Maciej Sowa

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.

Urea removal from aqueous solutions—a review

The abundance of urea in the natural environment is dictated by the fact that it is one of the major products of mammalian protein metabolism. Due to the extensive use of urea in many branches of industry, it is produced in large quantities. Urea enters into the environment not only with wastewater from the production plants but also by leaching from the fields, agro-breeding farms, and the effluents from the plants using it as a raw material. There are many methods of urea removal, but most of them are still being developed or are very new. The methods themselves differ in terms of physicochemical nature and technological ingenuity. Many wastewater treatment methods include processes such as hydrolysis, enzymatic hydrolysis, decomposition in the biological bed, decomposition by strong oxidants, adsorption, catalytic decomposition, and electrochemical oxidation. In this work, methods of urea removal from aqueous solutions have been reviewed. Particular attention was paid to electrochemical methods.Graphical Abstract

Modification of niobium surfaces using plasma electrolytic oxidation in silicate solutions

Herein, a study of the plasma electrolytic oxidation (PEO) of niobium in an anodising bath composed of potassium silicate (K2SiO3) and potassium hydroxide (KOH) is reported. The effects of the K2SiO3 concentration in the bath and the process voltage on the characteristics of the obtained oxide layers were assessed. Compact, barrier-type oxide layers were obtained when the process voltage did not exceed the breakdown potential of the oxide layer. When this threshold was breached, the morphology of the oxide layer changed markedly, which is typical of PEO. A significant amount of silicon, in the form of amorphous silica, was incorporated into the oxide coatings under these conditions compared with the amount obtained with conventional anodising. This surface modification technique led to an improvement in the corrosion resistance of niobium in Ringer’s solution, regardless of the imposed process conditions.

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 Ringers 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.

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.

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.

Galvanic Formation of Zn-Ni/Zn-Co Type Multilayer Alloy Coatings on Steel Substrate

Zn-Ni and Zn-Co monolayer and Zn-Ni/Zn-Co multilayer (from 2 to 128 layers) alloy coatings were formed on steel substrate by electrodeposition from acidic Zn-Ni bath and neutral Zn-Co bath. Samples were tested in salt chamber for corrosion resistance in neutral salt spray. Open circuit potential measurement and gravimetric study of corrosion were carried for samples immersed in the 5% NaCl solution.It was found that coatings of Zn-Ni surface layer occurred higher corrosion resistance then the coatings of Zn-Co surface layer. Sixteen-layer coating with Zn-Ni surface layer proved to be most effective in protecting the steel substrate. Zn-Ni monolayer showed the lowest corrosion potential, which affects the corrosion properties. Sample weight changes during exposure to a corrosive environment are related to digestion of the coating and the formation of corrosion products.

Anodic Treatment of Zn-Ni Alloy in Alkaline Solutions

The investigations on anodic oxidation of galvanic Zn-Ni alloy coating in the baths containing sodium hydroxide, sodium silicate and ammonium pentaborate was described in this paper. The surface morphology studies (SEM) and corrosion characterization was the main part of the work. It was found that the anodic treatment of the Zn-Ni alloy coating in the alkali solutions basis on NaOH permit to the obtaining the oxide layer with cracks formation. Application of the baths containing also sodium silicate and ammonium pentaborate cause the cracks decay. The corrosion studies may indicate that the cracks are shallow.