Wojciech Simka

Application of plasma electrolytic oxidation to bioactive surface formation on titanium and its alloys

In this work, a review of the literature concerning the surface modification of implants composed of titanium and titanium alloys by plasma electrochemical oxidation (PEO), also known as micro-arc oxidation (MAO), is presented. The application of this process allows for the formation of oxide layers with different porosities on implants. Moreover, it is possible to enrich these oxide layers with species contained in solutions used for anodising, yielding suitable surface chemical properties. Anodising titanium implants in solutions containing compounds of calcium and phosphorous leads to the formation of bioactive layers and significantly reduces the time required for the osseointegration of implant to bone. Studies of the PEO process with respect to titanium implants have been conducted by a large number of research centres, and their results have been applied to the production of a new generation of titanium implants.

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.

Electrochemical and biological characterization of coatings formed on Ti–15Mo alloy by plasma electrolytic oxidation

β-Type titanium alloys are considered the future materials for bone implants. To improve the bioactivity of Ti-15Mo, the surface was modified using the plasma electrolytic oxidation (PEO) process. Tricalcium phosphate (TCP, Ca3PO4), wollastonite (CaSiO3) and silica (SiO2) were selected as additives in the anodizing bath to enhance the bioactivity of the coatings formed during the PEO process. Electrochemical analysis of the samples was performed in Ringers solution at 37°C. The open-circuit potential (EOCP) as a function of time, corrosion potential (ECORR), corrosion current density (jCORR) and polarization resistance (Rp) of the samples were determined. Surface modification improved the corrosion resistance of Ti-15Mo in Ringers solution. In vitro studies with MG-63 osteoblast-like cells were performed for 1, 3 and 7 days. After 24h, the cells were well adhered on the entire surfaces, and their number increased with increasing culture time. The coatings formed in basic solution with wollastonite exhibited better biological performance compared with the as-ground sample.

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

Surface characterisation of Ti–15Mo alloy modified by a PEO process in various suspensions

This paper reports on the surface modification of a Ti-15Mo alloy by plasma electrolytic oxidation (PEO). This process was carried out in solutions of 0.1M Ca(H2PO2)2 with various concentrations of tricalcium phosphate (Ca3(PO4)2), wollastonite (CaSiO3), or silica (SiO2) using voltages of up to 350V. The surface microstructure (SEM, cross-section of coating), roughness and chemical composition (energy-dispersive X-ray spectroscopy, thin layer X-ray diffraction, X-ray photoelectron spectroscopy and Raman spectroscopy) of the porous oxide layers were investigated. The concentration of powder added to the solution changed the chemical composition and morphology of PEO coatings on the Ti-15Mo alloy surface. Calcium and phosphorous compounds were detected in the coatings formed on the substrate by the PEO process at 300V.

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.

Formation of bioactive coatings on Ti–13Nb–13Zr alloy for hard tissue implants

In an attempt to increase the bioactivity of a vanadium-free titanium alloy, Ti–13Nb–13Zr, the plasma electrolytic oxidation (PEO) process for surface modification was utilised. Select samples were subjected to further treatment, either thermal or alkali. The morphology, chemical composition, and phase composition of the treated Ti–13Nb–13Zr alloy were investigated using scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). It was observed that during the anodic process under sparking discharge conditions, the simultaneous incorporation of calcium and phosphorus in the forming oxide layer occurs. The resulting layers were porous and exhibited the typical morphology for layers formed during the PEO process. After the alkali treatment of samples oxidised at 150 V, a gel-like titanate layer was formed. The bioactivity investigations in simulated body fluid (SBF) solution indicated that after anodising at 150 V and following alkali treatment the Ti–13Nb–13Zr alloy exhibits osteoinductive properties. The approach presented here may be applied for fabricating Ti–13Nb–13Zr-based implants for hard tissue regeneration.

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.

α-Amidoalkylating Agents from N-Acyl-α-amino Acids: 1-(N-Acylamino)alkyltriphenylphosphonium Salts

N-Acyl-α-amino acids were efficiently transformed in a two-step procedure into 1-N-(acylamino)alkyltriphenylphosphonium salts, new powerful α-amidoalkylating agents. The effect of the α-amino acid structure, the base used [MeONa or a silica gel-supported piperidine (SiO(2)-Pip)], and the main electrolysis parameters (current density, charge consumption) on the yield and selectivity of the electrochemical decarboxylative α-methoxylation of N-acyl-α-amino acids (Hofer-Moest reaction) was investigated. For most proteinogenic and all studied unproteinogenic α-amino acids, very good results were obtained using a substoichiometric amount of SiO(2)-Pip as the base. Only in the cases of N-acylated cysteine, methionine, and tryptophan, attempts to carry out the Hofer-Moest reaction in the applied conditions failed, probably because of the susceptibility of these α-amino acids to an electrochemical oxidation on the side chain. The methoxy group of N-(1-methoxyalkyl)amides was effectively displaced with the triphenylphosphonium group by dissolving an equimolar amount of N-(1-methoxyalkyl)amide and triphenylphosphonium tetrafluoroborate in CH(2)Cl(2) at room temperature for 30 min, followed by the precipitation of 1-N-(acylamino)alkyltriphenylphosphonium salt with Et(2)O.

Novel bioactive polyester scaffolds prepared from unsaturated resins based on isosorbide and succinic acid.

In this study new biodegradable materials obtained by crosslinking poly(3-allyloxy-1,2-propylene succinate) (PSAGE) with oligo(isosorbide maleate) (OMIS) and small amount of methyl methacrylate were investigated. The porous scaffolds were obtained in the presence of a foaming system consisted of calcium carbonate/carboxylic acid mixture, creating in situ porous structure during crosslinking of liquid formulations. The maximum crosslinking temperature and setting time, the cured porous materials morphology as well as the effect of their porosity on mechanical properties and hydrolytic degradation process were evaluated. It was found that the kind of carboxylic acid used in the foaming system influenced compressive strength and compressive modulus of porous scaffolds. The MTS cytotoxicity assay was carried out for OMIS using hFOB1.19 cell line. OMIS resin was found to be non-toxic in wide range of concentrations. On the ground of scanning electron microscopy (SEM) observations and energy X-ray dispersive analysis (EDX) it was found that hydroxyapatite (HA) formation at the scaffolds surfaces within short period of soaking in phosphate buffer solution occurs. After 3h immersion a compact layer of HA was observed at the surface of the samples. The obtained results suggest potential applicability of resulted new porous crosslinked polymeric materials as temporary bone void fillers.