Tribooxidation is the main mechanism to adapt the cutting tool to extreme mechanical and thermal loads during high-speed cutting. Wear and tribooxidation processes in the single layer TiAlCrSiYN and multilayer TiAlCrSiYN/TiAlCrN non-stoichiometric coatings on cutting tools after dry cutting with speed of 500 m/min on the running-in and steady wear stages were studied by the set of modern surface analysis methods. The reasonable preference of the multilayer coating comparing to the single layer one was demonstrated. It was established that oxide films with an amorphous-nanocrystalline structure are formed on the surface of the wear hole. Their composition is close to k Cr2O3, TiO2, Al2O3 (sapphire) and Al2O3 · 2(SiO2) (Mullite 1:2). Prospects of yttrium addition in the complex nitride were estimated by quantum chemical calculations, which has shown that such polyvalent metals as Ti+4, Cr+5,6, Y+4, Al+3 in a multicomponent nitride form a very complex spatially organized electronic structure of double and triple bonds with unoccupied π*-orbitals of nitrogen atoms. Quantum-chemical calculations of the oxidation susceptibility of these coatings with Y microadditions confirmed that this element is more inert than chromium and it is predominantly involved in the formation of interatomic bonds with Al, Ti, Cr affecting the mechanical properties of nitride coatings.

The physical mechanism of self-organization of a multilayer nanolaminated coating based upon non-equilibrium (TiAlCrSiY)N/(TiAlCr)N nitride on a cutting tool during high-speed (600 m/min.) dry cutting of N13 steel is established. Using a set of modern surface analysis methods coating degradation and tribo-oxidation are studied within the running-in and steady stages of wear. It is shown that during cutting, amorphous-nanocrystalline films of oxides similar to Cr2O3, TiO2, Al2O3 (sapphire) and Al2O3 · 2 (SiO2) (mullite) are formed within a wear crater. Using computer calculations by a finite element method, heat transfer is considered in the cutting zone during formation of protective tribo-oxides. It is found that among all tribo-oxides, mullite has the best thermal barrier properties. Oxidation is the main adaptation mechanism of a cutting tool under extreme mechanical and thermal shock during high-speed cutting. The topography of chip contact surface is studied at various cutting stages, which makes it possible to establish a change in plastic deformation mechanisms of treated metal and friction cutting modes. Quantum chemical calculations of the electron structure of mullite show the highest degree of its electron polarization and explain the radical drop in friction coefficient during film formation upon a wear surface. In this case, mullite acts as a solid lubricant.

In order to predict the shelf life of non-ferrous metals, laboratory studies into the kinetics of corrosion processes of metals under various temperature and humidity conditions were performed. The results of 12-month corrosion tests of the following non-ferrous metals are presented: aluminum, cobalt, copper, nickel, tin, lead, and zinc at various relative humidity and air temperature conditions. All the metals studied were found to be corrosion-resistant under atmospheric conditions at a relative humidity of no more than 80

The paper presents the results of cobalt corrosion tests in air at different temperature and humidity values. It was demonstrated that corrosion losses in cobalt at temperatures of 20 and 30 °C and relative humidity of 70, 80, and 95

The high-entropy PVD coating (AlCrZrTiTa)N, characterized by its high hardness (50–60 GPa), elastic modulus above 300 MPa, and high heat resistance up to 1300 °C, is used for coating cutting tools operating under extreme metalworking conditions. The nanostructured monolayer 3 μm PVD coating was deposited on cutting plates in the hybrid arc deposition PVD coater. The coating had an amorphous nanocrystalline microstructure with a grain size of about 10–50 nm. The samples of SS 304 steel were investigated during dry high-speed (600 m/min) cutting. Raman spectroscopy was used to study the formation of tribooxides on the tool surface at the running-in stage of the cutting. After 130 m of cutting, Cr2O3 oxide appears on the wear surface while other elements are bound with N atoms. When the cutting length is increased to up to 260 m, oxide Al2O3 · ZrO2 (mullite) and amorphous oxides TaO2 and CrO2 are formed. The method EELFS made it possible to determine the amorphous nanocrystalline structure of triboceramics based on CrO2 and Al2O3 · ZrO2. The nearest atomic surrounding of Cr-Cr, O-O, and Cr-O and their subsequent comparison with the available literature data allow us to calculate the equilibrium lattice constants of the CrO2 unit cell, which are equal to (a, b) = 4.3754 Å and c = 0.5927. The triboceramic films on the base of non-equilibrium mullite Al2O3·ZrO2 have an amorphous structure. In the first coordination sphere, the interatomic distances of Zr-O and Al-O were 1.79 and 1.89 Å. An accelerated adaptive reaction to extreme external stimuli, at the very beginning of the running-in stage, is established. The tribological adaptability of the high-entropy ultra-fine amorphous nanocrystalline coating under extremely loaded dry high-speed cutting is based on non-equilibrium phenomena: the partial oxidation of fragments of the nitride and dynamic formation of protective tribooxides, which have a good thermal barrier and frictional properties. These factors interact synergistically and determine the life of the cutting tool.

A nano-multilayer Ti0.2Al0.55Cr0.2Si0.03Y0.02N/Ti0.25Al0.65Cr0.1N PVD coating was deposited on Kennametal carbide K 313 inserts. These coatings are widely used to protect cutting tools under severe exploitation conditions. Under equilibrium conditions, it was found that the Al2O3 oxide possessed better adhesive properties than the TiO2. The addition of chromium further enhanced the oxidation resistance of the coatings. Silicon significantly increased the oxidation resistance of this type of coating. The properties of the diffusion process in this coating have not been sufficiently investigated, despite the considerable number of articles published on this topic. For the purpose of this study, a multilayer ion-plasma (TiAlCrSiY)N/(TiAlCr)N coating was oxidized under equilibrium conditions; its chemical inhomogeneity was studied by time-of-flight mass spectroscopy using a TOF SIMS5-100 instrument. The data was collected from an area of 100 × 100 µ. A D-300 profilometer (KLA-Tencor Corp., Milpitas, California 95035, USA) was used to determine the rate of ion etching. It was found that oxidation commenced at the surface nanolayer of a TiAlCrN nitride, forming loose films of Cr2O3, TiO2, and Al2O3 oxides. This passivating film had a thickness of around 140 nm. For the first time, the interlayer diffusion coefficients of Si and Y were determined in multilayer coatings based on Ti0.2Al0.55Cr0.2Si0.03Y0.02N/Ti0.25Al0.65Cr0.1N, under open air annealing at 700 °C. The physical nature of the differences in the diffusion of these elements is discussed. The diffusion rate in the near-surface volumes was lower than in the deep layers of the multilayer coating, most likely due to the formation of passivating oxide films on the surface.

The article shows the possibilities of the method of time-of-flight secondary ion mass spectroscopy for solving a wide range of materials science problems on the examples of studying the oxidation of a multilayer wear-resistant coating based on TiAlCrSiYN/TiAlCrN, chemical inhomogeneity in rolled high-strength steel, free-machining steel, and multilayer planar plasmon coatings for solar cells, as well as for more precise attribution of historical art ceramic items.

Modern surface analysis techniques are expanding significantly possibilities in description and attribution of historical artifacts. The present study is aimed to compare analytical ability of the X-ray fluorescent analysis (XRF) typically applied for studies ceramic art items with novel surface analysis methods: time-of-flight secondary ions mass spectroscopy (SIMS) and X-ray photoelectron spectroscopy (XPS) that were applied on measurements of elemental compositions of powder raw materials for porcelain fabrication: pegmatite P-1, Vesco-prima clay, kaolin, bone earth, dolomite, and feldspar. It was shown that SIMS successfully measures light elements unnoticeable for XRF such as lithium, beryllium, boron and heavy impurities not found out by XRF such as cobalt, cerium, copper, rubidium, vanadium. XPS has found thorium in the kaolin sample that was not detected by SIMS and XRF. The paper provides also values of chemical shifts of some XPS lines observed in materials under examination. The obtained information on relations of basic and impurity elements revealed by XRF and SIMS together with XPS chemical shifts data could be used to expose contemporary falsifications of historical porcelain and to attribute porcelain items during conservation process.

The paper describes hydrometallurgical methods to recycle wastes of vanadium pentoxide chemical fabrication. Sludges containing a significant amount of V2O5 can be considered as an additional source of raw materials for vanadium production. We studied the one-stage leaching method using various iron-based reductants for converting V5+ to V4+ in a solution allowing to precipitate V when its concentration in the solution is low. As a result of the reduction leaching with further precipitation, we obtained concentrates with V2O5 content of 22–26% and a high amount of harmful impurities. Multistage counterflow leaching can be used to fabricate solutions with vanadium pentoxide concentration suitable for vanadium precipitation by hydrolysis and adding ammonium salts. The solutions with V2O5 content of ≈15 g/L can be obtained from the initial sludge by three-stage counterflow vanadium leaching. A concentrate with a content of 78 wt% V2O5 can be precipitated from these solutions at pH = 2.4 by adding ammonium chloride. Additionally, concentrate with V2O5 content of ≈94 wt% was precipitated from the solution with a concentration of >20 g/L V2O5 obtained from the roasted sludge. The concentrates were purified for increasing the vanadium content to 5–7%. The consumption and technological parameters of the considered processes are presented in the paper.

The micromechanism of the low-cycle fatigue of mono- and multilayer PVD coatings on cutting tools was investigated. Multilayer nanolaminate (TiAlCrSiY)N/(TiAlCr)N and monolayer (TiAlCrSiY)N PVD coatings were deposited on the cemented carbide ball nose end mills. Low-cycle fatigue resistance was studied using the cyclic nanoindentation technique. The obtained results were compared with the behaviour of the polycrystalline silicon reference sample. The fractal analysis of time-resolved curves for indenter penetration depth demonstrated regularities of damage accumulation in the coatings at the early stage of wear. The difference in low-cycle fatigue of the brittle silicon and nitride wear-resistant coatings is shown. It is demonstrated that when distinguished from the single layer (TiAlCrSiY)N coating, the nucleation and growth of microcracks in the multilayer (TiAlCrSiY)N/(TiAlCr)N coating is accompanied by acts of microplastic deformation providing a higher fracture toughness of the multilayer nanolaminate (TiAlCrSiY)N/(TiAlCr)N.

There were studied glaze layers of fragments of painted tiles estimated by art historians basing on external signs as fabricated in the Netherlands in the 18 th century. The paper presents results of glaze surface composition measurements by X-ray fluorescence (XRF) and X-ray photoelectron spectroscopy (XPS), time-of-flight mass-spectroscopy (TOF-$$$SIMS) methods in comparison with literature data. Information on composition of glaze layers including pigments will be used obtained in this research will be used in further conservation efforts.

Vanadium containing sludge is a by-product of vanadium pentoxide obtained by hydrometallurgical methods from vanadium slag that can be estimated as a promising technogeneous raw material for vanadium production. The phase analysis of vanadium-containing sludge by the X-ray diffraction method showed that it contains vanadium in spinel form (FeO∙V2O3). The various oxidation roasting methods for sludge treatment were studied for increasing vanadium extraction into the solution. It showed that the most effective additive is 1% CaCO3 at a roasting temperature of 1000 °C. Oxidation roasting of vanadium-containing sludge with the additive led to an increase in the acid-soluble form of V2O5 from 1.5% to 3.7% and a decrease in the content of FeO∙V2O3 from 3% to 0.4%. These results confirm the efficiency of the application of oxidation roasting to convert vanadium compounds into acid-soluble forms. The conversion mechanism of spinel to acid-soluble phases during oxidation roasting with additives was investigated by thermogravimetric analysis and thermodynamic simulation. It showed that the formation of acid-soluble calcium vanadates during oxidation roasting without additives occurs at temperatures above 800 °C while CaCO3 addition allows one to reduce this temperature to 600 °C.

In this work, the anomalous reduction in the thermal conduction observed for nanolaminate metal-dielectric multilayers has been extended to the case of oxides. For this purpose, Ag/Al2O3 coatings were produced with different layer thicknesses (from 1 to 5 nm for Ag and 8 to 40 nm for Al2O3) and numbers of stacks. It was found that the thermal conduction is significantly lower in such metal–oxide nanolaminates compared to the bulk oxide. Such anomalous behaviour is explained by the influence of plasmon and phonon propagation confinement in nanolayers and at the interfaces. To this end, the characteristics of the different types of acoustic and optical phonon waves propagating in the multilayer coating have been studied. In particular, the electronic structures of the different layers and their influences on the plasmon resonance are investigated as a function of the multilayer design. The plasmon-polariton mechanism of energy transfer through oxide–metal and metal–oxide interfaces is discussed.

A big amount of solid wastes or dump sludges is generated after leaching vanadium (V) from a roasted mixture. As the vanadium content in these tailings is comparable to its concentration in traditional vanadium sources such as titanomagnetite ores or a vanadium converter slag, these wastes could be recycled to extract additional vanadium. Therefore, this research was aimed on studies of vanadium-containing sludges resulting from hydrometallurgical production of vanadium pentoxide to find an optimal technology for V extraction. The material composition of industrial and synthetic sludge samples was studied by X-ray fluorescence analysis (XRF), X-ray diffraction (XRD), secondary ions mass spectroscopy (SIMS), and X-ray photoelectron spectroscopy (XPS, ESCA). The paper demonstrates the presence of vanadium in sludges, not only in spinels in 3+ oxidation degree, but also in other compounds containing V4+ and V5+. It was found that vanadium substitutes a set of elements in minerals except spinel. The dependence between the content of insoluble vanadium compounds and V oxidation degree was determined.

Metallurgical vanadium-containing converter slag could be used as an alternative vanadium source. The development of a physico-chemical basis for the comprehensive processing of industrial vanadium-containing debris requires information about their elemental composition as well as the oxidation degrees of the elements and forms of compounds in order to solve two key problems: a better utilization of industrial wastes and a lowering of environment impact. This research was aimed at the development of methods to determine the fractions of elements and their oxidation degrees in vanadium-containing industrial debris exemplified by basic oxygen converter vanadium slags. A set of bulk and surface analysis methods (X-ray fluorescence analysis (XRF), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS)) was used for this purpose: based on results of elemental analysis, SEM detects the oxide phases of metals, while an analysis of the XPS lines' fine structures provides fractions of corresponding elements with definite oxidation degrees. In this way, one can determine the fractions of vanadium in multiple oxidation degrees in slags and can properly select the chemicals and parameters of chemical processes for its fullest extraction.

Experimental investigations of nano-scale spatio-temporal effects that occur on the friction surface under extreme tribological stimuli, in combination with thermodynamic modeling of the self-organization process, are presented in this paper. The study was performed on adaptive PVD (physical vapor deposited) coatings represented by the TiAlCrSiYN/TiAlCrN nano-multilayer PVD coating. A detailed analysis of the worn surface was conducted using scanning electron microscopy and energy dispersive spectroscopy (SEM/EDS), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and Auger electron spectroscopy (AES) methods. It was demonstrated that the coating studied exhibits a very fast adaptive response to the extreme external stimuli through the formation of an increased amount of protective surface tribo-films at the very beginning of the running-in stage of wear. Analysis performed on the friction surface indicates that all of the tribo-film formation processes occur in the nanoscopic scale. The tribo-films form as thermal barrier tribo-ceramics with a complex composition and very low thermal conductivity under high operating temperatures, thus demonstrating reduced friction which results in low cutting forces and wear values. This process presents an opportunity for the surface layer to attain a strong non-equilibrium state. This leads to the stabilization of the exchanging interactions between the tool and environment at a low wear level. This effect is the consequence of the synergistic behavior of complex matter represented by the dynamically formed nano-scale tribo-film layer.

Multilayer nanolaminate TiAlN/Ag and Al2O3/Ag metal-insulator-metal (MIM) coatings with thicknesses of individual layers from a few to several hundreds of nanometers were fabricated by direct current magnetron sputtering. Their optical transmittance and reflectance spectra were measured for photon energies 1–5 eV (1240–248 nm). The spectra were non-monotonous as their transmission and reflection bands were strongly dependent on the coating architecture. A set of advanced electron spectroscopy methods was used to analyse the electronic structure of the coatings controlling optical properties. Energies of plasmons peaks and the distribution of their intensities are functions of the Ag layers thickness as well as the composition and thickness of the dielectric nanolayers in the MIM nanocomposite. Statistical analysis established the cross-correlations between geometrical parameters of the coatings, transmissions and reflection bands on the optical spectra and parameters of the electronic structure. Particularly, the blue side of the transmittance band is controlled by plasmons while the dielectric band gap determines the transmittance of the red side. The obtained experimental results allowed us to fulfil the computed architectural design of a multilayer Al2O3/Ag coating with a narrow bandwidth in the visible light region and strong reflection in the infrared and ultraviolet regions.

This paper generalizes the results of our research, which was aimed at the development of adaptive cutting tool coatings for high speed dry cutting, from the inception of the idea to complex multilayer coatings for processing tough metals. Typically, the streams of external energy and matter during high speed cutting are causing damage to the tool materials and to the hard, protective coatings through multiple mechanical and chemical processes including oxidation, however these oxidation processes could be used to improve the tools’ lifetime. The structure and the phase transformations on the wear surface in the nanostructured single layer and nanolaminated multilayer PVD coatings were investigated by a set of electron spectroscopy methods. The dynamics of the secondary phase formation on the various stages of tool life is demonstrated. The obtained results show that the enhancement of non-equilibrium processes during friction leads to a dominating formation of protective triboceramics on a base of sapphire-like, tungsten, and niobium polyvalent oxides with a structure which decisively improves the wear performance. The mechanisms of the formation of non-equilibrium protective oxides at high speed dry cutting and the non-equilibrium thermodynamics approaches for the tribooxidation description are discussed. Polyvalent metals and multilayer coatings provide a wider set of protective oxide nanofilms.