High-Temperature Oxidation Behavior of AlTiNiCuCox High-Entropy Alloys

In this study, the high-temperature oxidation behavior of a series of AlTiNiCuCo_x high-entropy alloys (HEAs) was explored. The AlTiNiCuCo_x (x = 0.5, 0.75, 1.0, 1.25, 1.5) series HEAs were prepared using a vacuum induction melting furnace, in which three kinds of AlTiNiCuCo_x (x = 0.5, 1.0, 1.5) alloys with different Co contents were oxidized at 800 °C for 100 h, and their oxidation kinetic curves were determined. The microstructure, morphology, structure, and phase composition of the oxide film surface and cross-sectional layers of AlTiNiCuCo_x series HEAs were analyzed using scanning electron microscopy (SEM), energy-dispersive spectrometry (EDS), and X-ray diffraction (XRD). The influence of Co content on the high-temperature oxidation resistance of the HEAs was discussed, and the oxidation mechanism was summarized. The results indicate that, at 800 °C, the AlTiNiCuCo_x (x = 0.5, 1.0, 1.5) series HEAs had dense oxide films and certain high-temperature oxidation resistance. With increasing Co content, the high-temperature oxidation resistance of the alloys also increased. With increasing time at high temperature, there was a significant increase in the contents of oxide species and Ti on the oxide film surface. In the process of high-temperature oxidation of AlTiNiCuCo_x series HEAs, the interfacial reaction, in which metal elements and oxygen in the alloy form ions through direct contact reaction, initially dominated, then the diffusion process gradually became the dominant oxidation factor as ions diffused and were transported in the oxide film.     

Resistance to High-Temperature Oxidation of Ti-Al-Nb Alloys

The research presented in this paper concerns the assessment of the resistance to high-temperature oxidation behaviour of a Ti-46Al-7Nb-0.7Cr-0.1Si-0.2Ni alloy and the explanation of the role of niobium during oxidation processes. The basic problem concerned the evaluation of the resistance of the studied alloy to cyclic oxidation in an air atmosphere, with particular attention to the influence of temperature, surface roughness and cooling rate from heating temperature to room temperature. The issue analysed was the effect of niobium addition on the corrosion kinetics as a high-melting element causing improved oxidation resistance, contributing to the reduction in the oxidation rate.     

A Short Review on the Phase Structures,Oxidation Kinetics,and Mechanical Properties of Complex Ti-Al Alloys

This paper reviews the phase structures and oxidation kinetics of complex Ti-Al alloys at oxidation temperatures in the range of 600–1000 °C. The mass gain and parabolic rate constants of the alloys under isothermal exposure at 100 h (or equivalent to cyclic exposure for 300 cycles) is compared. Of the alloying elements investigated, Si appeared to be the most effective in improving the oxidation resistance of Ti-Al alloys at high temperatures. The effect of alloying elements on the mechanical properties of Ti-Al alloys is also discussed. Significant improvement of the mechanical properties of Ti-Al alloys by element additions has been observed through the formation of new phases, grain refinement, and solid solution strengthening.     

Surface Modification of Biomedical MgCa4.5 and MgCa4.5Gd0.5 Alloys by Micro-Arc Oxidation

The aim of this work was to characterize the structure and corrosion properties of the MgCa_4.5(Gd_0.5) alloys surface treated by the micro-arc oxidation (MAO) process. The MgCa_4.5 and MgCa_4.5Gd_0.5 alloy samples were processed by MAO in an electrolyte composed of NaOH (10 g/dm³), NaF (10 g/dm³), NaH₂PO₄ (5 g/dm³), Na₂SiO₂·5H₂O (10 g/dm³) and water. Two different voltages (120 V and 140 V) were used in the MAO process. The alloys protected by an oxide layer formed in the MAO were then the subject of corrosion resistance tests in an environment simulating the human body (Ringer’s solution). After the experiments, the resulting samples were investigated using SEM, XPS and EDS techniques. The addition of Gd affected the fragmentation of the coating structure, thereby increasing the specific surface; higher voltages during the MAO process increased the number and size of surface pores. Corrosion tests showed that the MgCa_4.5Gd_0.5 alloys were characterized by low polarization resistances and high corrosion current densities. The studies indicated the disadvantageous influence of gadolinium on the corrosion resistance of MgCa_4.5 alloys. The immersion tests confirmed lower corrosion resistance of MgCa_4.5Gd_0.5 alloys compared to the referenced MgCa_4.5 ones. The MgCa_4.5 alloy with the MAO coating established at voltage 140 V demonstrated the best anticorrosion properties.     

Oxidation Behaviour of Microstructurally Highly Metastable Ag-La Alloy

A new silver-based alloy with 2 wt.% of lanthanum (La) was studied as a potential candidate for electric contact material. The alloy was prepared by rapid solidification, performed by the melt spinning technique. Microstructural examination of the rapidly solidified ribbons revealed very fine grains of α_Ag and intermetallic Ag₅La particles, which appear in the volume of the grains, as well as on the grain boundaries. Rapid solidification enabled high microstructural refinement and provided a suitable starting microstructure for the subsequent internal oxidation, resulting in fine submicron-sized La₂O₃ oxide nanoparticle formation throughout the volume of the silver matrix (α_Ag). The resulting nanostructured Ag-La₂O₃ microstructure was characterised by high-resolution FESEM and STEM, both equipped with EDX. High-temperature internal oxidation of the rapidly solidified ribbons essentially changed the microstructure. Mostly homogeneously dispersed nano-sized La₂O₃ were formed within the grains, as well as on the grain boundaries. Three mechanisms of internal oxidation were identified: (i) the oxidation of La from the solid solution; (ii) partial dissolution of finer Ag₅La particles before the internal oxidation front and oxidation of La from the solid solution; and (iii) direct oxidation of coarser Ag₅La intermetallic particles.     

Cyclic Oxidation of Titanium Grade 2

This paper presents the results of research into the cyclic oxidation of titanium Grade 2. The value of titanium Grade 2 oxidation activation energy was determined based on an analysis of the Arrhenius diagram. The result was 205.3 kJ/mol. After cyclic oxidation at a temperature of 600 °C, the presence of oxides in an acicular system was observed on the surface. The specimen surface after oxidation at 650 °C was characterised by the presence of fine oxide particles, while after oxidation at 700 °C, the obtained oxide layer was composed of large oxide particles. The layers obtained after oxidation at 600 °C had the lowest thickness (1.26 and 2.12 µm), while those obtained at 700 °C had the highest thickness (5.17 and 9.45 µm). Examination of the phase composition after cyclic oxidation showed that the oxide layers obtained at temperatures of 600, 650 and 700 °C were composed of TiO₂ (rutile) only. No presence of other phases was found. The oxide layers formed in the cyclic oxidation process were characterised by different thicknesses, depending on the oxidation parameters. It was found that cyclic oxidation contributed to a considerable increase in the surface hardness of titanium Grade 2.     

High-Temperature Oxidation of High-Entropic Alloys: A Review

Over the past few years, interest in high-entropic alloys (HEAs) has been growing. A large body of research has been undertaken to study aspects such as the microstructure features of HEAs of various compositions, the effect of the content of certain elements on the mechanical properties of HEAs, and, of course, special properties such as heat resistance, corrosion resistance, resistance to irradiation with high-energy particles, magnetic properties, etc. However, few works have presented results accumulated over several years, which can complicate the choice of directions for further research. This review article presents the results of studies of the mechanisms of high-temperature oxidation of HEAs of systems: Al-Co-Cr-Fe-Ni, Mn-Co-Cr-Fe-Ni, refractory HEAs. An analysis made it possible to systematize the features of high-temperature oxidation of HEAs and propose new directions for the development of heat-resistant HEAs. The presented information may be useful for assessing the possibility of the practical application of HEAs in the aerospace industry, in nuclear and chemical engineering, and in new areas of energy.     

Effect of (NH4)2ZrF6, Voltage and Treating Time on Corrosion Resistance of Micro-Arc Oxidation Coatings Applied on ZK61M Magnesium Alloys

The effects of (NH₄)₂ZrF₆ concentration, voltage and treating time on the corrosion resistance of ZK61M magnesium alloy micro-arc oxidation coatings were studied by orthogonal experiments. The SEM result shows that the surface roughness and porosity of MAO coatings increased with (NH₄)₂ZrF₆ concentration, voltage and treating time as a whole, except the porosity decreased with treating time. EDS, XRD and XPS analysis show that (NH₄)₂ZrF₆ was successfully incorporated into coatings by reactive incorporation, coatings are dominantly composed of ZrO₂, MgO, MgF₂ and amorphous phase Mg phosphate. Potentiodynamic polarization was used to evaluate the corrosion property of coatings. When the concentration of (NH₄)₂ZrF₆ is 6 g/L, the voltage is 450 V, and the treating time is 15 min, the coating exhibits the best corrosion resistance which corrosion current density is four magnitudes lower than substrate attributed to the incorporation of ZrO₂ and the deposition of MgF₂ in the micropores.     

Effect of Ga on the Oxide Film Structure and Oxidation Resistance of Sn–Bi–Zn Alloys as Heat Transfer Fluids

The effect of gallium on the oxide film structure and overall oxidation resistance of low melting point Sn–Bi–Zn alloys was investigated under air atmosphere using thermogravimetric analyses. The liquid alloys studied had a Ga content of 1–7 wt.%. The results showed that the growth rates of the surface scale formed on the Sn–Bi–Zn–Ga alloys conformed to the parabolic law. The oxidation resistance of Sn–Bi–Zn alloys was improved by Ga addition and the activation energies increased from 12.05 kJ∙mol⁻¹ to 22.20 kJ∙mol⁻¹. The structure and elemental distribution of the oxide film surface and cross-section were found to become more complicated and denser with Ga addition. Further, the results of X-ray photoelectron spectroscopy and X-ray diffraction show that Ga elements accumulate on the surface of the liquid metal to form oxides, which significantly slowed the oxidation of the surface of the liquid alloy.     

Design of Low-Cost and High-Strength Titanium Alloys Using Pseudo-Spinodal Mechanism through Diffusion Couple Technology and CALPHAD

The high cost of development and raw materials have been obstacles to the widespread use of titanium alloys. In the present study, the high-throughput experimental method of diffusion couple combined with CALPHAD calculation was used to design and prepare the low-cost and high-strength Ti-Al-Cr system titanium alloy. The results showed that ultra-fine α phase was obtained in Ti-6Al-10.9Cr alloy designed through the pseudo-spinodal mechanism, and it has a high yield strength of 1437 ± 7 MPa. Furthermore, application of the 3D strength model of Ti-6Al-xCr alloy showed that the strength of the alloy depended on the volume fraction and thickness of the α phase. The large number of α/β interfaces produced by ultra-fine α phase greatly improved the strength of the alloy but limited its ductility. Thus, we have demonstrated that the pseudo-spinodal mechanism combined with high-throughput diffusion couple technology and CALPHAD was an efficient method to design low-cost and high-strength titanium alloys.     

High Temperature Oxidation Behaviors of BaO/TiO2 Binary Oxide-Enhanced NiAl-Based Composites

High temperature lubricating composites have been widely used in aerospace and other high-tech industries. In the actual application process, high temperature oxidation resistance is a very importance parameter. In this paper, BaO/TiO₂-enhanced NiAl-based composites were prepared by vacuum hot-press sintering. The oxidation resistance performance of the composites at 800 °C was investigated. The composites exhibited very good sintered compactness and only a few pores were present. Meanwhile, the composite had excellent oxidation resistance properties due to the formation of a dense Al₂O₃ layer which could prevent further oxidation of the internal substrate; its oxidation mechanism was mainly decided by the outward diffusion of Al and the inward diffusion of O. The addition of BaO/TiO₂ introduced more boundaries and made the K_p value increase from 1.2 × 10⁻¹⁴ g²/cm⁴ s to 3.3 × 10⁻¹⁴ g²/cm⁴ s, leading to a slight reduction in the oxidation resistance performance of the composites—although it was still excellent.     

Microstructure and Mechanical Properties of As-Aged Mg-Zn-Sn-Mn-Al Alloys

The microstructure and mechanical properties of as-aged Mg-6Zn-4Sn-1Mn-xAl (ZTM641-xAl, x = 0, 0.2, 0.5, 1, 2, 3 and 4 wt.%) alloys are studied in this paper. In terms of microstructure, the results reveal that the addition of Al mainly leads to the formation of the Al₈Mn₅, Al₁₁Mn₄, Al₂Mg₅Zn₂ and Mg₃₂(Al,Zn)₄₉ phases. With increases in the addition of Al, the average grain size first decreases and then increases, while the undissolved phases increase. The average grain size of the ZTM641-0.5Al alloy is the smallest, and the single-aged and double-aged grain size is 14 μm and 12 μm, respectively. As for mechanical properties, with increases in the Al element, the strength decreases, and the elongation first increases and then decreases. The double-aged ZTM641-0.2Al alloy exhibits favorable mechanical properties at room temperature, and the UTS, YS and elongation are 384 MPa, 360 MPa and 9%, respectively. Further, the double-aged ZTM641-0.2Al alloy exhibits the comprehensive mechanical properties at 150 °C, that is, the UTS, YS and elongation are 212 MPa, 196 MPa and 29%, respectively, which is about 45% higher than that of the elongation of ZTM641. The ZTM641-xAl alloys exhibits mixed fracture at room temperature, and, with increases in the addition of Al, the fracture mechanisms of alloys are mixed fracture, ductile fracture and mixed fracture at 200 °C.     

Recrystallization Behavior of a Mg-5Zn Alloy Influenced by Minor SiCp during Hot Compression

The influence of minor SiC_p on the dynamic recrystallization (DRX) and dynamic precipitation behaviors of the Mg-5Zn matrix were investigated through the hot compression test. The results showed that the addition of SiC_p improved the DRXed ratio of Mg-5Zn matrix, but the recrystallized grains in 1 vol.% 5 μm SiC_p/Mg-5Zn material were mainly formed by the “bulging” nucleation of the grain boundary at a low compressive strain (~0.05, ~0.1 and ~0.35), and PDZ (particle deformation zone) around SiC_p had little effect on the recrystallization nucleation. However, the fine recrystallized grains appeared around the particles when the compressive strain reached ~0.7, which was attributed to the promotion effect of PDZ on recrystallization nucleation. This shows that PDZ around particles can promote DRX nucleation under large strain. Meanwhile, compared to the Mg-5Zn alloy, the volume fraction and size of the secondary phase in the SiC_p/Mg-5Zn material increased due to the influence of SiC_p on the recrystallization behavior of Mg-5Zn matrix.     

Environmental STEM Study of the Oxidation Mechanism for Iron and Iron Carbide Nanoparticles

The oxidation of solution-synthesized iron (Fe) and iron carbide (Fe₂C) nanoparticles was studied in an environmental scanning transmission electron microscope (ESTEM) at elevated temperatures under oxygen gas. The nanoparticles studied had a native oxide shell present, that formed after synthesis, an ~3 nm iron oxide (Fe_xO_y) shell for the Fe nanoparticles and ~2 nm for the Fe₂C nanoparticles, with small void areas seen in several places between the core and shell for the Fe and an ~0.8 nm space between the core and shell for the Fe₂C. The iron nanoparticles oxidized asymmetrically, with voids on the borders between the Fe core and Fe_xO_y shell increasing in size until the void coalesced, and finally the Fe core disappeared. In comparison, the oxidation of the Fe₂C progressed symmetrically, with the core shrinking in the center and the outer oxide shell growing until the iron carbide had fully disappeared. Small bridges of iron oxide formed during oxidation, indicating that the Fe transitioned to the oxide shell surface across the channels, while leaving the carbon behind in the hollow core. The carbon in the carbide is hypothesized to suppress the formation of larger crystallites of iron oxide during oxidation, and alter the diffusion rates of the Fe and O during the reaction, which explains the lower sensitivity to oxidation of the Fe₂C nanoparticles.     

Surface Treatment of Zn-Mn-Mg Alloys by Micro-Arc Oxidation in Silicate-Based Solutions with Different NaF Concentrations

Newly developed Zn-Mn-Mg alloys can be invoked as biomedical materials because of their excellent mechanical properties. However, the corrosion behavior of Zn-Mn-Mg alloys was still lacking in research. It had grown to be a hot research topic to improve the corrosion behavior of Zn alloys by surface treatment to meet the application of degradable Zn alloys in biomedical applications. Micro arc oxidation (MAO) is a simple and effective method to improve the corrosion behavior of the alloy. MAO coatings were successfully prepared on the surface of Zn-Mn-Mg alloys by MAO in silicate-based solutions with different NaF concentrations. The microstructure and phase composition of MAO coatings prepared on Zn-Mn-Mg alloys with different NaF concentrations in the electrolyte was examined by a scanning electron microscope and X-ray diffraction. The results showed that the MAO coatings are porous and mainly composed of ZnO. With the increasing NaF concentration in the electrolyte, the average thickness increases. The distribution of the micro/nanopores was uniform, and the pore size ranged from the submicron scale to several micrometers after MAO treatment in the electrolyte containing different concentrations of NaF. Potential dynamic polarization curves and electrochemical impedance spectroscopy were employed to assess the corrosion behavior of MAO coatings in Hank’s solution. The highest corrosion rate can be achieved after MAO treatment, with an electrolyte concentration of 1.5 g/L NaF in Hank’s solution. These results indicated that MAO coating can accelerate the corrosion resistance of a Zn-Mn-Mg alloy.     

Study of an Organic Binder of Cold-Bonded Briquettes with Two Different Iron Bearing Materials

The aim of this study was to investigate the properties of an organic binder used in cold-bonded briquettes (CBBs) prepared from two different iron bearing materials. The applied binder is a type of starch as indicated by chemical analysis, iodine-starch staining and Fourier transform infrared analyses. Thermogravimetric differential scanning calorimetry showed that the binder pyrolysis undergoes four stages: moisture desorption, ash volatilization, pyrolysis of organic matter and decomposition of materials with high activation energy. The difference between the dry and heat-treated samples during the macroscopic failure process is the instability propagation of the crack. The CBB shows a low decrepitation index at 700 °C. The returned fines of CBBs used with the organic binder were applied in two blast furnaces. The industrial trials showed that the CBBs do not influence the performance of the blast furnace and can reduce the fuel consumption rate. The curing rate of the binder decreases, and the growth rate of compressive strength decreases during the curing process. Iron ore particles are bonded together and exist in the form of aggregation after mixing with water and binder. The edges and corners of the particles become blurred, and the original surfaces of the particles are covered with binder film, the surface of which is covered with fine particles. The multi-branched structure of amylopectin provides omnibearing adhesion sites, thus forming binder agglomeration and film leading to a strong adhesion between binder and iron ore particles. Binder film and binder agglomeration work together to make the CBB perform well.     

High Temperature Dry Tribological Behavior of Nb-Microalloyed Bearing Steel 100Cr6

100Cr6 steel is one of the most widely used bearing steels and a representative of first-generation bearing steel. Many engineering applications require rolling bearings to run at a high temperature. Therefore, it is necessary to improve the high temperature properties of 100Cr6 steel. In this paper, the effect of Nb on high temperature dry tribological behavior, including worn surface and friction coefficient, was analyzed by a wear test when Nb content was 0.018% and 0.040%. The results show that the microstructure is refined gradually, the hardness is improved, and wear volume decreases by 31.8% at most with the increase of Nb content. At 50 °C, the friction coefficient of 100Cr6 steel can be reduced by adding a small amount of Nb, but this effect will be weakened if the content of Nb is too high. In addition, excess Nb increases the hard precipitation of NbC, which aggravates the abrasive wear and leads to the increase in the depth of the worn surface. At 125 °C, the effect of Nb on tribological properties is weaker. With the increase of temperature, the steel substrate softens, and the oxide particles increase, which aggravates the abrasive wear and oxidation wear and makes the wear volume increase significantly.     

Experimental and Simulation Study for the Influence of Thermal Pre-Deformation on Subsequent Aging Precipitation Kinetics of Al-Zn-Mg-Cu Alloy

Deformation and heat treatment are important means to strengthen aluminum alloys. However, the influence mechanism of pre-strain on aging precipitation kinetics and its effect on mechanical properties are still not clear. In this work, uniaxial isothermal tensile tests with different strains and artificial aging treatments for Al-Zn-Mg-Cu alloys have been carried out. Then, a model describing the precipitates kinetic behavior has been developed to investigate the effect of thermal pre-strain on subsequent aging precipitation kinetics and peak aging microhardness based on the microstructure characterization by TEM, SAXS and XRD tests. In addition, the role of dislocations on the aging precipitation kinetics is also explored. The experimental results show that the peak aging microhardness of the Al-Zn-Mg-Cu alloy reveals a tendency to decrease and increase and then the peak aging time firstly decreases and then keeps almost constant with the increase in the strain. The calculations demonstrate that the precipitate average size almost remains unchanged, while the precipitate volume fraction decreases and then increases with the increase in strain, which is consistent with the change in peak aging microhardness. It also indicates that dislocations can promote precipitate nucleation and growth, while the actual effect depends on the dislocation density, which is closely dependent on the pre-deformation condition, especially for the precipitate nucleation. In particular, when the dislocation density after thermal pre-deformation is not enough, it will slightly inhibit precipitate nucleation but promote precipitate growth, which could shorten the peak aging time, with the peak aging strength being guaranteed.     

Influence of Magnetite Nanoparticles Shape and Spontaneous Surface Oxidation on the Electron Transport Mechanism

The spontaneous oxidation of a magnetite surface and shape design are major aspects of synthesizing various nanostructures with unique magnetic and electrical properties, catalytic activity, and biocompatibility. In this article, the roles of different organic modifiers on the shape and formation of an oxidized layer composed of maghemite were discussed and described in the context of magnetic and electrical properties. It was confirmed that Fe₃O₄ nanoparticles synthesized in the presence of triphenylphosphine could be characterized by cuboidal shape, a relatively low average particle size (9.6 ± 2.0 nm), and high saturation magnetization equal to 55.2 emu/g. Furthermore, it has been confirmed that low-frequency conductivity and dielectric properties are related to surface disordering and oxidation. The electric energy storage possibility increased for nanoparticles with a disordered and oxidized surface, whereas the dielectric losses in these particles were strongly related to their size. The cuboidal magnetite nanoparticles synthesized in the presence of triphenylphosphine had an ultrahigh electrical conductivity (1.02 × 10⁻⁴ S/cm at 10 Hz) in comparison to the spherical ones. At higher temperatures, the maghemite content altered the behavior of electrons. The electrical conductivity can be described by correlated barrier hopping or overlapping large polaron tunneling. Interestingly, the activation energies of electrons transport by the surface were similar for all the analyzed nanoparticles in low- and high-temperature ranges.     

Formation of Nanoscale Al2O3 Protective Layer by Preheating Treatment for Improving Corrosion Resistance of Dilute Fe-Al Alloys

In this work, an attempt was made to improve the corrosion resistance of dilute Fe-Al alloys (1.0 mass% Al) by preheating treatment at 1073 K in H₂ atmosphere. In comparison with pure Fe and unpreheated Fe-Al alloys, the resistance to oxidation at 673 K in pure O₂ and to electrochemical corrosion in 5 wt.% NaCl solution is significantly improved for preheated Fe-Al alloys. This improvement is attributed to the formation of a 20 nm thin, but dense Al₂O₃ protective layer on the surface of preheated Fe-Al alloys.