Sn Deposits Research Articles

In-situ zircon and cassiterite LA-ICP-MS geochronology and implications for granite-hosted Sn deposit models and exploration: Insights from the Cameroon Line

Abstract Tin mineralization of significant economic importance occurs across the continental portion of the Cameroon Line (CL). Tin deposits therein occur as both primary and secondary (residual and alluvial) ore. Though the temporal and, by inference, the genetic link between Sn mineralization and the host granite had long been modeled and widely accepted worldwide, in the CL, however, the age of the granite hosting cassiterite is poorly constrained, preventing a robust assessment of the temporal and genetic relationship between the Sn mineralization and its host rock. Here, we present in-situ zircon and cassiterite laser ablation inductively coupled mass spectrometry (LA-ICP-MS) U-Pb data in order not only to constrain the age of the granitic rock hosting the primary Sn ore but also to bracket the time frame of Sn mineralization, with respect to the magmatic-hydrothermal evolution of the parental magma of the host granite. Zircon from two greisen-altered, cassiterite-bearing granite samples yield overlapping and concordant ages of 64.21 ± 0.59 Ma and 65.46 ± 0.95 Ma, respectively, which are also overlapping with regional granite magmatism in the CL (ca. 65–30 Ma). On the other hand, cassiterite, which is spatially associated with the Paleocene zircon, yields Lower Eocene ages of 54.99 ± 0.35 Ma and 56.08 ± 0.46 Ma. The ca. 10 Myr time gap between zircon and cassiterite suggests that the granite is a passive host not genetically related to the Sn mineralization, which may be linked to a younger, concealed intrusion of ca. 55 Ma. This finding contrasts with the most widely accepted petrogenetic model of tin granite, according to which Sn mineralization and the host granite are cogenetic.

Cassiterite and zircon U-Pb ages and compositions from ore-bearing and barren granites in Thailand: Constraints on the formation of tin deposits in Southeast Asia

The Southeast Asian Tin Province comprises western, central, and eastern belts and hosts significant granite-related Sn deposits. The genetic links between granites and Sn mineralization are still unclear. Most Sn deposits are in Thailand’s western and central belts, but their origin remains poorly elucidated due to the absence of direct dating of mineralization. Herein in-situ U-Pb age data of wolframite and cassiterite grains from nine representative Sn deposits in Thailand are obtained, which fall into two stages. Triassic deposits (224–210 Ma) are found in the Central belt, with Cretaceous deposits (78–67 Ma) in the Central belt being younger than those in the Western belt (84–74 Ma). However, ore-bearing granites, spanning two periods (227–205 Ma and 85–69 Ma), occur in central and western belts. Some Triassic ore-bearing granites exhibit significantly older ages than ore-forming ages. Newly identified ore-forming granites contain zircon grains with relatively low εHf(t) values (−29.5 to + 4.1; average = − 11.8), indicative of an origin from supracrustal sediments from the Sibumasu block. In contrast, barren granites have ages from 303–224 Ma and higher zircon εHf(t) values (−9.9 to + 13.2; average = +1.2), which suggests that they were derived from the juvenile mafic crust. Even after experiencing hydrothermal fluids exsolution, some low-fractionated ore-forming granites (D.I. < 90) still maintain remarkably high tin contents. Both ore-forming and barren granites crystallized under reducing conditions. Our study highlights the importance of Sn-rich sources of parental magmas in forming Sn deposits. The metasediment-rich basement of the Sibumasu block distributing along the continental margin is likely the Sn-rich source. These sources played a crucial role in forming two stages of tin deposits in distinct tectonic settings, that are syn-collisional crustal thickening in Paleo-Tethys and post-collisional extension-related settings in Neo-Tethys.

Correction to: Cassiterite geochronology and geochemistry of the Yunling Sn deposit: implication for late Cenozoic mineralization in western Yunnan, China

Correction to: Cassiterite geochronology and geochemistry of the Yunling Sn deposit: implication for late Cenozoic mineralization in western Yunnan, China

Geochronology and decoupling controls of Sn-(Ta-Li) and W-(Sn) mineralization in the Iberian Variscan Massif, Spain and Portugal

Sn-W mineralization in the Iberian Variscan Massif (corresponding with the western zone of the Iberian Peninsula, in Spain and Portugal) occurs closely related to metaluminous to peraluminous granitoids of Variscan age. The deposits are grouped into two main styles of mineralization; Sn-(Ta-Li) and W-(Sn) deposits. Within this work we present a first attempt to correlate timing of W-Sn mineralization and plutonic events at a regional scale. We report new 40Ar/39Ar dates of muscovite related to the quartz-muscovite alteration of eleven deposits, molybdenite Re-Os dates from six deposits and two new zircon U-Pb dates of granitoids genetically related to the mineralization. The dates obtained support the relationship between W-Sn mineralization with specific, but not uniquely just one, granite suites. The dominant S-type peraluminous Variscan granitic suites in Iberia, the S1-type dated at ca. 330–311 Ma and the S2-type at ca. 314–296 Ma, are related to both, Sn-(Ta-Li) and W-(Sn) mineralization. A subgroup of deposits of the W-(Sn) group, generally enriched only in W but not in Sn is associated with the youngest but volumetrically less abundant I-type (ca. 303–280 Ma) metaluminous magmatism. The relationship of both the Sn-rich and W-(Sn)-rich deposits with the highly peraluminous S-type granites suggest that the ultimate source of the melts is not related to the decoupling between Sn and W. Therefore, the causes of W and Sn separation may be related to late-stage magmatic and magmatic-hydrothermal processes.

Cassiterite geochronology and geochemistry of the Yunling Sn deposit: implication for late Cenozoic mineralization in western Yunnan, China

Cassiterite geochronology and geochemistry of the Yunling Sn deposit: implication for late Cenozoic mineralization in western Yunnan, China

Urea Induces Uniform Tin Deposition for Long Cycle‐Life Tin‐based Redox Flow Battery

AbstractAmong multivalent redox flow batteries, the Zn‐based redox flow battery (RFB) has the advantages of high energy density, nontoxicity, and low cost. However, the severe dendrite issue hinders its deployment. Therefore, the Sn‐based RFB is reported as a prospective alternative, particularly in alkaline systems, due to its lower redox potential and four electrons transfer in redox reactions. However, the continuous growth of Sn during charge forms large Sn bulk, which increases the risk of “dead Sn” formation. By combining experiments and theoretical calculations, urea is proposed as an electrolyte additive to regulate Sn deposition on graphite felt. This is achieved through the enhanced adsorption and robust reaction of Sn(OH)62− with graphite felt. Consequently, a more uniform morphology ensues, reducing “dead Sn” formation and thus improving the average discharge voltage and areal capacity. Moreover, the Columbic efficiency becomes more stable, extending the cycle life to over 420 h (&gt;200 cycles) without deep discharge during cycling. This study demonstrates the role of urea in achieving high‐performance Sn‐I flow battery with long cycle life, paving the way for further development of metal‐based hybrid RFBs.

Regulating Sn Metal Growth Towards Highly Reversible Anode in Aqueous Acidic Batteries

Safe and cost-effective aqueous acidic batteries (AABs) offer substantial promise for renewable energy storage, as it have the potential to achieve greater energy and power density by utilizing non-metal hydrate protons as charge carriers.1 However, most of traditional aqueous anode electrodes (Zn, Fe, etc.) have incompatibility with AABs due to the instability in acid, resulting in the quite limited choice of anode materials in acidic environment.In prior research, we successfully demonstrated that Sn metal can serve as a highly suitable anode material for AABs.2 This is attributed to its comparatively high overpotential for the hydrogen evolution reaction (HER), substantial theoretical capacity (451.6 mAh g−1), and negative redox potential (−0.14 V vs. SHE).3 The critical issue is that Sn tends to form polyhedral particles during the electro-deposition due to the small difference in surface energy between different planes.4 Along with the increase of capacity, the polyhedron Sn particles may become detach and fragment, ultimately leading to the formation of inactive, or dead Sn, which significantly impacts the cycling stability of Sn anode and even cause severe HER.We will present our efforts of developing reversible Sn anode for AABs by regulating Sn metal growth. Our first work applies interfacial alloying regulation to achieve smaller grain size and more uniform Sn deposition by higher propensity for nucleation and Sn migration energy barrier, thus increased the anode reversibility. The following work successfully selected a HER-inert crystal plane and achieved its preferential growth used cationic surfactants electrolyte additive. A dense and compact Sn film is obtained by adjusting the adsorbed species on the Sn surface, and no dead Sn was observed after cycling. Based on these regulated Sn metal anodes, we demonstrated several Sn-based AABs (MnO2//Sn, PbO2//Sn, etc.), with promising performance on output voltages, specific energy densities, kinetics, and lifespans. References X. Wu, J. J. Hong, W. Shin, L. Ma, T. Liu, X. Bi, Y. Yuan, Y. Qi, T. W. Surta, W. Huang, J. Neuefeind, T. Wu, P. A. Greaney, J. Lu, X. Ji. Nat. Energy 2019, 4, 123-130.H. Zhang, D. Xu, F. Yang, J. Xie, Q. Liu, D. Liu, M. Zhang, X. Lu, Y. S. Meng. Joule 2023, 7, 971-985.W. Zhou, S. Ding, D. Zhao, D. Chao. Joule 2023, 7, 1099-1110.Y. Yao, Z. Wang, Z. Li, and Y. Lu. Adv. Mater. 2021, 33, 2008095.

Magmatic evolution and sources of metals and fluids in the large granite-related Xiasai vein-type Ag–Pb–Zn(–Sn) deposit, northern Yidun terrane, SW China

The Xiasai Ag–Pb–Zn–(Sn) deposit in the northern Yidun terrane (eastern Tethys), hosted in Late Triassic metasandstones, is genetically associated with Late Cretaceous granites. We present chemical and Sr–Nd–Pb–Li–B isotope data of Late Cretaceous granites and their mafic microgranular enclaves (MME), late aplites, and Late Triassic metasedimentary rocks. The narrow range of 87Sr/86Sr99 (0.70627–0.70953) and εNd99 (–6.1 to –5.2) values of most Late Cretaceous granites reflects a mixed source with contributions from the mantle and Paleoproterozoic felsic crust. These granites have high SiO2 contents (>69 wt%) and strong depletions in Sr, Ba, and Eu. Major and trace element contents correlate with the fractionation index 1/TiO2, indicating that they experienced extensive fractionation. Local late aplite dikes were derived from similar source rocks, but seem to be younger.The Pb isotopic compositions reflect that the metal Pb was derived from the granite with variable contributions from the Late Triassic sedimentary rocks. Weakly and moderately altered metasandstones have similar δ7Li and δ11B values as most granites (δ7Li: 0.00 to 2.68 ‰; δ11B values: –14.93 to –12.36 ‰), indicating magmatic fluid sources. The magmatic fluids resulted in the initial enrichment of Sn, Cu, Pb, and Zn. Strong alteration of feldspar and biotite resulted in the metasandstones in negligible change of Li concentrations, significant loss of Sr, Na2O, CaO, MgO, and Fe2O3, but significant addition of B. This alteration lowered δ7Li from 1.01 to –3.65 ‰ and lowered δ11B from –9.43 to –19.18 ‰. The low δ7Li values and extremely low δ11B values reflect external fluids from the Late Triassic sedimentary wall rocks, which interacted with granites and mobilized metals (e.g., Sn, Ag, Pb, and Zn) from the granite and/or the sedimentary wall rocks. The location of the Xiasai deposit is controlled by regional NNW-trending faults induced by Late Cretaceous extension.

Pulsatile extractions of Lower Cretaceous silicic volcanic plumbing system beneath the Baiyunzhang and Lianhuashan basins, eastern Guangdong: silicic magma evolution and related mineralization

Highly differentiated magmas are closely related to the formation of tin deposits. The Lianhuashan Basin and Baiyunzhang Basin, surrounded by multiple coeval tin deposits, developed various types of volcanic and subvolcanic rocks. The diagenetic connections between different types of rocks within the two basins provide new insight into the evolution of the silicic magma systems and the impact of highly differentiated magmas on tin mineralization. Both basins have consistent zircon U–Pb ages (143–138 Ma) and similar whole-rock Nd isotopes ( ε Nd ( t ) = −5.7 to −3.4) and zircon Hf–O isotope ranges ( ε Hf ( t ) = −9.0 to −2.5; δ 18 O = 5.1–7.9), suggesting that both basins originate from the same deep-level magma reservoir, followed by different degrees of crystal differentiation and several episodes of crystal–melt separation in their respective shallow-level magma reservoirs. The multiple pulses of magma extraction eventually produced different volcanic rocks (granite porphyry and rhyolite porphyry), whereas the remaining crystal mush consolidated in situ to form quartz monzonite porphyry. Further studies show that the tectonic regime changed from a compressive to an extensional environment at c . 140 Ma. Consequently, mantle-derived magmas with low oxygen fugacity injected shallow magma reservoirs that were able to evolve to a high degree of differentiation through multiple recharge, thus favouring the formation of the Sn deposit.

Designing a Stable Alloy Interlayer on Li Metal Anodes for Fast Charging of All-Solid-State Li Metal Batteries

The deposition of a thin LixSny alloy layer by plasma vapor deposition (PVD) on the surface of a Li foil is reported. The formation of a Li-rich alloy is confirmed by the volume expansion (up to 380%) of the layer and by the disappearance of metallic Sn peaks in the X-ray diffractogram. The layer has a much higher hardness than bare Li and can withstand aggressive cycling at 1C. Post-mortem scanning electron microscope observations revealed that the alloy layer remains intact even after fast cycling for hundreds of cycles. A concept of double modification by adding a thin ceramic/polymer layer deposited by a doctor blade on top of the LixSny layer was also reported to be efficient to reach long-term stability for 500 cycles at C/3. Finally, a post-treatment after Sn deposition consisting of a plasma cleaning of the LixSny alloy layer led to a strong improvement in the cycling performance at 1C. The surface is smoother and less oxidized after this treatment. The combination of a Li-rich alloy interlayer, the increase in hardness at the electrolyte/Li interface, and the absence of dissolution of the layer during cycling at high C-rates are reasons for such an improvement in electrochemical performance.

The role of protolith composition in the formation of tin-enriched granitic melts: A modeling study using the example of the southwest China tin province

Important features of Sn mineralization are the heterogeneous geographic distribution and frequent regional separation from W mineralization in spite some similarities of Sn and W behavior during magmatic processes. Major Sn and W mineralization is often spatially associated with peraluminous granites, which are derived from partial melting of metasediments. Several concepts have been suggested to explain those features, such as a weathering-related Sn-enriched source, Sn redistribution between melts and restite during protolith melting, and extensive fractional crystallization. We demonstrate the importance of protolith composition for the formation of Sn (and W) granites by using a comprehensive bulk-rock composition dataset from Precambrian metasediments of the South China Sn-W province and employing a thermodynamic modeling approach. We used four compositional proxies for phase equilibria calculations, which are the metasediments of the Mengdong, Sibao, Pingbian, and Shuangqiaoshan Groups. It is well documented that those Precambrian metasediments are important protoliths of Sn granites in South China. We present quantitative evaluation of the control of protolith composition in the generation of Sn-enriched granitic melts using South China as example, but our conclusions may also be applicable to worldwide Sn–enriched granites. Our results indicate that the protolith major-element geochemistry controls the anatectic reactions and melt productivity at specific melting conditions, and consequently the partitioning behavior of Sn. Further, pre-enrichment of Sn is crucial to the fertility of granitic melt and may be a prerequisite, particularly for the formation of giant Sn deposits. We propose that the heterogeneous distribution of favorable source rocks is one of the important factors that control the spatial distribution of major Sn (and W) districts in South China and other regions worldwide.

Influence of Nb substrate morphology and atomic structure on Sn nucleation and early Nb3Sn growth

The enhanced accelerating performance of Nb3Sn-coated Nb superconducting radio frequency (SRF) cavities is severely limited by quenching sites at material defects formed during the Nb3Sn film growth procedure. In this work, we aimed to understand the complex surface-mediated interactions that drive initial Nb3Sn formation during the Sn vapor deposition procedure used to fabricate Nb3Sn coated SRF cavities. Nb substrates were modified, coated with Sn, and then characterized using an ultra-high vacuum (UHV) chamber equipped with metal deposition and in situ surface analysis capabilities. The atomic structure of the Nb oxide surface was modified to assess how the Nb surface defect density and crystallographic orientation impact the size of nucleated Sn islands and relative Nb3Sn growth rates. Formed Nb3Sn/Nb surfaces were visualized using ex situ scanning electron microscopy (SEM) and post-deposition annealing revealed Sn desorption and Nb3Sn degradation pathways. Finally, we showed that the Sn deposition conditions can be modified to overcome the growth barriers that are imposed by the Nb morphology. This study provides a unique bridge between fundamental growth studies in pristine conditions with observed phenomena of Nb3Sn grown on realistic cavity surfaces.

Electrochemical preparation and characterization of a new configuration SnO2 anode and its application for treating petroleum refinery wastewater

In the present work, the feasibility of removing chemical oxygen demand (COD) from petroleum refiner wastewater (PRW) was examined through an anodic oxidation process using a SnO2-copper substrate anode in a prototype tubular batch electrochemical reactor. The SnO2 anode was prepared by cathodic deposition from a nitrate solution and characterized by techniques such as X-ray diffraction (XRD) and scanning electron microscopy (SEM). Effects of current density, [Sn2+]/[HNO3] molar ratio, and time on the properties of the prepared anode were investigated. The XRD results showed that main peaks corresponded to deposition of tetragonal SnO2. Besides, broad peeks were observed indicating that the deposits have a lower degree of crystallinity. The results confirmed that increasing current density higher than 10 mA/cm2 results in formation of a mixture of SnO2 and Sn deposits. Additionally, the results proved that [Sn2+]/[HNO3] molar ratio has the main effect on the electrodeposition process, where keeping this ratio lower than 0.33 is recommended to ensure pure SnO2 film deposition. The best conditions for electrodeposition of SnO2 as a compact film on a copper substrate were a current density of 10 mA/cm2, [Sn2+] of 25 mM, [HNO3] of 125 mM to make a molar ratio of 0.2, and 30 min to confirm the formation of deposits without cracks and having an atomic percent (Sn/O) of 20.6/65. The application of the prepared anode for removing of COD from PRW confirmed a good performance with a removal efficiency of 79 % at current density of 12 mA/cm2, pH of 7.8, and operating time of 150 min in which an energy consumption of 9.93 kWh/kg COD was required. The degradation of COD using the SnO2 electrode was found to obey a pseudo first-order kinetic. The application of anodic oxidation using the new configuration of the SnO2 anode can be considered an eco-friendly process for treating wastewater, featuring easy scale-up to an industrial scale at high removal efficiency and lower cost.

Geochronology and geochemistry of zircon and columbite–tantalite group minerals from the Weilasituo Sn–polymetallic deposit, northeastern China: Implications for the relationship between mineralization and the magmatic–hydrothermal transition

The Weilasituo Sn–polymetallic deposit, located in the southern portion of the Great Xing'an Range of Inner Mongolia, China, is a super-large Sn deposit associated with abundant Li, Rb, Nb, Ta, Zn, and Cu resources. Despite that previous studies have characterized the age, hydrothermal evolution, and genetic relationship between the alkali feldspar granite porphyry and associated Sn–polymetallic mineralization, the magmatic–hydrothermal evolution and ore–forming processes remain ambiguous. To address these ambiguities and bridge this knowledge gap, this contribution characterizes the texture, geochemistry, and U–Pb isotope composition of zircon and columbite–tantalite group minerals (CGMs) from amazonitized alkali feldspar granite (AMG) and albitized alkali feldspar granite (ABG) in the Weilasituo deposit. Type-I zircon (Zr1) is inclusion-poor, translucent, and is characterized by low light rare earth element (LREE) contents, high (Sm/La)N ratios (mean = 655.7), and low Th/U (mean = 0.21 < 0.3), Zr/Hf (mean = 5.46), and Y/Ho ratios (mean = 4.42), indicating that it formed during the magmatic–hydrothermal transition. Type-II zircon (Zr2) is inclusion-rich, porous, has a low CL response, and is characterized by low Th/U ratios (0.08–0.32, mean = 0.17), high LREE contents, weakly positive Ce anomalies, and low (Sm/La)N ratios (mean = 20.7), indicating that it formed via hydrothermal alteration of Zr1 (i.e., magmatic–hydrothermal zircon). Type-I CGM (CGM1) generally lacks oscillatory zoning, and has similar and positively correlated Ta/(Nb + Ta) and Mn/(Mn + Fe) values (AMG: R2 = 0.93; ABG: R2 = 0.75), indicative of a magmatic origin. Type-II CGMs (CGM2) occur as rims on CGM1 and are characterized by higher Ta/(Nb + Ta) and lower Nb/Ta ratios than CGM1, indicative of precipitation from a hydrosilicate liquid during the magmatic–hydrothermal transition. Based on the characteristics of CGMs, two stages are evident in the evolution of the Weilasituo granite porphyry: an earlier magmatic differentiation stage and a later magmatic–hydrothermal transition stage. Furthermore, the magmatic–hydrothermal transition stage can be subdivided into the AMG and ABG substages within the porphyry system based on petrological and mineralogical characteristics. The U–Pb ages for zircons and CGMs from the alkali feldspar granite porphyry range from 137.2 ± 2.0 Ma to 129.8 ± 1.4 Ma, without a notable age gap. The similarity in U–Pb ages between CGM1–CGM2 and Zr1–Zr2 indicates that the magmatic stage and the magmatic–hydrothermal transition at Weilasituo were continuous processes that occurred during the Early Cretaceous.

Zircon in tin granite as tracer for fluid metasomatism and Sn mineralization

Most tin deposits in the world are genetically related to tin granite and form during complex magmatic-hydrothermal processes. Zircon is a common accessory mineral in granite and related ore systems and can host a number of ore metals, such as Sn, W, Nb, Ta, U and Th, in its crystal lattice. However, whether metal enrichment/depletion can trace ore-forming processes is still unclear. Here, we report that the metal concentrations in various types of zircons from the Mopanshan tin granites in the southern Great Xing'an Range (Northern China) can be used as good indicators of fluid metasomatism and Sn mineralization. Two lithological zones are developed in the Mopanshan pluton, including porphyritic syenogranite (PG) in the center and fine-grained syenogranite (FG) at the margin. Zircons in the PG (PGZ-1, PGZ-2, and PGZ-3) are all magmatic in origin, while zircons in the FG can be categorized into magmatic zircons (FGZ-1 and FGZ-2) and metasomatic zircons (FGZ-3). The PGZ-1 and FGZ-1 grains are transparent prismatic crystals with bright oscillatory zonation, whereas the PGZ-2 grains are murky crystals with dark oscillatory zonation. PGZ-3 and FGZ-2 grains occur as overgrowths of previously formed zircon (PGZ-1, PGZ-2, and FGZ-1) or as brown individual crystals, showing dark and homogeneous cathodoluminescence (CL) textures. The metasomatic FGZ-3 grains are translucent-opaque porous crystals with vermicular CL zonation and commonly replace FGZ-2. The trace element compositions of magmatic zircons are completely melt controlled, providing a record of magmatic evolution as a constant decrease in Zr/Hf ratios and a gradual increase in Th, U, Nb, and Ta contents. Moreover, the structure of magmatic zircons transforms from a crystalline state to an amorphous state as a consequence of radioactive decay of U and Th. A coupled dissolution-reprecipitation process is proposed for the formation of metasomatic FGZ-3. The reactive fluid is the magmatic fluid that exsolved from the melt in the late magmatic stage. The magmatic fluid replaced biotite and rare earth phosphates (mainly monazite and apatite) enclosed within biotite, resulting in significant amounts of Nb, Ta, Sn, P, Al, Ca, Fe, and REEs, which subsequently reacted with the FGZ-2 zircons to leach Th, U, Y, and HREEs. Eventually, REEs, Y, Th, and U in the fluid combined with P to form monazite and xenotime, while the other elements partially precipitated with the crystallization of the FGZ-3 zircons. Although the alteration of biotite only released approximately 190 ppm of Sn into the fluid, this is still a significant Sn source for the Sn deposits surrounding the Mopanshan pluton, taking the granite size (∼50 km2) and the volume proportion of biotite (∼5%) into account. Furthermore, based on previous studies on tourmaline from the Mopanshan granite and regional geochemistry, it may be inferred that the addition of wall rock components may also play an important role in Sn mineralization.

Origin of fluids in the Lancangjiang tin belt, southwestern Yunnan Province, China: Evidence from trace element and boron isotopic compositions of tourmaline

The Lancangjiang tin belt is located on the eastern margin of the Tibetan Plateau, which is in the northern part of the Southeast Asian tin belt that contains Sn, W, and base metal ore deposits. Tourmaline alteration and high B contents are typical features of the magmatic–hydrothermal systems in the Lancangjiang tin belt. Our new data for tourmaline intergrown with cassiterite reveal complex geochemical features that provide important insights into the origins of ore-forming fluids in this B-rich tin belt. Most of the tourmaline in the Sn deposits and metamorphic rocks belongs to the alkali-group dravite series, except for some that is part of the X-vacant group. The tourmaline compositions differ among the ore districts, but all exhibit Fe-poor (0.61–1.08 apfu) and Mg-rich (1.43–2.06 apfu) compositions, with Fe/(Fe + Mg) = 0.18–0.46. Most trace elements in the tourmaline occur at low contents (<50 ppm), including the large-ion lithophile elements (e.g., Cs and Ba) and high-field-strength elements (e.g., Nb, Ta, Hf, and Th). However, some trace elements (e.g., Zn, Sr, and V) and Sn have high contents (up to several hundreds or thousands of ppm). The δ11B values of tourmaline from the Sn deposits range from −14.7 ‰ to −11.3 ‰, except for those in the Man Makhsan Sn deposit, which range from −12.0 ‰ to −8.1 ‰. The δ11B values (−14.7 ‰ to −8.1 ‰) and the positive correlation between Sn contents and Nb/Ta, Al/Ga, and K/Cs ratios in the ore-related tourmaline indicate that the exsolved ore-forming fluids were derived from highly fractionated S − type granitic magmas. The fluids were mainly B-, Sn-, and Al-enriched. The low Fe/(Mg + Fe) ratios, high oxygen fugacity, and Al saturation were favorable for cassiterite precipitation, and are proxies for the ore-forming potential of large-scale Sn deposits.

Unravelling the deposition of Zn and Sn as corrosion inhibitor on aluminum (Al) surface for Al-air battery application with sodium chloride electrolytes

Recently, Aluminum (Al) has been extensively developed as an anode material for Al-air batteries. High corrosion rate and slow kinetic reactions of Al in anode application drive the recent research to coat with other more noble metals. Therefore, the primary objective of this work is identifying the effect of zinc (Zn) and tin (Sn) coating on high purity Al surface for electrochemical properties improvement. The employed method of metal oxide coating was electrodeposition process. The structural and morphological of electrodeposition was investigated by scanning electron microscopy (SEM). The surface of Zn-Al was finer than Sn–Al. Additionally, the observed cracks on the surface were analyzed and interpreted as indicative of mixed metal oxide (MMO) coating behavior. In electrochemical performance, the Zn–Al half-cell exhibits a consistent open circuit potential value of −0.94 V. This value is the most stable compared with other variables. Remarkably, the discharge time that represents full-cell of Zn–Al and N-doped carbon-based cathode performance was about 14 h, which is nearly fourteen orders compared with Al variables that can only sustain in an hour. The electrodeposition also contributes to enhancing the specific capacity from 40.763 m Ah g−1 to become 324.627 mAh g−1. In line with other measurements, the corrosion rate with linear polarization measurement placed Zn–Al with the smallest corrosion rate, that is 3.71 × 10-5 mm/year. All the electrochemical measurements used 3.5 % NaCl as the model of seawater electrolytes. This finding could be a reliable option of aluminum air battery development on larger scale in the future.

Crater-free monolayer graphene above the 2D Si film on SiC(0001) formed via SiSn cointercalation and Sn deintercalation

When Si atoms are intercalated under the graphene-like zero layer (ZL) generated on the SiC(0001) substrate, the resulting quasi-free-standing monolayer graphene (QFMLG) has lots of crater-like defects due to a strong Si-C reaction. Here, a method for creating crater-free QFMLG above a two-dimensional Si film is investigated using scanning tunneling microscopy and photoemission spectroscopy. The method involves forming a SiSn interfacial film as a precursor via cointercalation performed by sequential Sn and Si deposition on the ZL at room temperature and annealing at 650–700 °C. The Sn atoms prevent reactive Si atoms from directly contacting the ZL, which would otherwise cause SiC defects. The sample is then annealed at 750 °C to selectively remove the Sn atoms from the SiSn interfacial film, leaving a well-ordered Si film. The SiSn film composed of a bottom Si layer and top Sn atoms has a short-range-ordered “2 × 2” or a long-range-ordered 2×7 superstructure depending on the annealing temperature and the Sn coverage. Both the superstructures are semiconducting and induce less n-doped QFMLG than the pure Si film.

Tin (Sn) Geochemical Mapping Based on a Fixed-Value Method: A Case Illustration in Gejiu Area, Southwest China

Geochemical maps play an important role in mineral resource exploration. There are three traditional methods for creating geochemical maps: the cumulative frequency method, the logarithmic interval method, and the Avg±k∗Std (where Avg and Std are the abbreviations of average and standard deviation, and k is a multiple of Std) method. However, with the increasing scope of the study area and cumulative data, the limitations of traditional methods, which depend on the amount of data, are exposed. A fixed-value method for Sn geological mapping is proposed to overcome the limitations of traditional methods. In the fixed-value method, Sn concentrations are divided into 19 levels on 18 fixed values ranging from 1 μg/g (corresponding to the detection limit) to 1000 μg/g (corresponding to the cut-off grade of Sn in hard rocks). The 19 levels are mapped in six color tones. The first to fifth levels are the lowest background areas in blue tones, which correspond to Sn concentrations ranging from the minimum to 3.4 μg/g. The sixth to ninth levels are high background areas in yellow tones corresponding to concentrations less than 10 μg/g, the 10th to 12th are low anomaly areas in pink tones less than 28 μg/g, the 13th to 15th are high anomaly areas in red tones less than 200 μg/g (corresponding to the placer cut-off grade), the 16th to 18th in gray tones less than 1000 μg/g, and the 19th level is in black corresponding to Sn ores with Sn concentration not less than 1000 μg/g. The fixed-value method along with three traditional methods was used to contour the Sn geochemical maps in the Gejiu area in Southwest China. The illustration results of the presented fixed-value method and three traditional methods for geochemical mapping of Sn are all feasible for Sn deposit exploration in the Gejiu area, Southwest China. Compared to traditional methods, the presented fixed-value method overcomes the flaws of traditional methods and is also more meaningful in geochemistry.

Surface Modification of Bi2Te3 Nanoplates Deposited with Tin, Palladium, and Tin/Palladium Using Electroless Deposition

Surface-modified nanoplate-shaped thermoelectric materials can achieve good thermoelectric performance. Herein, single-crystalline Bi2Te3 nanoplates with regular hexagonal shapes were prepared via solvothermal techniques. Surface modification was performed to deposit different metals onto the nanoplates using electroless deposition. Nanoparticle-shaped tin (Sn) and layer-shaped palladium (Pd) formed on the Bi2Te3 nanoplates via electroless deposition. For the sequential deposition of Sn and Pd, the surface morphology was mostly the same as that of the Sn-Bi2Te3 nanoplates. To assess the thermoelectric properties of the nanoplates as closely as possible, they were compressed into thin bulk shapes at 300 K. The Sn-Bi2Te3 and Sn/Pd-Bi2Te3 nanoplates exhibited the lowest lattice thermal conductivity of 1.1 W/(m·K), indicating that nanoparticle-shaped Sn facilitated the scattering of phonons. By contrast, the Pd-Bi2Te3 nanoplates exhibited the highest electrical conductivity. Thus, the highest power factor (15 μW/(m∙K2)) and dimensionless ZT (32 × 10−3) were obtained for the Pd-Bi2Te3 nanoplates. These thermoelectric properties were not as high as those of the sintered Bi2Te3 samples; however, this study revealed the effect of different metal depositions on Bi2Te3 nanoplates for improving thermoelectric performance. These findings offer venues for improving thermoelectric performance by sintering nanoplates deposited with appropriate metals.