Electron Probe X-ray Microanalysis Research Articles

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.

The Effect of W, Cr, Mo Content on the Microstructure and Mechanical Properties of the Weld Interface of TiC Cermet and Low-Carbon Steel

In this study, the influence of W, Cr, and Mo on the microstructure and mechanical properties of the arc-welded interface of TiC cermet and low-carbon steel was investigated. MIG arc welding was employed to deposit muti-alloyed low-carbon steel flux-cored wire onto the surface of the TiC cermet to create the arc-welded interface. Analysis of the microstructure, phase composition, and shear fracture of the interface were conducted by OM (optical microscopy), SEM (scanning electron microscope), EMPA (Electron Probe X-ray Micro-Analyzer), and XRD (X-ray diffraction) methods. The results indicate that the order of influence on the performance of the welded interface is perceived as Cr > W > Mo. The preferred ratio of element content is W at 1.0 wt.%, Cr at 0.5 wt.%, and Mo at 2.0 wt.%. During the arc-welding process, W and Mo formed a rim structure of TiC particles to inhibit the dissolution of TiC particles, while Cr formed dispersed carbides in the bonding phase. The synergistic impact of these components resulted in the simultaneous enhancement of both the TiC particles and the bonding phase. This led to a significant increase in the shear strength of the TiC cermet welded interface to 787 MPa, marking an 83% improvement compared to the welded interface without reinforcement, which exhibited a shear strength of 430 MPa.

Analysis of slag chemistry in WEEE smelting using experimental and modelling study of the “CuO0.5”-ZnO-FeO-FeO1.5-CaO-SiO2-AlO1.5 system in equilibrium with Cu metal

The variability of the composition of recycled copper-containing materials requires enhanced control and understanding of slag chemistry in the secondary pyrometallurgical processing, when compared to primary copper smelting. In the black copper route for recycling waste electronic and electrical equipment (WEEE), slags exhibit high concentrations of alumina and zinc oxide. The simplest system governing phase equilibria at the reducing smelting stage of the black copper process is “CuO0.5”-ZnO-FeO-FeO1.5-CaO-SiO2-AlO1.5. In the present study, slags within this system were equilibrated with liquid copper Cu and solid Fe metallic alloys, quenched and characterized by the Electron Probe X-ray Microanalysis (EPMA). The range of compositions was selected based on the information about the process available in literature. The study focused on the liquidus and proportion of solid spinel in the temperature range from 1100 to 1300 °C. Precise control of the proportion of solids can enhance the stability of refractory materials against corrosive slags while maintaining entrained metal droplets at reasonably low level. Additionally, experimental correlations between the solubility of copper in the oxide liquid and the partial pressure of oxygen were developed for the Zn-free slags in equilibrium with metallic copper at 1200 and 1300 °C. All experimental results were compared to thermodynamic predictions using recent models and FactSage® software. Uncertainties were identified to be used in further model improvement.

Development and application of matte/speiss/metal thermodynamic database for optimization of processing of drosses, dusts and reverts from lead, zinc and copper production

Detrimental elements such as arsenic and antimony tend to accumulate in dusts and drosses of lead-zinc as well as copper smelters. These by-products are commonly treated in dedicated reductive smelting units producing Cu-rich matte, As-Sb-collecting speiss and Pb-rich metal, as well as liquid slag. Such process would have a complex distribution of elements (Cu, Fe, Pb, Zn, Ni, Sn, Sb, As, Ag, Au, S, etc.) among four liquid phases. Thermodynamic calculations can be used for predictions and optimization of such processes. They must rely on accurate models developed in integration with experimental program. Present study reports results of recent progress in experimental and modelling studies of As, Sb-containing speiss systems and demonstration of calculations relevant for industrial conditions. Experimental methodology consisted of equilibration, quenching and electron probe X-ray microanalysis. Calculations were performed using FactSage software and thermodynamic database developed based on the dedicated recent experiments. The main findings of the paper are: a set of binary and ternary diagrams relevant to matte and speiss formation conditions; distribution of Ag and Au among liquid Pb and speiss in key quaternary systems; and distributions of 10 main elements for industrially relevant matte/speiss/metal multicomponent equilibria.

Fundamental experimental and thermodynamic modelling study in support of the lead battery recycling slag

Antimony, tin, and other higher value metals, as well as elements such as arsenic and lead, can be found in the slags produced during the lead battery recycling process. Gopher Resources operates lead battery recycling furnaces that use sodium slag systems for which there has been less thermodynamic research than more common slag systems. Better thermodynamic information could help improve the process efficiency and control of these furnaces, as well as the recovery of higher value metals. The present study focuses on experimental research and thermodynamic modeling of slags belonging to the Na-Si-Fe-O system, with minor elements including S, Sb, Sn, Pb, and As. Examples of important systems studied extensively for the first time include Fe-Sb-Si-O and Na-Sn-Si-O. Phase equilibria methods are used to determine all the interaction parameters between the impurity metals and the main components of the slag. The experimental methodology involves equilibration, quenching, and electron-probe X-ray microanalysis of the samples. The modified Quasichemical model is used to describe the thermodynamics of the slags. The model also takes into account possible formation of matte/metal/speiss liquids, and numerous solid phases, which is important for understanding of fundamentals operation of various process units.

Metallogenetic epoch and material source of Be-pegmatite differentiated from biotite granite in Mufushan complex

The Mufushan Complex (MFSC) is a significant rare metal mineralized in the central China district and is renowned for its marked economic value of rare metal deposits. While the main rare metal mineralization (RMM) stage in the MFSC relates to the magmatic event of two-mica monzogranite, the mineralization event related to biotite monzogranite remains unknown. To fill this gap, this study focuses on porphyritic biotite monzogranite and adjacent Be-rich pegmatite samples obtained from Changqing Pegmatite No. 1, which is situated in the southeastern part of the MFSC. We subjected these samples to zircon U–Pb dating and Hf isotope analysis using laser ablation inductively coupled plasma mass spectrometry (LA–ICP–MS) and utilized an electron probe X-ray microanalyzer (EPMA) and LA–ICP–MS to examine the major and trace elements present in the muscovite samples. Our findings revealed precise chronological data for the geological history of Changqing, pinpointing the intrusion age of biotite monzogranite to 145.8 ± 1.1 Ma and the crystallization age of Be-rich pegmatite to 144.9 ± 1.1 Ma, firmly situating these events within the Late Jurassic to Early Cretaceous epoch. Regarding isotopic composition, zircon εHf (t) for granite ranged from −9.29 to −5.09, and their corresponding TDM2 ranged from 1788 to 1520 Ma. Similarly, zircon εHf (t) for pegmatite ranged from −7.89 to −5.47, and their corresponding TDM2 ranged from 1699 to 1544 Ma. These isotopic signatures strongly indicate a shared origin for the initial magma of granite and pegmatite. The partial melting of the thick Lengjiaxi Group tasedimentary strata serves as a material source for RMM. The transition from granite to pegmatite exhibits remarkable constancy in the primary components of muscovite. By examining its geochemical attributes, we observed synchronous decreases in FeO, MgO, SiO2, MnO, Be, Rb, and Cs, coupled with synchronous increases in Nb and Ta contents, along with Ta/Nb values. These findings strongly imply that the Changqing biotite monzogranite and Be-rich pegmatite originate from the continuous differentiation and evolution of a common magmatic source, establishing a clear genetic relationship between them. The MFSC has its origins in three distinct stages of magmatic activity and RMM spanning from 160 Ma to 120 Ma. Considering the distribution patterns of similar pegmatite veins, the metallogenic potential observed during the biotite granite stage may serve as an external indicator of marked mineralization within large batholiths.

Phase equilibria in the NiO-ZnO-SiO2 and PbO-NiO-ZnO-SiO2 systems

Experimental investigation and thermodynamic modeling of the phase equilibria in the (PbO)-NiO-ZnO-SiO2 system has been undertaken to characterize Ni behavior in high-Zn slags. Phase equilibria data at 790–1700 °C were obtained through equilibration of synthetic mixtures in sealed silica ampoules or Pt-Ir / Au foils, rapid quenching, and electron probe X-ray microanalysis. Phase equilibria and liquidus isotherms of the NiO-ZnO-SiO2 system in the tridymite/cristobalite SiO2, monoxide (Ni,Zn)O, zincite (Zn,Ni)O, olivine (Ni,Zn)2SiO4 and willemite (Zn,Ni)2SiO4 phase fields were measured and the extent of the 2-liquid immiscibility gap over cristobalite was determined. Additional solid solutions: larsenite Pb(Zn,Ni)SiO4 and melilite Pb2(Zn,Ni)Si2O7 were measured in the PbO-NiO-ZnO-SiO2 system. It was found that NiO partially substitute ZnO in larsenite and melilite and may form a complete range of solubility in barysilite Pb8(Zn,Ni)Si6O21. New data were used for developing a thermodynamic database to describe the Pb/Cu-containing complex system for characterizing Ni behavior in Zn-containing slags.

Behavior of Tantalum in a Fe-Dominated Synthetic Fayalitic Slag System—Phase Analysis and Incorporation

Pyrometallurgical processes produce slags that may contain valuable elements because of their high oxygen affinity. However, the concentration is extremely low, which causes losses. In fact, these elements, for example, tantalum and rare earth elements, are less than 1% recycled. To return such technologically important elements to the material cycle, pyrometallurgically is used to enrich them in the simplest possible compounds within the slag, which have favorable properties for recovery (morphology, crystal size, magnetic properties), allowing further mechanical separation. The purpose of modification of the slag system is to obtain engineered artificial minerals” (EnAM), a process in which targeted minerals with high element concentration are formed. In this article, this approach is investigated using tantalum-rich fayalitic slag, since this slag is commonly found in the industry for the pyrometallurgical treatment of waste electric and electronic equipment. Synthetic fayalitic slags in reducing environment under different cooling rates were produced with Ta addition. The characterization of the produced samples was carried out using powder X-ray diffraction (PXRD) and electron probe microanalysis (EPMA). Additionally, the speciation of Fe and Ta was accessible through X-ray absorption near-edge structure (XANES) spectroscopy. EPMA also provided a semiquantitative assessment of the Ta distribution in these individual compounds. In these slags, tantalum accumulated in perovskite-like oxidic and silicate compounds as well as in magnetic iron oxides. The enrichment factor is highest in tantalite/perovskite-type oxides (FexTayO6, CaxFeyTazO3) with up to 60 wt.% Ta and ‘tantalomagnetite’ (FeII(FeIII(2-5/3x)Tax)O4) with a maximum of ~30 wt.% Ta (only fast cooling). This is followed by a perovskite-like silicon containing oxide (XYO3) with 12–15 wt.% Ta (only slow cooling), and a hedenbergite-like compound (XYZ2O6) with a varying content of 0.3–7 wt.%. The Ta concentration in pure Fe, Fe(1-x)O, hercynitic spinel and hematite is negligible. Despite the very low phase fraction, the most promising EnAM compound is nevertheless perovskite-like tantalum oxide, as the highest enrichment factor was obtained. Tantalum-rich magnetite-like oxides also could be promising.