Search Results (12)

This study investigates pegmatites with exceptionally rare mineralogical and chemical signatures, hosted by the 1.8 Ga peralkaline albite-enriched granite, which corresponds to the renowned Madeira Sn-Nb-Ta-F (REE, Th, U) deposit in Pitinga, Brazil. Four distinct pegmatite types are identified: border pegmatites, pegmatitic albite-enriched granite, miarolitic pegmatite, and pegmatite veins. The host rock itself has served as the source for the fluids that gave rise to all these pegmatites. Their mineral assemblages mirror the rare-metal-rich paragenesis of the host rock, including pyrochlore, cassiterite, riebeckite, polylithionite, zircon, thorite, xenotime, gagarinite-(Y), genthelvite, and cryolite. These pegmatites formed at the same crustal level as the host granite and record a progressive magmatic–hydrothermal evolution driven by various physicochemical processes, including tectonic decompressing, extreme fractionation, melt–melt immiscibility, and internal fluid exsolution. Border pegmatites crystallized early from a F-poor, K-Ca-Sr-Zr-Y-HREE-rich fluid exsolved during solidification of the pluton’s border and were emplaced in contraction fractures between the pluton and country rocks. Continued crystallization toward the pluton’s core produced a highly fractionated melt enriched in Sn, Nb, Ta, Rb, HREE, U, Th, and other HFSE, forming pegmatitic albite-enriched granite within centimetric fractures. A subsequent pressure quench—likely induced by reverse faulting—triggered the separation of a supercritical melt, further enriched in rare metals, which migrated into fractures and cavities to form amphibole-rich pegmatite veins and miarolitic pegmatites. A key process in this evolution was melt–melt immiscibility, which led to the partitioning of alkalis between two phases: a K-F-rich aluminosilicate melt (low in H₂O), enriched in Y, Li, Be, and Zn; and a Na-F-rich aqueous melt (low in SiO₂). These immiscible melts crystallized polylithionite-rich and cryolite-rich pegmatite veins, respectively. The magmatic–hydrothermal transition occurred independently in each pegmatite body upon H₂O saturation, with the hydrothermal fluid composition controlled by the local degree of melt fractionation. These highly F-rich exsolved fluids caused intense autometasomatic alteration and secondary mineralization. The exceptional F content (up to 35 wt.% F in pegmatite veins), played a central role in concentrating strategic and critical metals such as Nb, Ta, REEs (notably HREE), Li, and Be. These findings establish the Madeira system as a reference for rare-metal magmatic–hydrothermal evolution in peralkaline granites. Full article

The problem of the adhesion of aluminum slag to the inner wall of a vacuum ladle is essential but has not been addressed. Using a high-temperature wettability experimental setup, this paper investigates the mechanism of interfacial wettability, adhesion, and penetration between Na₃AlF₆-Al₂O₃-CaF₂ cryolite-based molten salt and SiC refractory substrate. The composition of the slag was determined based on the slag obtained in the transfer ladle during the aluminum electrolysis process. We mainly study the effects of different Al₂O₃ contents in cryolite-based molten salt and temperatures on the contact angle and surface tension. The results indicate that as the Al₂O₃ content in the slag increases, the contact angle decreases, enhancing the slag’s wettability on the SiC substrate. Additionally, a higher Al₂O₃ content leads to higher slag melting temperatures and surface tension, which improves the slag mobility and enhances the mass transfer and diffusion capabilities of molecules or ions within the slag. The work of adhesion, calculated using the Mills model, also increases with the increasing Al₂O₃ content. The increased Al₂O₃ concentration activates the activity of Na₃AlF₆ in the slag, facilitating the dissolution reactions and improving the wettability between the slag and SiC. Moreover, the wetting behavior of the Na₃AlF₆-Al₂O₃-CaF₂ slag is primarily influenced by the initial Al₂O₃ content and its compositional changes. The results show that the slag penetration resistance and mechanical erosion resistance of the ladle lining can be improved by using an SiC-based refractory with an optimized Al₂O₃ content. This will have important guiding significance for the development, design, and application of inner wall materials for aluminum electrolysis industrial vacuum ladles. Full article

Niobium (Nb) and tantalum (Ta) are quoted as “strategic” or “critical” elements for contemporaneous society. The main sources of Nb and Ta are minerals of the pyrochlore supergroup (PSGM) and the columbite group (CGM) mined from different magmatic lithologies. Textures and chemical compositions of PSGM and CGM often provide key information about the origin of NbTa mineralization. Therefore, we decided to carry out a detailed study of the relations between the PSGM and CGM and their post-magmatic transformations, and the Madeira peralkaline pluton (Brazil) is an ideal object for such a study. Textures of the PSGM and CGM were studied using BSE imaging and SEM mapping, and their chemical compositions were determined using 325 electron microprobe analyses. Pyrochlore from the Madeira granite can be chemically characterized as Na, Ca-poor, U- and Pb-dominant, and Sn- and Zn-enriched; REE are enriched only during alteration. Two stages of alteration are present: (i) introduction of Fe + Mn, with the majority of them consumed by columbitization; (ii) introduction of Si and Fe, and in lesser amounts also Pb and U: Si, Pb, and U incorporated into pyrochlore, iron forming Fe-oxide halos around pyrochlore. During both stages, F and Na decreased. In the case of a (nearly) complete pyrochlore columbitization, U and Th were exsolved to form inclusions of a thorite/coffinite-like phase. In contrast to altered pyrochlores from other localities, pyrochlore from Madeira shows a relatively high occupancy of the A-site. Although Madeira melt was Na-, F-rich, contemporaneous crystallization of cryolite consumed both elements and pyrochlore was, from the beginning, relatively Na-, F-poor. Full article

The Dakalasu No.1 pegmatitic rare-element deposit is a representative of Be-Nb-Ta pegmatites in Altai, Xinjiang, China. Beryl is the most important beryllium-carrying mineral in Dakalasu No.1 pegmatite. To constrain the concentration mechanism of Be, we conducted a study of the textural relationships and chemical compositions (major and trace elements) of beryl, along with microthermometry and Raman spectroscopy on beryl-hosted fluid inclusions. Two generations of beryl were recognized. The early beryl I was formed in the magmatic stage, whereas the late beryl IIa and IIb were formed in the magmatic-hydrothermal stage. Lithium and Cs contents increased from beryl I, beryl IIa, to beryl IIb, whereas Mg and Rb contents decreased. Scandium, V, and Ga contents of beryl IIa are similar to beryl IIb, but different in beryl I. Titanium is enriched in beryl IIa. The high FeO contents and Na/Cs ratios of beryl (I, IIa, and IIb) reveal the low degree of differentiation evolution of the Dakalasu No.1 pegmatite. Two types of melt inclusions and four types of fluid inclusions were identified in beryl IIa, IIb, and associated quartz. The microthermometry results indicated that beryl II is formed at 500 °C–700 °C, and 200 MPa–300 MPa. The Dakalasu No.1 pegmatite melt is enriched in volatiles, such as B, F, and CO₂, evidenced by a large amount of tourmaline in the wall zone, the occurrence of a variety of tiny cryolite (Na₃AlF₆) inclusions, and CO₂-rich fluid inclusions in beryl IIa. The enrichment mechanism of Be may be related to the crystallization of beryl at highly undercooled states of melt, and melt–melt–fluid immiscibility during the evolution and differentiation of the melt. Full article

A new way to reduce the energy consumption during the operation of powerful aluminum reduction cells is suggested via reducing the resistance of the electrolyte, i.e., increasing its electrical conductivity. The electrical conductivity of molten cryolite mixtures NaF-AlF₃-CaF₂-Al₂O₃ with cryolite ratio (CR) of 2.1–3.0 and content of CaF₂ and Al₂O₃, up to 8 wt%, was measured at the temperatures from liquidus to 1300 K. Based on the experimental results, a multifunctional equation for the electrical conductivity of oxide-fluoride cryolite melts was evaluated. The experimental and calculated values of the electrical conductivity agree within 1.5%. The activation energy of the electrical conductivity of the NaF-AlF₃-CaF₂-Al₂O₃ melts was estimated. The activation energy of electrical conductivity for molten NaF-AlF₃ mixtures with CR 3.0 and 2.1, determined by the most mobile cations Na⁺, increased from 15.8 kJ/mol up to 18.5 kJ/mol. It was found that CR had a greater impact on the activation energy than the changes in the Al₂O₃ or CaF₂ concentrations. Based on the ratio of the activation energies of the electrical conductivity and the viscous flow, the correlation between the electrical conductivity and viscosity of molten cryolite mixtures NaF-AlF₃-CaF₂-Al₂O₃ was illustrated. Full article

Electrolysis experiments to produce Al-Sc alloys were carried out in galvanostatic mode using a cryolitic melt with a NaF/AlF₃ molar ratio of 2.2 at 980 °C, using both synthetic and waste feeds. After elucidation of the cryolite electrolyte bath chemistry when adding Sc₂O₃, small-laboratory scale trials allowed for the demonstration of the process and the study and for the optimisation of the electrolysis parameters. Experiments in large-scale electrolysis cells allowed us to run long-term trials in continuous operation, while the on-line monitoring of the cell off-gases ensured the environmentally benign performance of the process. The aluminium product obtained contained 0.6–2.6 wt% Sc, depending on the current density applied. The material is suited to prepare Al-Sc master alloys for 3D printing powders. Full article

Gas bubble behavior on a carbon anode in a cryolite melt has been studied using a see-through cell. The phenomena studied have been growth, coalescence, detachment, and wetting during electrolysis. The surface orientation affects bubble behavior. Therefore, two different anode designs were tested, an anode with a horizontal downward-facing surface and an anode with a vertical surface. At the horizontal anode, it was found that one large bubble was formed by the growth and coalescence of smaller bubbles, and finally, the large bubble detached periodically. For the vertical anode surface, the detaching bubbles were smaller, and most of them had been going through a coalescence process prior to detachment. The bubbles detached randomly. The coalescence process from the initiation to the final bubble shape at the vertical surface took about 0.016–0.024 s. The current density did not affect the duration of the coalescence. The bubble diameter was decreasing with increasing current density for both anodes. The values were in the range 7.2 to 5.7 mm for the horizontal anode in the current density interval 0.2–1.0 A cm⁻² and in the range 3.7 mm to 1.5 mm for the vertical anode in the current density interval 0.1–2.0 A cm⁻². The wetting contact angle for the vertical anode stayed more or less constant with an increase in current density, which likely can be attributed to the decreasing bubble size rather than an increase in polarization. In addition to the bubble phenomena described and bubble properties found, the impact of the results for better design of laboratory-scale studies is discussed. Full article

The phase relations in the Si-Al-Na-K-Li-F-H-O model granite system are studied experimentally at T = 800, 700 °C and P = 1 and 2 kbar, as well as at T = 600, 550, 500 and 400 °C and P = 1 kbar and different water content from 2 to 50 wt.%. The initial composition was set in such a way that the composition of the resulting silicate melt was close to the granite eutectic. It is shown that in the presence of Li, two immiscible melts are formed in the system—an aluminosilicate (L) and a salt alkali-aluminofluoride (LF). It is shown that at Т = 800 °С, Р = 1 kbar and 2 kbar and water content > 10 wt. %, three phases are equilibrium in the system: L, LF, and fluid (Fl). Cryolite (Crl), which does not contain REE, begins to crystallize from the salt melt at 700 °C. Quartz (Qtz) crystallizes from the silicate melt at 600 °C and the equilibrium phases are L, LF, Crl, Qtz. At T = 500 °C Qtz, Na and K aluminofluorides and polylithionite crystallize from the aluminosilicate melt. The joint crystallization of Crl and Qtz is observed. Large crystals of cryolite and elpasolite are formed in both the salt and silicate melts. At the same time, the residual salt melt enriched in Li and REE is partially preserved. LF is completely crystallized at 400 °C, and L is in a metastable state. It is established that REE, Sc, Y and Li accumulate in the salt melt up to 500 °C with partition coefficients >> 1. REE and Sc enter into composition of the crystal phases at T = 500 °C and 400 °C. Sc partially isomorphically replaces Al. REE most often forms its own fluoride phases of the LnF3 type. Full article

Gas bubble behavior on a carbon anode in a cryolite melt has been studied by visual observation using a see-through cell. The bubble phenomena studied have included growth, coalescence, and detachment during electrolysis. Two different anode designs were tested, an anode with a horizontal facing-downwards surface and an anode with a vertical surface. At the horizontal anode, it was found that one large bubble was formed by the growth and coalescence of smaller bubbles, and finally, the large bubble detached periodically. For the vertical anode surface, many smaller bubbles were formed and detached randomly. The bubble diameter was decreasing with increasing current density for both anodes. Full article

This work aims to study the CO-CO₂ gas composition at low potentials and low current densities in cryolite melt with relatively low alumina content (≤2 wt%). There is a scarcity of data in the literature regarding the low current density region and also for bath low in alumina. The experimental setup was constructed to minimize the back reaction as well as the Boudouard reaction. For potentials up to 1.55 V and corresponding current densities up to 0.07 A cm⁻², it was found that CO is the dominant product. Between 1.55 and 1.65 V (corresponding current density region 0.07 to 0.2 A cm⁻²), CO₂ becomes the dominant gas product. These potential values are probably slightly large due to suspected Boudouard reaction between CO₂ and carbon particles in the melt formed by disintegration of the graphite anode. The results are discussed in relation to the literature data and thermodynamic calculations. Full article

Pyrochlore group minerals are the main raw phases in granitic rocks of the Katugin complex-ore deposit that stores Nb, Ta, Y, REE, U, Th, Zr, and cryolite. There are three main types: Primary magmatic, early postmagmatic (secondary-I), and late hydrothermal (secondary-II) pyrochlores. The primary magmatic phase is fluornatropyrochlore, which has high concentrations of Na₂O (to 10.5 wt.%), F (to 5.4 wt.%), and REE₂O₃ (to 17.3 wt.%) but also low CaO (0.6–4.3 wt.%), UO₂ (to 2.6 wt.%), ThO₂ (to 1.8 wt.%), and PbO (to 1.4 wt.%). Pyrochlore of this type is very rare in nature and is limited to a few occurrences: Rare-metal deposits of Nechalacho in syenite and nepheline syenite (Canada) and Mariupol in nepheline syenite (Ukraine). It may have crystallized synchronously with or slightly later than melanocratic minerals (aegirine, biotite, and arfvedsonite) at the late magmatic stage when Fe from the melt became bound, which hindered the crystallization of columbite. Secondary-I pyrochlore follows cracks or replaces primary pyrochlore in grain rims and is compositionally similar to the early phase, except for lower Na₂O concentrations (2.8 wt.%), relatively low F (4 wt.%), and less complete A- and Y-sites occupancy. Secondary-II pyrochlore is a product of late hydrothermal alteration, which postdated the formation of the Katugin deposit. It differs in large ranges of elements and contains minor K, Ba, Pb, Fe, and significant Si concentrations but also low Na and F. Its composition mostly falls within the field of hydro- and keno-pyrochlore. Full article

Fe-Ni-based alloys are promising materials of inert anodes for use in aluminum electrolysis and adding Al can further improve the corrosion resistance. Fe-Ni-Al alloys with 1.4–8.6 wt.% Al were prepared by vacuum melting, and their corrosion as anodes during the production of pure Al (98.14–99.68%) by electrolysis was studied in a melt of NaF-AlF₃-NaCl-CaF₂-Al₂O₃ at 850 °C. The corrosion layer on the anode contains fluorine salt that corrodes the oxide film, and the inner layer is Ni-enriched while the outer layer is enriched with Fe and O due to the preferential oxidation of Fe. The electrolytically deposited oxide films on Fe-Ni-Al alloys with different compositions contains Fe₂O₃, Fe₃O₄, NiO, Al₂O₃, FeAl₂O₄, NiFe₂O₄, and other protective oxides, making the alloys very corrosion-resistant. The linear voltammetric curves can be divided into three parts: active dissolution, passivation transition, and over-passivation zones. The alloy with 3.9 wt.% Al (57.9Fe-38.2Ni-3.9Al) has a relatively negative passivation potential, and therefore, is easier to become passivated. According to the Tafel curve, this alloy shows a relatively positive corrosion potential as anode (1.20 V vs. Al/AlF₃), and thus can form a protective film. Full article