstruction applications because of its excellent corrosion resistance and successful clinical records. However, a bare Ta surface is not capable of directly bonding to the bone upon implantation and requires some method of bioactivation. In this study, this was realized by direct current (DC) plasma electrolytic oxidation (PEO). Susceptibility to corrosion is a major factor determining the service-life of an implant. Therefore, herein, the corrosion resistance of the PEO coatings on Ta was investigated in Ringer's solution. The coatings were formed by galvanostatic anodization up to 200, 300 and 400 V, after which the treatment was conducted potentiostatically until the total process time amounted to 5 min. Three solutions containing Ca(H2PO2)2, Ca(HCOO)2 and Mg(CH3COO)2 were used in the treatment. For the corrosion characterization, electrochemical impedance spectroscopy and potentiodynamic polarization techniques were chosen. The coatings showed the best corrosion resistance at voltages low enough so that the intensive sparking was absent, which resulted in the formation of thin films. The impedance data were fitted to the equivalent electrical circuits with two time constants, namely R(Q[R(QR)]) and R(Q[R(Q[RW])]). The inclusion of W in the circuit helped to fit the low-frequency part of the samples PEO-ed at 400 V, hinting at the important role of diffusion in the corrosion resistance of the PEO coatings described in the research.

On influence of anodic oxidation on thrombogenicity and bioactivity of the Ti-13Nb-13Zr alloy.

PURPOSE: This paper reports on the results of investigations on the blood response to the modified of surfaces titanium alloys. METHODS: To enhance biocompatibility of the Ti-13Nb-13Zr alloy, anodisation was performed at 80 and 150 V. The oxidation process was carried out in a solution containing 4 mol dm-3 H3PO4 and 0.59 mol dm-3 Ca(H2PO2)2. RESULTS: The haemolytic activity of the titanium alloy surface was not altered much by the anodisation. The obtained values of the percentage of haemolysis were well below the levels required for the materials intended for blood contact. The clotting time of the blood was similar for the as-ground sample and the sample anodised at 80 V. For the sample anodised at 150 V the clotting time was shorter. The differences between these samples were observed in partial thromboplastin time after activation, prothrombin time and thrombin time, after 24 h. Extracts taken from the samples were not toxic towards the L-929 mouse fibroblast cells. CONCLUSIONS: The proposed treatment might be appropriate for the preparation of modified Ti-13Nb-13Zr surfaces intended for bone reconstruction or cardiovascular implants depending on process parameters.

Bioactivity of coatings formed on Ti-13Nb-13Zr alloy using plasma electrolytic oxidation.

In this work, we investigated the bioactivity of anodic oxide coatings on Ti-13Nb-13Zr alloy by plasma electrolytic oxidation (PEO) in solutions containing Ca and P. The bioactive properties of the films were determined by immersion in simulated body fluid (SBF), and their biocompatibility was examined using adult human bone marrow derived mesenchymal stem cells (hBMSCs). The oxide layers were characterised based on their surface morphology (SEM, AFM, profilometry) as well as on their chemical and phase compositions (EDX, XRF, XRD, XPS). We report that anodic oxidation of Ti-13Nb-13Zr led to the development of relatively thick anodic oxide films that were enriched in Ca and P in the form of phosphate compounds. Furthermore, the treatment generated rough surfaces with a significant amount of open pores. The surfaces were essentially amorphous, with small amounts of crystalline phases (anatase and rutile) being observed, depending on the PEO process parameters. SBF soaking led to the precipitation of small crystals after one week of experiment. During culturing of hBMSCs on the bioactive Ti-13Nb-13Zr surfaces the differentiation of human mesenchymal stem cells toward osteoblasts was promoted, which indicated a potential of the modified materials to improve implant osseointegration.

Influence of electropolishing and anodic oxidation on morphology, chemical composition and corrosion resistance of niobium.

The work presents results of the studies performed on electropolishing of pure niobium in a bath that contained: sulphuric acid, hydrofluoric acid, ethylene glycol and acetanilide. After the electropolishing, the specimens were subjected to anodic passivation in a 1moldm(-3) phosphoric acid solution at various voltages. The surface morphology, thickness, roughness and chemical composition of the resulting oxide layers were analysed. Thusly prepared niobium samples were additionally investigated in terms of their corrosion resistance in Ringer's solution. The electropolished niobium surface was determined to be smooth and lustrous. The anodisation led to the growth of barrier-like oxide layers, which were enriched in phosphorus species.