Electron Probe X-ray Microanalysis Research Articles

Distribution of Pb, Zn, Fe, As, Sn, Sb, Bi, and Ni Between Oxide Liquid and Metal in the ‘CuO0.5’-CaO-AlO1.5 System in Equilibrium with Cu Metal at 1400 °C

AbstractThe increasing complexity of ore resources and recycled materials in the feed of pyrometallurgical processes present a technical challenge to the metallurgical engineers working on maximizing the recovery of the valuable elements and minimizing the environmental impact of the processes. To address this challenge, the availability of computational tools that can predict the mass and energy balance in complex systems is required. Then, the accurate description of phase equilibria in the complex multicomponent systems describing the chemistry of the pyrometallurgical processes becomes critical for the correct implementation of the indicated tools and facing the outlined industrial challenges. In the present study, the distribution of selected elements (Pb, Zn, Fe, As, Sn, Sb, Bi, and Ni) between oxide liquid and metal in the ‘CuO0.5’–CaO–AlO1.5 system in equilibrium with Cu metal at 1400 °C (liquidus of CaAl2O4) was experimentally studied using the equilibration and quenching technique followed by the electron probe X-ray microanalysis of the resulted samples. The study covered a wide range of effective p(O2) over the system from 10−11 to 10−3.5 (corresponding to formation of immiscible CuO0.5-rich slag). To avoid loss of volatile elements (Pb, Zn, As, Sn, Sb, and Bi), a correlation between ‘CuO0.5’ in oxide liquid and p(O2) in open system was obtained first, followed by studying the volatile elements distribution in closed conditions (Al2O3 crucible sealed in SiO2 ampoule), where ‘CuO0.5’ concentration was used as a marker to evaluate the effective p(O2) over the system. The experimental results were then used for the optimization of the thermodynamic model parameters of the system as part of the integrated experimental and self-consisting thermodynamic modeling research program of phase equilibria in the Cu–Pb–Zn–Fe–Ca–Si–Al–Mg–O–S–(As, Sn, Sb, Bi, Ag, Au, Ni, Cr, Co, and Na) gas/oxide liquid/matte/speiss/metal/solids system. Graphical Abstract

Formation of aluminum nitride in dross by contact-diffusion reaction during aluminum recycling

Secondary aluminum dross is a solid waste after aluminum extraction from the slag produced during aluminum recycling. It is classified as a hazardous waste due to the high content of active aluminum nitride (AlN). This work studied the thermodynamics and kinetics of AlN formation in aluminum dross. Aluminum tends to react with N2 to form AlN, when the partial pressure of nitrogen (N2) is much greater than that of oxygen (O2) (PN2≫PO2) in thermodynamics. Additionally, the reaction between aluminum and N2 is accelerated with the increasing temperature. Approximately 36.37 wt% of aluminum was transformed into AlN at 700°C according to kinetic analysis. Aluminum recycling involves smelting, refining, and dross processing. The dross produced from these different processes has various compositions and hazardous properties. The formation mechanism of AlN from the three processes was revealed based on the thermodynamic and kinetic analyses. The reaction mechanisms in these processes were identified as surface contact reaction, internal and surface contact reaction, and rotational surface contact reaction between the aluminum melt and N2, respectively. X-ray diffraction (XRD) and electron probe microanalysis (EPMA) analyses were used to determine the phase and composition of the aluminum dross. The nitrogen content in the aluminum dross from smelting, refining, and dross processing was found to be 3.3 wt%, 5.2 wt%, and 9.6 wt%, respectively. The monthly dross production were 276.3 tons, 22.7 tons, and 318.2 tons, respectively, according to statistics. It was calculated that the nitrogen generated in the three process was 9.12 tons, 1.18 tons, and 20.25 tons, respectively. Therefore, dross processing is the primary source of AlN. A rapid dross processing method with small-scale vertical stirring was proposed to shorten the reaction between the aluminum melt and N2, thereby reducing AlN formation. This work could provide guidance for reducing hazardous AlN in aluminum dross and optimizing the aluminum recycling process.

Thermodynamic re-optimization of the CaO-FeO-Fe2O3 system integrated with experimental phase equilibria studies (Part II – Thermodynamic optimization)

The Ca-Fe-O system is essential for understanding the chemical equilibria involved in copper production using calcium ferrite slags. It forms a core component of a complex 20-component Cu-Pb-Zn-Fe-Ca-Si-O-S-Al-Mg-Cr-Na-As-Sn-Sb-Bi-Ag-Au-Ni-Co system developed for diverse applications in ferrous and non-ferrous metallurgy. This study re-evaluates the Ca-Fe-O system using recent experimental phase equilibrium data acquired by the authors (Cheng et al., 2024) [1] through advanced equilibration, quenching, and Electron Probe X-ray Microanalysis (EPMA) techniques. Thermodynamic properties of solid phases have been revised in accordance with the recommendations for the third generation of Calphad databases. Liquid endmember heat capacities have been refined to describe glass transition behaviour in supercooled liquids. The updated properties of liquid endmembers significantly extend the applicability of the database, enabling lower-temperature applications related to toxic element leaching from amorphous and partially crystallized slags. The revised, higher melting temperature of CaO enhances predictive accuracy in multicomponent systems. Liquid slag phase has been modelled within the Modified Quasichemical Formalism to account for short-range ordering phenomena. Recent advances in modelling and optimization technique made it possible to assess experimental data within the Ca-Fe-O system as an integral part of a large multicomponent dataset, applicable for industrial conditions.

Substrate modification for high performance CrAl/CrAlBN multilayers coated TiCN-based cermet through plasma nitriding

The plasma nitriding process was conducted on a TiCN-based cermet that had been coated with a multilayer CrAl/CrAlBN coating deposited via cathodic arc. The intensity of the plasma nitriding was modified by adjusting the anode current of the ionization source. To investigate the interface conditions, techniques such as electron probe X-ray microanalysis, electron backscatter diffraction, and transmission electron microscopy were employed. The results indicated that increasing the anode current led to the formation of a thicker nitrided layer and an increase in the texture coefficient of the (111) plane. Specifically, at an anode current of 200 A, the lattice mismatch degree at the TiCN/CrAlN interface decreased from 16.4 % to 3.7 %, resulting in the formation of a nearly coherent interface. The hardness, adhesion strength, and H/E ratio of the coating reached their peak values, and the coated cutting tool exhibited optimal cutting performance when machining the GH4149 superalloy.

Oxidation behavior of 9Cr-RAFM steel at high temperature

The effect of yttrium on the mechanism of oxidation film formation of the 9Cr reduced activation ferritic/martensitic (9Cr-RAFM) steel was investigated. Four alloys yttrium contents ranging from 0 to 0.065% were melted in a vacuum induction furnace and subjected to continuous isothermal oxidation experiments. The alloys were oxidized in air at 600, 700, 800 and 900 °C for 100 h. Oxidation kinetic curves were obtained and analyzed to study the effect of yttrium on the oxidation resistance of the alloys at high temperatures. The oxide films formed on the alloys were observed and analyzed by X-ray diffractometry, scanning electron microscopy and electron probe X-ray microanalysis. The results indicated that the oxidation weight gain of the samples varied with the yttrium content, with the highest gain observed in the yttrium-free alloy sample, and the least in those containing 0.065% yttrium. Adding yttrium significantly enhanced the high temperature oxidation resistance of 9Cr-RAFM alloy by promoting the formation of a selective Cr2O3 oxide film. The film improved the adhesion of the oxide layer to the base metal, reduced the oxidation rate, and thereby enhanced the high-temperature oxidation resistance of the alloy.

Integrated experimental and thermodynamic modelling study of phase equilibria in the “CuO0.5”-PbO-CaO system in equilibrium with Cu/Pb metal

Phase equilibria studies were undertaken on the “CuO0.5”-PbO-CaO system in equilibrium with Cu/Pb metal as part of the integrated experimental and thermodynamic modelling study of phase equilibria in the Cu-Pb-Zn-Fe-Ca-Si-Al-Mg-O-S-(As, Sn, Sb, Bi, Ag, Au, Ni, Cr, Co and Na) gas/oxide liquid/matte/speiss/metal/solids system in support of the development and optimisation of pyrometallurgical processes. The equilibration and quenching technique followed by the electron probe X-ray microanalysis (EPMA) was used in the present study. The primary phase fields of massicot (PbO), copper plumbite (Cu2PbO2), cuprite (Cu2O) and lime (CaO) were experimentally characterised. The experimental data obtained in the present study, as well as available literature data on the phase equilibria and thermodynamics of the “CuO0.5”-PbO-CaO system in equilibrium with Cu/Pb were used for the optimisation of the model parameters of the discussed system in agreement with the Cu-Pb-Zn-Fe-Ca-Si-Al-Mg-O-S-(As, Sn, Sb, Bi, Ag, Au, Ni, Cr, Co and Na) gas/oxide liquid/matte/speiss/metal/solids system to obtain a self-consistent set of parameters of the thermodynamic model for all phases. The predicted liquidus surface of the “CuO0.5”-PbO-CaO system was presented for the first time in the complete range of temperatures and compositions.

Thermal stability of a newly developed Mn containing β-solidifying γ-TiAl intermetallic compound at 750 °C

A newly low-cost β-solidifying γ-TiAl alloy Ti-44Al-3Mn-0.4Mo-0.4W-0.1B-0.1C (in at. %, named as TMMW) was invented. The rolled bars with a diameter of 12 mm were successfully fabricated by conventional hot rolling process, directly carrying out from the ingot without the pre-forging or hot-packing. The heat-treated TMMW rolled bar, which had a fine-grained nearly lamellar (NL) microstructure, was then air-exposed at 750 °C for up to 3000 h. The changes of the microstructure during this exposure were characterized using electron probe X-ray micro-analyzer (EPMA), transmission electron microscope (TEM), electron backscattered diffraction (EBSD) and high-energy X-ray diffraction (HEXRD). The tensile properties of the samples before and after thermal exposure were also tested. The fine-grained NL microstructure is found to be thermodynamically stable during the exposure. Meanwhile, the combined addition of Mo and W shows a positive effect on the stabilization of βo phase at colony boundaries, with only slight precipitation of the nanometer βo phases with no other brittle phases, such as Laves, in the metastable α2 lamellae. It is found that the thickness of the α2 lamellae decreases after 500 h exposure, while remains basically unchanged from 500 h to 3000 h, which is contributed by the effective pinning effect of the precipitated βo phase in α2 lamellae. As a result, the exposure-induced embrittlement under room temperature and elevated temperature does not take place. Interestingly, the ductility tested at 800 °C improves significantly after exposure. As for the tensile strength, it is only reduced by less than 10 % after 500 h exposure, while it remains essentially unchanged when increasing the exposure time from 500 h to 3000 h. Finally, the mechanisms of the precipitation of βo phases in the α2 lamellae and the tensile properties evolution during the exposure were carefully discussed.

Research on the Mechanism of Oxygen-Induced Embrittlement Fracturing in Industrial Electrolytic Nickel.

In this study, severe cracking occurred during an investigation of the direct hot rolling of industrial electrolytic nickel plates. To determine the cause of hot-rolling cracking, the microstructure phase composition was analyzed through the utilization of various techniques, including optical microscopy, scanning electron microscopy, electron backscattering diffraction, transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS) and electron probe micro-analysis. The comparative microstructural analysis took place between specimens heat treated in atmospheric and vacuum environments. The characterization and analysis of the hot-rolled plates considered the crack microstructure and fracture morphology. It was shown that holes appeared along the large angular grain boundaries after annealing at 1100 °C for 8 h. Possible reason: In a high-temperature environment, the decomposition of residual additives in the electrolytic nickel releases oxidizing gases, which oxidizes the grain boundaries. The reaction with carbon diffused into the grain boundaries and produced carbon monoxide gas, which induced holes and severely reduced the grain boundary plasticity. The heat treatment time did not need to be very long for severe grain boundary degradation to occur. After severe cavitation, the electrolytic nickel was severely cracked at grain boundaries cracks due to a shear force, and brittle fractures occurred along grains with very low plasticity.

Evolution of fluid redox in a fault zone of the Pic de Port Vieux thrust in the Pyrenees Axial Zone (Spain)

Abstract. In mountain ranges, crustal-scale faults localize multiple episodes of deformation. It is therefore common to observe current or past geothermal systems along these structures. Understanding the fluid circulation channelized in fault zones is essential to characterize the thermochemical evolution of associated hydrothermal systems. We present a study of a palaeo-system of the Pic de Port Vieux thrust fault. This fault is a second-order thrust associated with the Gavarnie thrust in the Axial Zone of the Pyrenees. The study focused on phyllosilicates which permit the constraint of the evolution of temperature and redox of fluids at the scale of the fault system. Combined X-ray absorption near-edge structure (XANES) spectroscopy and electron probe microanalysis (EPMA) on synkinematic chlorite, closely linked to microstructural observations, were performed in both the core and damage zones of the fault zone. Regardless of the microstructural position, chlorite from the damage zone contains iron and magnesium (Fetotal / (Fetotal + Mg) about 0.4), with Fe3+ accounting for about 30 % of the total iron. Chlorite in the core zone is enriched in total iron, but individual Fe3+/Fetotal ratios range from 15 % to 40 %, depending on the microstructural position of the grain. Homogeneous temperature conditions about 280–290 °C have been obtained by chlorite thermometry. A scenario is proposed for the evolution of fluid–rock interaction conditions at the scale of the fault zone. It involves the circulation of a single hydrothermal fluid with homogeneous temperature but several redox properties. A highly reducing fluid evolves due to redox reactions involving progressive dissolution of hematite, accompanied by crystallization of Fe2+-rich and Fe3+-rich chlorite in the core zone. This study shows the importance of determining the redox state of iron in chlorite to calculate their temperature of formations and to consider the fluid evolution at the scale of a fault.

Study of Effects of Post-Weld Heat Treatment Time on Corrosion Behavior and Manufacturing Processes of Super Duplex Stainless SAF 2507 for Advanced Li-Ion Battery Cases.

Lithium-ion batteries are superior energy storage devices that are widely utilized in various fields, from electric cars to small portable electric devices. However, their susceptibility to thermal runaway necessitates improvements in battery case materials to improve their safety. This study used electrochemical analyses, including open-circuit potential (OCP), potentiodynamic polarization, and critical pitting temperature (CPT) analyses, to investigate the corrosion resistance of super duplex stainless steel (SAF 2507) applied to battery cases in relation to post-weld heat treatment (PWHT) time. The microstructure during the manufacture, laser welding, and PWHT was analyzed using field-emission scanning electron microscopy, X-ray diffraction, and electron backscatter diffraction, and the chemical composition was analyzed using dispersive X-ray spectroscopy and electron probe micro-analysis. The PWHT increased the volume fraction of austenite from 5% to 50% over 3 min at 1200 °C; this increased the OCP from -0.21 V to +0.03 V, and increased the CPT from 56 °C to 73 °C. The PWHT effectively improved the corrosion resistance, laying the groundwork for utilizing SAF 2507 in battery case materials. But the alloy segregation and heterogeneous grain morphology after PWHT needs improvement.

Phase equilibria in the low-TiO2 part of the CaO–MgO–SiO2–Al2O3–TiO2 system at a fixed MgO/CaO mass ratio of 0.2 and Al2O3/SiO2 mass ratio of 0.4

Adding titanium oxide has become a common practice in modern blast furnace operating procedures. The blast furnace slag is based on the CaO–MgO–Al2O3–SiO2–TiO2 low titanium slag system rather than CaO–MgO–Al2O3–SiO2 system. Phase equilibria in the CaO–SiO2–Al2O3–MgO–TiO2 system in the low-TiO2 part have been experimentally determined by means of high temperature equilibration and quenching technique followed by electron probe X-ray microanalysis. Introducing a small quantity of titanium-bearing materials can lower the liquidus temperature. The TiO2 content in the slag should be controlled below 4.6 wt%, otherwise it will enter the perovskite phase region where the liquidus temperatures increases rapidly. The compositions of the solid solutions corresponding to the liquidus have been precisely measured and should be utilized for developing the thermodynamic database.

Effect of Ce on structural evolution and corrosion resistance of HRB500E rebar corrosion layer

HRB500E rebar is a low-alloy high-strength steel with excellent mechanical properties and good plasticity but suffers from deficient corrosion resistance. This can be solved by adding trace elements, including rare earth elements. Herein, the corrosion-resistant behavior of rebar was evaluated by weightlessness testing and electrochemical measurements, and the effects of Ce on the structural evolution of the corrosion product layer were investigated by scanning electron microscopy (SEM), Electron Probe X-ray Micro-Analyzer (EPMA), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The results showed that adding Ce to the rebar improved the densification of the reinforcing surface corrosion products, as well as reduced the corrosion rate of the experimental rebar. Compared to C0 sample without Ce, the rebar sample containing 0.044 wt.% Ce displayed increased Ecorr by 0.051 V, decreased Icorr by 15.573 mA cm−2, enhanced Rc of the corrosion product layer by 112.71 Ω cm2, incremented α-FeOOH content in the corrosion product layer, and boosted ratio of α/γ* in the corrosion product layer by 10.11%. Furthermore, the oxide (CeO2) formed by Ce in the corrosion layer of the rebar bar surface existed in the rust layer, resulting in a stable corrosion product layer with improved blocking ability of the corrosive medium. Overall, the addition of Ce at certain ratios looks promising to produce HRB500E rebar with excellent corrosion resistance and extended service life under harsh conditions.

Integrated experimental and thermodynamic modeling study of slag-matte-metal equilibrium in the Pb–Fe–O–S–Si-(Al, Ca, Zn) systems at 1100–1200 °C

Integrated experimental and thermodynamic modeling study was undertaken to characterize the effect of Al, Ca and Zn on the partitioning of elements between the slag, matte and metal phases in the Pb–Fe–O–S–Si-(Al), (-Ca), and (-Zn) systems in equilibrium with tridymite at 1100–1200 °C. The experimental methodology involved closed system equilibration in sealed ampoules, quenching and electron probe X-ray microanalysis (EPMA) of compositions of phases. FactSage thermodynamic database obtained by combining earlier assessments of sub-systems was used to plan the targeted experiments, and the results of new experiments were used to improve the thermodynamic database. Important effects were revealed for the conditions of the present study: CaO decreases the concentration of Pb and S in slag; Al2O3 has small effect on Pb in slag, but significantly decreases the concentration of S in slag; ZnO has small effect on Pb in slag, but increases the concentration of S in slag. These experimentally measured effects were reproduced by the model.

Micromechanical property evolution and damage mechanism of coal subjected to ScCO2 treatment

Carbon dioxide (CO2) injection into deep coal seams holds considerable significance in both carbon mitigation and enhanced recovery of clean coalbed methane (CBM). The CO2-coal interaction leads to changes in the physicochemical properties, potentially impacting the stability of the target sequestration coal reservoir. This study applied the nanoindentation, scanning probe microscopy (SPM), X-ray diffraction (XRD), and electron probe X-ray Micro-Analyzer (EPMA) techniques to probe the micromechanical property change and damage mechanism of coal subjected to ScCO2 injection. The result shows that the load-displacement behavior of the tested coal changes with continuous ScCO2 treatment, and the mechanical strength significantly weakens after 4 days of ScCO2 treatment. The nanoindentation test indicates that the peak and creep displacements of tested coal increased by 168.79 % and 1046.32 % respectively with 4-day ScCO2 treatment, inferring that the coal deformation increases and changes from elastic to plastic after ScCO2 injection. As the ScCO2 treatment time increases, Young's modulus and hardness of coal exhibit an exponential decay trend and rapidly decrease by 77.77 %∼89.76 % and 68.37 %∼81.63 % respectively after the initial 3-day treatment, followed by a slow decrease with the ScCO2 duration prolonging. The XRD and EPMA results show that the carbonate minerals reacted preferentially with ScCO2, and silicate minerals experienced gradual dissolution, while the amorphous carbon fluctuated almost unchanged in the tested coal. Carbonate minerals in tested coal have decreased by 70.68 % within the first 1-day ScCO2 treatment, making the most significant contribution to the initial rapid weakening of coal mechanics. The mineral distribution is closely related to the mechanical anisotropy of coal, which is confirmed by the phenomenon that the coal anisotropy gradually weakens with the mineral reaction process. It is inferred that the mineral component and distribution of coal seams are important indicators for evaluating the intensity of physical and chemical reactions in ScCO2-injected reservoirs, which directly determines the mechanical damage behavior of sequestration reservoirs. This research provides basic support for site selection and safety assessment of carbon sequestration in deep coal seams.

Thermodynamic re-optimization of the CaO–SiO2 system integrated with experimental phase equilibria studies

CaO–SiO2 is the key system in ferrous and non-ferrous metallurgy, ceramic manufacture, cement production, and other applications. A number of discrepancies and gaps in knowledge has been identified and resolved since the last thermodynamic optimization of this system. This study reports new experimental phase equilibria data measured using recent advances in equilibration, sample quenching, and Electron Probe X-ray Microanalysis (EPMA) technique. An updated self-consistent set of thermodynamic model parameters is provided. Most importantly, these updates are integrated with a complete re-assessment of the 20-component Cu–Pb–Zn–Fe–Ca–Si–O–S–Al–Mg–Cr–Na–As–Sn–Sb–Bi–Ag–Au–Ni–Co system directly relevant to applications in the ferrous and non-ferrous metallurgical industries. To obtain a large single set of model parameters, significant advances were made in the computational approach, with a focus on simultaneous parallel optimization of binary and ternary model parameters using an experimental dataset combining binary, ternary, and multicomponent information. The Modified Quasichemical Formalism is used for the liquid slag phase. Thermodynamic properties of solid phases and liquid endmembers are completely revised following the recommendations for the third generation of CALPHAD databases. Other notable changes include the revision of the melting temperature of CaO, justified by extrapolations from the multicomponent systems, as well as a physically realistic heat capacity function for metastable SiO2 below the glass transition temperature. These updated properties expand the areas of application of the database to amorphous and partially crystallized slags at ambient temperatures, such as thermodynamics and kinetics of leaching of toxic elements in an aqueous environment. The fundamental limitations of the existing Modified Quasichemical Formalism are also discussed, along with strategies for addressing them.

Effects of Cr and Ni addition on critical crack tip opening displacement (CTOD) and supercritical CO2 corrosion resistance of high-strength low-alloy steel (HSLAs)

The effects of Cr and Ni content on the low-temperature toughness and supercritical CO2 corrosion resistance of high-strength low-alloy steel (HSLAs) were investigated by optical microscopy, scanning electron microscope, electron backscattered diffraction, transmission electron microscope, X-ray Photoelectron Spectroscopy, electron probe X-ray micro-analyzer, critical crack tip opening displacement, and supercritical CO2 corrosion experiments. In this study, the complex structure of high-strength low-alloy steel is identified and quantified, and related to the critical crack tip opening displacement (CTOD). The further addition of Ni and Cr promotes the formation of granular bainite (GB) and martensite-austenite (MA). The proportion of high-angle grain boundaries in the GB structure is small and does not significantly hinder crack expansion, while MA frequently leads to the initiation and expansion of cracks, deteriorating the low-temperature toughness of the material. Supercritical CO2 corrosion experiments displayed that further addition of Cr and Ni will improve the density and protection of corrosion products. But high-density dislocations will destroy the integrity of the lattice structure of the material and may serve as diffusion channels to affect the formation of the passivation layer and repair. Moreover, dislocation-dense areas are more likely to capture impurity elements, forming a micro-battery effect and accelerating local corrosion. This reduces the extent to which Cr and Ni alloy elements improve the corrosion resistance of HSLA steel.

Characterizing oxidation, thickness, and composition of metallic glass thin films with combined electron probe microanalysis and X-ray photoelectron spectroscopy

Metallic glass thin films (MGTFs) are a recently developed class of alloy coatings with potential applications ranging from biomedical devices to electrical components. Their tribological performance in service conditions is dictated by MGTF bulk composition but can be limited by the native oxide surface that inevitably forms upon exposure to atmosphere. Surface oxidation, thickness, and composition of ZrCuNiAl MGTFs were characterized using a combination of X-ray photoelectron microscopy (XPS) and electron probe microanalysis (EPMA). MGTF samples with nominal thicknesses of 50, 500, and 1500 nm were sputtered onto Si and SiN wafer substrates within a high vacuum deposition chamber and their amorphicity was confirmed by X-ray diffraction. XPS depth profiling identified the thin film composition and showed that the surface oxide was dominated by a mixed layer of mostly ZrO2, a little oxidized Al, and some metallic Zr. EPMA X-ray intensities were acquired as a function of beam energy to excite characteristic X-rays from different depths of the MGTFs and reconstructed using open-source thin film analysis software BadgerFilm, to determine the composition and thickness of sample layers. EPMA results constrain the composition to be Zr54Cu29Al10Ni7 within 0.7 at. % variation and total thicknesses to be 49, 470, and 1546 nm. Using the oxide composition identified from XPS depth profiling as an input for BadgerFilm analysis, EPMA results indicate the surface oxidation layer on each of the thin film samples was 6.5 ± 1.1 nm thick and uniform across a 0.25 mm region of the film.

Experimental Investigation of Phase Equilibria in the Al–Mo–Hf Ternary System at 400 °C and 600 °C

This study investigates the phase equilibria of the Al-Mo-Hf ternary system at 400 °C and 600 °C using X-ray diffraction (XRD) and electron probe microanalysis (EPMA/WDS) techniques. Seven three-phase and five two-phase regions were identified at 400 °C, while eight three-phase and four two-phase regions were identified at 600 °C. Despite variations in the solid solubility ranges of certain compounds, the distribution of phase zones in the isothermal cross-section remained consistent at both temperatures. Using the experimental results and logical deductions, isothermal cross-sections were constructed for the Al-Mo-Hf ternary system at 600 °C and 400 °C.

High-Temperature Cyclic Oxidation Behavior and Microstructure Evolution of W- and Ce-Containing 18Cr-Mo Type Ferritic Stainless Steel.

Due to the recurrent starting and stopping operations of automobiles during service, their engines' hot ends are continually subjected to high-temperature cyclic oxidation. Therefore, it is crucial to develop ferritic stainless steels with better high-temperature oxidation resistance. This study focuses on improving the high-temperature cyclic oxidation performance of 18Cr-Mo (444-type) ferritic stainless steel by alloying with high-melting-point metal W and the rare earth element Ce. For this purpose, a high-temperature cyclic oxidation experiment was designed to simulate the actual service environment and investigate the high-temperature cyclic oxidation behavior and microstructure evolution of 444-type ferritic stainless steel alloyed with W and Ce. The oxide structure and composition formed during this process were analyzed and characterized using scanning electron microscopy/energy dispersive spectroscopy (SEM-EDS) and electron probe X-ray micro-analyzer (EPMA), in order to reveal the mechanism of action of W and Ce in the cyclic oxidation process. The results show that 18Cr-Mo ferritic stainless steel alloyed with W and Ce exhibits an excellent resistance to high-temperature cyclic oxidation. The element W can promote the precipitation of the Laves phase between the matrix and the oxide film, and the small-sized Laves phase can inhibit the interfacial diffusion of oxidation reaction elements and prevent the inward growth of the oxide film. The element Ce can refine oxide particles and reduce the thickness of the oxide film. CeO2 particles within the oxide film can serve as nucleation sites for the formation of oxide particles from reactive elements, and they also contribute to pinning the oxide film, thereby enhancing its adhesion.

Studying the features of complex beryllium-containing silicate phases co-crystallization in zonal samples using the x-ray electron probe microanalysis method

Research subject. Silicate ingots containing four species-forming components Be, Mg, Al, and Si and belonging to the crystallization region of beryllium indialite (with the formula of Mg2BeAl2Si6O18 and a beryl-type structure). Aim. To investigate the fundamental problem of identifying the patterns of matter differentiation and the stable and metastable phase formation in silicate matrices. Methods. The evolution of the phase composition of silicate melts was registered using a temperature gradient method. Results. New data on the features of phase transformations in silicate melts belonging to the region of beryllium indialite were obtained by electron probe microanalysis (EPMA). Co-existing metastable and stable mineral phases were identified, and the similarity of their compositions with different structures was shown. The nature of impurity phases at each stage of crystallization was established. Conclusions. The evolutionary sequence of phase associations ensuring the crystallization of beryllium indialite and metastable phases of a similar composition, the nature of which is determined by the initial ratio of components, was experimentally recorded. The range of possible phase associations that co-crystallize or replace a stable phase with a beryl structure in melts from the region of existence of beryllium indialite in the BeO–MgO–Al2O3–SiO2 system was extended. The selectivity of the coloring element chromium entry into various phases of the studied system is shown depending on the capabilities of their structure. The addition of a chromophore is a reliable criterion for visualizing successive layers, zones, and areas of changing phase associations in the final ingot.