Search Results (165)

Phase formation characteristics during the thermochemical reduction of metals from natural coltan using aluminum and calcium–aluminum alloy at 1400–1450 °C were investigated to develop methods for extracting niobium and tantalum from rare metal raw materials. The studied coltan sample consists of a columbite–tantalite solid solution with the composition (Mn,Fe)(Nb,Ta)₂O₆, cassiterite Sn_0.9O₂, tapiolite (Ta,Nb)₂(Mn,Fe)O₆, and calcioolivine Ca₂SiO₄. This study established that the choice of reducing agent determines the sequence of oxide phase transformations. During the aluminothermic process, orthorhombic columbite–tantalite is completely reduced, while tetragonal tapiolite persists even at 1400 °C. The use of a calcium–aluminum alloy containing 69.4 wt.% Ca results in a reversal of this trend: tapiolite is reduced at the early stages (800–1250 °C) through an intermediate (Ta,Nb)O₂ phase, whereas the columbite–tantalite solid solution remains up to 1250 °C. Calcium, having a high affinity for oxygen, forms intermediate perovskite-type oxide phases that act as diffusion barriers, limiting the access of the reducing agent to residual mineral inclusions (mainly Nb-Ta minerals of the orthorhombic crystal system). A temperature rise to 1450 °C initiates the redistribution of oxide components: the content of CaNbO₃ decreases, the Ca₂(Nb,Ta)AlO₆ phase disappears, and its components are involved in the formation of Ca(Nb,Ta)_0.25MnO_2.74 and Ca₄Nb₂O₉. Diffusion constraints are reduced, and the residual columbite–tantalite solid solution is reduced, as confirmed by its complete absence in the products at 1450 °C. In the metallic phase, solid solutions of tantalum and niobium, Ta-Nb-Sn intermetallic compounds (Ta,Nb)₃Sn, titanium aluminide, and ferroalloys with an increased (Ta,Nb)/(Fe,Mn) ratio are formed. The phase transformations elucidated during metallothermic reduction of coltan using different reducing agents, together with the formation of metallic and intermetallic phases, establish a scientific foundation for the development of advanced rare metal extraction processes. Full article

The West Kunlun represents one of the largest and most economically significant rare metal metallogenic belts in NW China. The newly discovered Dahongliutandong Li deposit is the first Li deposit identified within the Permian Huangyangling Group in this region, and its discovery has important implications for regional lithium exploration. In this study, whole-rock major and trace-element geochemistry and cassiterite U–Pb isotope data from both Li-poor and Li-rich pegmatites of the Dahongliutandong deposit were analyzed to constrain the mineralization age and tectonic setting. Geochemically, the pegmatites are characterized by high SiO₂ (70.57–78.50 wt%), low TiO₂, MnO, and MgO (<0.2 wt%), and strongly peraluminous signatures (A/CNK = 1.45–1.95). They exhibit coherent chondrite-normalized REE patterns with LREE enrichment and negative Eu anomalies (Eu/Eu* = 0.03–0.77), along with consistent enrichment in LILEs (e.g., Rb, U, K) and depletion in HFSEs (e.g., Nb, Ti) on primitive mantle-normalized spider diagrams, suggesting a common magmatic source or evolutionary path. Cassiterite U–Pb dating yielded consistent lower-intercept ages of 208 ± 11 Ma (MSWD = 0.86) for Li-poor pegmatites and 206 ± 5 Ma (MSWD = 1.7) for Li-rich pegmatites, both indicating Late Triassic mineralization. Combined with regional geology, these data suggest that Li mineralization was likely related to post-collisional extension following the closure of the Paleo-Tethys Ocean. This study provides new insights into regional rare metal mineralization in the West Kunlun orogenic belt. Full article

Archaeological evidence for prehistoric placer tin mining is rare due to the ephemeral nature of the workings and the associated tools in the dynamic setting of active river systems. Here, we report an additional line of evidence for metallurgical activities at stream tin mining in Serbia at Mt. Cer and Bukulja. Rivers at these locations contain Pb-rich-glass grains, many of which are also enriched in Cu and Sn. Compositionally, the detrital grains of glass are similar to the vitreous infillings on a bleached ceramic sherd found at Spasovine, an archaeological site situated on the bank of the tin-rich Milinska River. The high-Pb-bearing (average 42 wt%) and Sn-bearing (average 0.7 wt%) composition of the glass, along with the inclusions of secondary cassiterite, indicate that the slag was derived from the refinement of leaded bronze (i.e., lead removal). Although the detrital glass slag grains lack direct archaeological context, broader archaeological observations limit their production to either the Roman or Medieval Periods. The presence of Pb-Cu-Sn metallurgical glass grains in a river at Bukulja provides the first concrete evidence of prehistoric tin mining at this locality, which demonstrates that sluicing for crushed glassy residues is a viable means to prospect for as yet undiscovered sites of ancient metallurgical activities. Full article

Metallogeny of low-K tholeiitic magmas in volcanic arcs is poorly documented and understood. The Mutnovsky volcano in Kamchatka erupted low-K tholeiitic basalt, basaltic andesite, andesite and dacite formed through partial melting of a depleted mantle wedge beneath the active front of the Kamchatka arc, followed by fractional crystallization in subarc magmatic conduits. Mineral microinclusions in Mutnovsky lavas are dominated by Cu-Ag chlorides and sulfides (±cerussite, baryte, cassiterite and Sb oxide), which show, along with the bulk rock Ag, Sn and Sb concentrations, a general increase during magmatic differentiation. Mutnovsky rocks are characterized by higher cumulative proportions of Cu-Ag sulfides and chlorides in comparison with the neighboring rear-arc Gorely and Bakening volcanoes, emphasizing the importance of S- and Cl-bearing fluids for their metallogenic evolution. Microinclusions in Mutnovsky tholeiites display certain similarities with ore mineral associations from epithermal and porphyry deposits in Kamchatka. Together with the enrichment of Mutnovsky lavas in Ag, Cu and Sb in reference to the bulk continental crust, this indicates a potential link between low-K tholeiitic magmas and Cu-Ag (±Sb, Sn) mineralization in volcanic arcs. Full article

This study investigates the genesis of gold mineralization at the Rodruin prospect in the central Eastern Desert (CED) of Egypt, with the aim of constraining the relative contributions of metamorphic and magmatic fluids to ore formation. Gold mineralization at Rodruin is hosted by quartz–carbonate veins emplaced within a shear zone that transects low-grade metasedimentary sequences intruded by Ediacaran post-tectonic granitoids. It exhibits characteristics transitional between orogenic turbidite-hosted and polymetallic vein-type mineralization. Although metamorphic devolatilization is interpreted to have generated the dominant ore-forming fluids, adjacent granitoid intrusions acted primarily as a thermal engine, with only a limited direct input of magmatic-hydrothermal fluids. This interpretation is supported by the occurrence of magmatic-affiliated mineral inclusions (monazite, cassiterite, and zircon) coupled with generally low concentrations of trace elements typically enriched in granitic magmatic-hydrothermal fluids (Sb, Bi, Mo, W, Sn, Nb, and Ta), collectively indicating a subordinate magmatic contribution. Rare earth element (REE) patterns of the ore samples closely resemble those of the nearby granitoids, displaying LREE enrichment; however, a distinct positive Eu anomaly is restricted to the ore assemblages and is attributed to hydrothermal feldspar alteration supporting magmatic involvement in ore formation. Carbon and oxygen isotope compositions (δ¹³C = −6.6 to −2.36‰; δ¹⁸O = +15.7 to +19.7‰), together with REE signatures comparable to primitive mantle values and textural evidence for synchronous sulfide–carbonate precipitation, manifested by rhythmic banding of carbonates and sulfides unequivocally indicate a hydrothermal–metasomatic origin. Collectively, these lines of evidence support a hybrid metamorphic–magmatic model in which gold and associated base metals were predominantly transported by metamorphic fluids, whose mobilization and focusing were enhanced by the thermal influence of Younger granitic intrusions, whereas magmatic-hydrothermal fluids contributed only a minor proportion to the overall metal budget. Full article

The new alluaudite-group mineral manganobadalovite (IMA 2020-035), ideally NaNaMn(MgFe³⁺)(AsO₄)₃, was found in the Arsenatnaya fumarole, the Second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption 1975–1976, Tolbachik volcano, Kamchatka peninsula, Far-Eastern Region, Russia. Manganobadalovite is a fumarolic mineral, and its aggregates are found overgrowing basalt scoria or exhalative hematite crystal crusts. Associated minerals are badalovite, hematite, cassiterite, sanidine, glauberite and metathénardite. Manganobadalovite occurs as prismatic to equant crystals up to 0.8 mm long typically combined in open-work clusters; it also forms grains that are irregular in shape and cavernous granular crusts up to 0.5 cm. The mineral is transparent, with vitreous luster, and its color varies from red to yellow. Manganobadalovite is brittle and has a noticeable cleavage in one direction and uneven fracture. The calculated density is 4.108 g cm⁻³. Manganobadalovite is optically biaxial (+), α = 1.790 (7), β = 1.800 (7), γ = 1.815 (8) and 2V_meas = 80 (5)°. Chemical composition (wt.%, electron-microprobe): Na₂O 8.75, K₂O 0.17, MgO 5.32, CaO 3.68, MnO 10.09, CuO 0.42, Al₂O₃ 0.18, Fe₂O₃ 13.90, V₂O₅ 0.42, As₂O₅ 56.75, total 99.68. The empirical formula calculated based on 12 O apfu is Na_1.69K_0.02Ca_0.39Mn_0.85Mg_0.79Cu_0.03Fe³⁺_1.04Al_0.02(As_2.96V_0.03)_∑2.99O₁₂. The crystal structure was solved using single-crystal XRD data, R = 2.30%. Manganobadalovite is monoclinic, C2/c, a = 12.1848(5), b = 12.8924(4), c = 6.6970(3) Å, β = 113.113(5)°, V = 967.60(7) ų and Z = 4. The strongest reflections of the powder XRD pattern are [d,Å(I)(hkl)]: 6.43(30)020, 3.589(32)(−131, 310), 3.215(38)(040, −112), 3.079(23)(221, 002), 2.941(32)(−312, −222, −331), 2.852(15)(041), 2.788(100)(330, 400, 240, 022), 2.649(22)(−402, 112), 2.626(25)(−132). Manganobadalovite is named as an analogue of badalovite NaNaMg(MgFe³⁺)(AsO₄)₃ with Mn²⁺ prevailing in the M(1) site. Full article

The new mineral polyarsite, ideally Na₇CaMgCu₂(AsO₄)₄F₂Cl, was discovered in high-temperature incrustations of the active Arsenatnaya fumarole at the Second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption, Tolbachik volcano, Kamchatka, Russia. It is associated with aegirine, sanidine, ferrisanidine, hematite, halite, sylvite, cassiterite, evseevite, axelite, badalovite, johillerite, arsmirandite, aphthitalite, tridymite, potassic-magnesio-fluoro-arfvedsonite and litidionite. Polyarsite forms short-prismatic, equant or tabular crystals up to 0.15 mm across, their clusters up to 0.3 mm in size or crusts up to 0.5 mm across and up to 0.03 mm thick. Polyarsite is transparent, sky-blue to light blue, with vitreous lustre. It is brittle, no cleavage is observed and the fracture is uneven. D_calc. = 3.592 g cm⁻³. Polyarsite is optically biaxial (+), α = 1.624 (4), β = 1.645 (4), γ = 1.682 (4) (589 nm), 2V_meas. = 70 (10)°. The empirical chemical formula calculated based on 19 O+F+Cl apfu is Na_7.04Ca_1.00Mg_0.92Cu_2.06Fe³⁺_0.06(As_3.96S_0.05)_Σ4.01O_16.28F_1.66Cl_1.06. Polyarsite is monoclinic, space group I2/m, a = 8.4323(4), b = 10.0974(4), c = 10.7099(6) Å, β = 90.822(4)°, V = 911.79(8) ų and Z = 2. The crystal structure was determined based on SCXRD data, R = 0.0391. Polyarsite demonstrates a novel structure type. The structure is based on the (1 0 1) heteropolyhedral layers formed by Cu₂O₈Cl dimers built by CuO₄Cl tetragonal pyramids sharing common Cl vertex, AsO₄ tetrahedra and MgO₄F₂ octahedra. Adjacent layers are linked via CaO₈ cubes to form a pseudo-framework which hosts octahedrally coordinated Na cations. Polyarsite was named based on the Greek words πολύς, poly, “many” and due to belonging to arsenates: this arsenate contains many chemical components ordered between different positions in crystal structure. Full article

Transparent conductive oxides (TCOs), such as indium tin oxide (ITO), are essential for flexible electronics; however, conventional vacuum-based deposition is costly and thermally aggressive for polymers. This study investigated the surface functionalization of PET substrates with ITO thin film-based forced hydrolysis as a low-cost, reproducible alternative. $\mathrm{S}\mathrm{n}{\mathrm{O}}_2$ nanoparticles were synthesized by forced hydrolysis at 180 °C for 3 h and 6 h, yielding crystalline nanoparticles with a cassiterite phase and an average crystallite size of 20.34 nm. The process showed high reproducibility, enabling consistent structural properties without complex equipment or high-temperature treatments. The $\mathrm{S}\mathrm{n}{\mathrm{O}}_2$ sample obtained at 3 h was incorporated into commercial ${\mathrm{I}\mathrm{n}}_2{\mathrm{O}}_3$ to form a mixed In–Sn–O oxide, which was subsequently deposited onto PET substrates by spin coating onto UV-activated PET. The resulting 1.1 µm ITO films demonstrated good adhesion (4B according to ASTM D3359), a low resistivity of 1.27 × 10⁻⁶ Ω·m, and an average optical transmittance of 80% in the visible range. Although their resistivity is higher than vacuum-processed films, this route provides a superior balance of mechanical robustness, featuring a hardness of (H) of 3.8 GPa and an elastic modulus (E) of 110 GPa. These results highlight forced hydrolysis as a reproducible route for producing ITO/PET thin films. The thickness was strategically optimized to act as a structural buffer, preventing crack propagation during bending. Forced hydrolysis-driven PET sheet functionalization is an effective route for producing durable ITO/PET electrodes that are suitable for flexible sensors and solar cells. Full article

The Jiulongnao W–Sn ore field in the eastern Nanling Range is characterized by large-scale early Yanshanian magmatic activity and W–Sn mineralization. In recent years, increasing attention has been given to the close relationship between Indosinian magmatic activity and Sn mineralization. The Aotou quartz vein-type Sn deposit is unique for only Sn mineralization without W during the Indosinian period. Seventeen thin-to-thick cassiterite–quartz veins are densely distributed in Ordovician metasandstone and slate, and these veins extend down to the top of the concealed granite. However, both the diagenetic age and the petrological characteristics of the concealed granite remain unclear. This contribution shows that the Aotou muscovite intrusion is a highly fractionated S-type pluton, characterized by a peraluminous, high-K composition, enrichment in LREEs, and depletion of Ba, Sr, Ti, and Eu. In this study, LA–ICP–MS zircon U–Pb dating of the concealed muscovite granite yields emplacement ages of 238.7 ± 1.0 Ma and 225.4 ± 0.9 Ma, indicating that at least two stages of magmatic intrusion occurred in the Triassic, with the diagenetic environment transitioning from a compressional setting to an extensional setting. The ε_Hf(t) values during the two stages are −0.98 to −0.95 and −0.98 to −0.96, and the T_DM2 values are 1.78–2.08 Ga and 1.78–2.06 Ga, indicating that two-stage magma was derived from the late Paleoproterozoic lower crustal materials. Comprehensive analysis reveals that the second stage of Indosinian magma intrusion (232–225 Ma) in the Jiulongnao ore field is closely related to Sn mineralization, and the northern Wenying pluton has good prospecting potential for quartz vein-type Sn(–W) deposits. Full article

This work prepared SnO₂ coatings on 304 stainless steel via the sol–gel and dip-coating techniques, using tin (II) chloride (SnCl₂) and tin (II) oxalate (SnC₂O₄) as precursors. The crystal structure analyzed by X-ray Diffraction (XRD) confirmed the cassiterite-type SnO₂ in both cases. The corrosion resistance in a 3 wt.% NaCl solution was evaluated by polarization resistance (Rp) and anodic potentiodynamic polarization. Coatings derived from the SnC₂O₄ precursor demonstrated exceptional performance, reducing the corrosion rate by up to three orders of magnitude (from 0.0973 mpy for uncoated steel to 0.00015 mpy), corresponding to a protection efficiency of 99.8%. In contrast, coatings from the SnCl₂ precursor increased the corrosion rate. X-ray Photoelectron Spectroscopy (XPS) analysis confirmed that this detrimental effect was due to the presence of chlorine (5.54 wt.%), which acted as an initiation site for pitting corrosion. Atomic force microscopy (AFM) and XRD of the effective SnC₂O₄-derived coatings revealed a homogeneous surface with low roughness and a textured cassiterite structure. The primary limitation of this work is that the sol–gel synthesis route using SnCl₂ is unsuitable for corrosion protection in chloride environments due to the incorporation of aggressive chlorine ions, whereas the chlorine-free SnC₂O₄ precursor yields highly protective SnO₂ coatings. Full article

Tin slags generated during cassiterite smelting in Brazil contain significant amounts of technologically important metals such as niobium, tantalum, and zirconium. Improper disposal of these materials represents both an environmental concern and the loss of a valuable secondary source of critical elements. This study aimed to characterize a Brazilian tin slag sample to evaluate its composition, morphology, and potential for metal recovery. The material was homogenized and analyzed by laser diffraction (particle size), ICP-OES (chemical composition), X-ray diffraction (mineral phases), differential scanning calorimetry (metallic tin), and scanning electron microscopy with energy-dispersive spectroscopy (morphology). The slag exhibited a heterogeneous particle size distribution (D90 = 0.75 mm, D50 = 0.30 mm, D10 = 0.09 mm) and a complex multiphase structure composed mainly of silica, calcium silicate, and zirconia. The chemical analysis revealed 4.8 wt% Nb and 0.8 wt% Ta, along with high concentrations of Zr (11.1 wt%), confirming the material’s potential as a secondary resource. Thorium (2.7 wt%) and uranium (0.3 wt%) were also detected, indicating the presence of radioactive constituents. The detailed characterization of the slag provides essential insights into its chemical and mineralogical complexity, which directly influence the selection of suitable recovery routes. Understanding the distribution of Nb- and Ta-bearing phases within the refractory silicate–zirconia matrix is fundamental for defining pretreatment and leaching strategies. Therefore, this study establishes a necessary foundation for the design of efficient hydrometallurgical processes aimed at recovering critical metals from Brazilian tin slags. Full article

Tungsten is a series of metals considered strategic by the European Union, so there is great interest in its recovery from both raw materials and secondary products. Within these raw materials, there are cassiterite deposits containing tungsten. It is from one of these deposits (located in the northwest of Spain) that after electrostatic separation, a scheelite concentrate (4.8% tungsten) has been obtained. This concentrate has been processed through two hydrometallurgical procedures. In one case, alkaline leaching in sodium carbonate medium is used to obtain sodium tungstate solutions, which in turn allows synthetic scheelite (calcium tungstate) or tungstic acid to be obtained. The second procedure, which uses acidic leaching (hydrochloric acid medium), yields tungstic acid as the final product. In all of the above cases, the experimental conditions to yield the best tungsten recovery rates are defined. The different products (sodium tungstate solutions and tungstic acid) afforded were used as precursors to yield synthetic scheelite and nanotungsten compounds as amorphous meta- and paratungstate salts and non-stoichiometric tungsten blue oxides. Full article

This work employed a design-of-experiments (DoE) strategy, specifically a 2³ full factorial design, to assess how suspension concentration (0.001–0.002 g/mL), substrate temperature (60–80 °C), and deposition height (10–15 cm) influence tin dioxide (SnO₂) thin films produced by ultrasonic spray pyrolysis (USP). The response variable was the net intensity of the principal diffraction peak, used as an operational metric for detecting the deposited phase. All patterns matched the SnO₂ phase cassiterite reference without impurity peaks. Statistical analyses (ANOVA, Pareto and half-normal plots, and response surface methodology, RSM) identified suspension concentration as the most influential factor, followed by significant two- and three-factor interactions. The model exhibited a high coefficient of determination (R² = 0.9908) and low standard deviation (12.53), validating its predictive capability. The optimal deposition process was achieved at the highest suspension concentration (0.002 g/mL), lowest substrate temperature (60 °C), and shortest deposition height (10 cm). These results demonstrate the utility of full factorial DoE for quantifying and controlling deposition outcomes in USP and provide a robust statistical framework to guide the synthesis of SnO₂ thin films. Full article

We report here, for the first time on the Nubian Shield, the western half of the Arabian–Nubian Shield (ANS), pegmatite-hosted pockets with a unique mineralogy, including pyroxmangite. It represents the second discovery on the ANS, where the first one was at Jabal Aja on the Arabian Shield, the eastern half of the ANS. One of the most remarkable aspects of pyroxmangite is its rarity and the potential economic value of its use in jewelry and decorative applications. Pegmatites are associated with A-type granites of the Gabal El-Bakriya intrusion (GEBI), Eastern Desert, Egypt. Mineralized pegmatites occur at the margin of the alkali-feldspar granite and exhibit gradational contacts with the host rocks. The pegmatites were emplaced as plugs and dikes within the intrusion and along its periphery. Pyroxmangite appears as coarse-grained, massive black aggregates or as disseminated crystals. The pegmatites are composed of K-feldspars and quartz, with subordinate amounts of albite, micas, and mafic minerals. Accessory phases include monazite-(Ce), zircon, fergusonite, xenotime, fluorite, pyrochlore, allanite, thorite, bastnäsite, samarskite, cassiterite, beryl, and pyrochlore. Pyroxmangite-bearing assemblages consist essentially of pyroxmangite and garnet, with accessory pyrochroite, quartz, zircon, magnetite, and fluorite. Geochemically, the pegmatites are highly evolved, with elevated SiO₂ content (76.51–80.69 wt.%) and variable concentrations of trace elements. They show significant enrichment in Nb (Nb > Ta), Y, REE, Zr, Th, U, and F, consistent with NYF-type pegmatites. REE contents range from 173.94 to 518.21 ppm, reflecting diverse accessory mineral assemblages. Tectonically, the pegmatites crystallized in a post-collisional setting, representing a late-stage differentiate of the A-type GEBI magma. Mineralization is concentrated in the apical and marginal zones of the granitic cupola and is dominated by barite, fluorite, Nb-Ta oxides, REE minerals, and uranium-bearing phases. The highly evolved granites, greisens, pegmatites, and quartz-fluorite veins of the GEBI have a high economic potential, deserving further exploration. Full article

Colquiri is one of several deposits from the Central Andean tin belt, where sphalerite and cassiterite are mined. Although this is a high-grade Zn-Sn deposit, processing results in a low overall yield, with significant amounts of zinc and tin being discarded as tailings. In this study, mineralogical research was conducted to identify the causes of the low yield, so that the flow diagram could be modified to improve recovery. Particle size was measured, and chemical and mineralogical analyses were performed using optical and electron microscopy and X-ray diffraction. The mineral chemistry of the ores was determined using electron probe microanalysis (EPMA), and mineral liberation analyses were performed to complete the characterization. Mineralization occurred in four stages: (1) formation of silicates and oxides; (2) main precipitation of sulfides, including pyrrhotite, sphalerite, and stannite; (3) precipitation of fluorite and the replacement of pyrrhotite by pyrite, which was then replaced by siderite; and (4) weathering of previously formed minerals. The run-of-mine material contains approximately 12 wt.% ZnO and 1.5 wt.% SnO₂. The Zn concentrate contains up to 43.90 wt.% ZnO, and the Sn concentrate contains 52 wt.% SnO₂. The final tailings still retain more than 3–4.5 wt.% ZnO and 1.2 wt.% SnO₂. The average grain size of sphalerite is 200 µm, while that of cassiterite and stannite is 45 µm. The liberated fraction of sphalerite is 51.43%, and binary particles of sphalerite plus stannite account for 60 wt.%. Cassiterite is liberated at 54.68 wt.%. To increase the recovery of sphalerite (with stannite) and cassiterite, as well as the grade of the concentrates, it is necessary to reduce the particle size of the processed ores to less than 100 µm. Full article