A. Yu. Ustinov

The effect of the conditions of formation on ferromagnetic properties of iron-containing oxide coatings on titanium

Oxide coatings formed on titanium by plasma-electrolytic oxidation in a Na3PO4 + Na2B4O7 + Na2WO4 + Fe2(C2O4)3 electrolyte-suspension at different current densities and different durations of treatment are shown to have ferromagnetic properties. The coercive force of the specimens reaches maximum values of 124 and 380 Oe at 300 and 10 K, respectively, when the thickness of coatings is about 3–5 mm. Crystallites with a mean size of ∼50 nm are found to be present in pores of the coatings. Based on the experimental data, combined with the results of theoretical modeling carried out previously, crystallites are concluded to be iron particles surrounded with a shell composed of oxides and/or hydroxides. The existence of crystallites and their spatial sizes determine the ferromagnetic properties of the coatings.

Magnetoactive oxide layers formed on titanium by plasma-electrolytic technique

Two kinds of iron-containing coatings, specifically those obtained from electrolytes containing polyphosphate iron complexes (no. 1) and from electrolyte suspensions (no. 2), are formed and studied. According to the microprobe analysis, the iron content in the coatings is 6–7 at %. Coatings of type 1 are paramagnetic, while coatings of type 2 are ferromagnetic. The distribution of elements over the depth of coatings is heterogeneous and the typical components of the surfaces have different compositions. Iron and titanium are concentrated at the bottom and walls of pores. Upon annealing in air, iron and titanium phosphates crystallize in coatings no. 1, while maghemite is formed in coatings no. 2. Based on the results obtained, the supposition is made that the ferromagnetic properties of type 2 coatings are determined by the presence of fine-dispersed magnetite and/or maghemite particles in them, as well as titanium-magnetite and/or titanium-maghemite grains.

Comparative analysis of the composition, structure, and catalytic activity of the NiO-CuO-TiO2 on Titanium and NiO-CuO-Al2O3 on aluminum composites

The catalytically active oxide structures based on Al and Ti prepared by plasma-electrolytic oxidation (PEO) and additionally modified by impregnation with an aqueous solution of nickel and copper nitrates followed by annealing were studied. The oxide film-metal composites were studied using X-ray diffraction and X-ray spectroscopic analysis, X-ray electron spectroscopy, and electron microscopy. The catalytic activity of the composites in the reaction of CO oxidation was studied. In spite of differences in the elemental composition and morphology, the initial oxide layers on Al and Ti were comparable in terms of activity. Microgranules of size ∼ 1 µm and formations from tens to hundreds of nanometers in size were detected on the surface of PEO layers. The modified layers contained crystalline CuO, NiO, and Al2O3 or TiO2 phases. The surface layers of the modified structures about 3 nm in thickness on AMg5 aluminum alloy and VT1-0 titanium had the same elemental composition but exhibited different activity in the reaction of CO oxidation to CO2.

Protective oxide coatings on Mg-Mn-Ce, Mg-Zn-Zr, Mg-Al-Zn-Mn, Mg-Zn-Zr-Y, and Mg-Zr-Nd magnesium-based alloys

Protective coatings are formed on different magnesium-based alloys (Mg-Mn-Ce, Mg-Zn-Zr, Mg-Al-Zn-Mn, Mg-Zn-Zr-Y, and Mg-Zr-Nd) by plasma electrolytic oxidation. Electrochemical and mechanical properties of the coatings are studied, as well as their chemical and phase compositions and structures. Analysis of the data obtained revealed the reasons for the differences in the corrosion and mechanical characteristics between plasma electrolytic layers formed on different magnesium alloys used in aviation and space engineering.

Magnetic properties of plasma-electrolytic iron-containing oxide coatings on aluminum alloy

Applications of the plasma-electrolytic oxidation technique for the formation of magnetically active oxide coatings on aluminum and titanium are reviewed. Specimens of aluminum-, iron-, and tungsten-containing oxide layers on aluminum substrates with ferro- and ferrimagnetic properties are experimentally produced and studied, as well as specimens that can be remagnetized at certain external magnetic field intensities and specimens the magnetization of which is opposite to the external field. The existence of nano- and microscale crystallites, in which aluminum and metals from the electrolyte are accumulated, are found in pores of the coatings. The crystallites supposedly determine the magnetic properties of the specimens. A correlation between the Fe/Σ(W, Al) atomic ratio in crystallites and the magnetic properties of the systems studied is discovered.

Carbon in oxide layers formed under electric discharge conditions

The presence of carbon on the surface and in deep layers of oxide coatings produced by plasmaelectrolytic oxidation is studied. Graphite is found in the coatings formed on titanium under the conditions of cathodic polarization in an organic electrolyte. Carbon in the amount of 16–40 at % is present on the surface of coatings produced on aluminum at the anodic polarization in aqueous electrolytes. Compounds with C-O (oxidized carbon), C-C or C-H (aliphatic carbon), and C-M (carbide carbon) bonds are determined. The carbon content decreases to a few atomic percents upon etching the surface with a high-energy argon beam and removing a nearly 3-nm layer. Aliphatic and metal-oxide carbon is present at this depth. The carbon content on either the surface or in deep layers of the coatings is the same, regardless of the stage of the coating formation, namely, prespark, spark, or microarc anodizing.

Catalytic properties of aluminum/nickel-, copper-containing oxide film compositions

The possibility of the single-step formation of nickel- and copper-containing thin-film oxide systems on aluminum by plasma electrolytic oxidation was demonstrated. The resulting structures were found to be active in the reaction of CO oxidation to CO2 in the temperature region 300–500°C. However, the resulting structures exhibited stable catalytic activity only in the simultaneous presence of nickel and copper compounds. The films were studied using X-ray diffraction, X-ray spectroscopic analysis, X-ray photoelectron spectroscopy, and electron microscopy. The resulting films exhibited an essentially inhomogeneous composition through the thickness. Electrolyte elements such as nickel, copper, sodium, and phosphorus were concentrated at the surface. Nickel occurred as Ni2+, and copper occurred as Cu+ and Cu2+. The surface contained carbon in detectable amounts.

Fabrication of polytetrafluoroethylene- and graphite-containing oxide layers on aluminum and titanium and their structure

Stable aqueous electrolyte emulsions with negatively charged micelles containing dispersed particles of polytetrafluoroethylene (PTFE) or graphite are obtained using siloxane-acrylate emulsion as an emulsifier. The oxide coatings formed in such electrolytes contain carbon, polytetrafluoroethylene, or graphite. The coatings with PTFE particles are similar to monolithic polytetrafluoroethylene with respect to its hydrophobic characteristics. According to X-ray photoelectron spectroscopy data, the surface of the formed coatings predominantly contains aliphatic carbon (C-C and C-H bonds) and some fraction of oxidized (or, in the case of PTFE-containing electrolytes, fluorinated) carbon.

Obtaining ZrO2 + CeOx + TiO2/Ti compositions by plasma-electrolytic oxidation of titanium and investigating their properties

Regularities of the effect produced by Ce2(SO4)3 salt introduced in an aqueous electrolyte containing Zr(SO4)2 on the plasma-electrolytic formation of oxide coatings on titanium, their composition, and structure are studied. ZrO2 + CeOx + TiO2 three-phase oxide coatings with a thickness about 10 μm are obtained. The coatings involve ZrO2 cubic phase. The ZrO2-to-TiO2 phase ratio in the coatings can be controlled. The zirconium content in the coatings reaches 20 at %, while that of cerium is 3–5 at %. The surface layer (∼3-nm thick) contains Ce3+ (∼30%) and Ce4+ (∼70%). Pores in the surface part of coatings have diameters around or smaller than 1 μm and are regularly arranged. The obtained systems have a certain catalytic activity with respect to the oxidation of CO to CO2 at temperatures above 400–450°C. The coatings are corrosion-resistant in chloride-containing environments. The thickness h of coatings depending on the charge Q supplied to the cell is described by the equation h = h0(Q/Q0)n, where n = 0.35 and h0 is the thickness of the coating formed at Q0 = 1 C/cm2.

Magnetic properties of iron-containing coatings formed by plasma-electrolytic oxidation

The magnetic properties of iron-containing coatings formed on aluminum by plasma-electrolytic oxidation were investigated. It was shown that the magnetic state of the samples studied is most likely induced by chemically inhomogeneous (multiphase) ferromagnetic particles.