Search Results (24)

The Dajing giant Cu–Sn polymetallic deposit is located in the Cu–Sn–Ag–Pb–Zn polymetallic belt of the southern Great Xing’an Range, NE China. Research on its ore genesis is of great significance for understanding Sn polymetallic mineralization in this region. In this study, pyrite, arsenopyrite, and sphalerite were analyzed by electron-microprobe analysis (EMPA) and in situ S–Pb isotope analysis. Previously published fluid-inclusion microthermometric and H–O isotope data were also incorporated to constrain fluid evolution and ore genesis. Both in situ S and Pb isotopic compositions fall within short ranges. The δ³⁴S values suggest a sulfur reservoir with possible magmatic contribution, whereas Pb isotopes indicate a mainly crustal Pb signature in an orogenic setting. Arsenopyrite records variations in As, S, Fe, and Co contents from core to rim. The Co-rich core shows Co enrichment accompanied by Fe depletion, consistent with Co-for-Fe isomorphous substitution. These features indicate changes in local fluid chemistry during arsenopyrite growth. Sulfur isotope geothermometry based on coexisting late-stage pyrite–sphalerite pairs yields 118–233 °C, with an average of 159 ± 49 °C, indicating medium- to low-temperature hydrothermal activity during the late sulfide stage. The Dajing deposit is interpreted as a fault-controlled hydrothermal vein-type Cu–Sn polymetallic deposit formed in a Late Jurassic extensional setting. Ore precipitation was likely promoted by cooling during upward fluid migration away from the magmatic heat source, pressure release, meteoric-water mixing, and fluid–rock interaction with granitic rocks and Linxi Formation wall rocks. This study provides mineral-scale constraints on fluid evolution and ore genesis in the Great Xing’an metallogenic belt. Full article

Zinc oxide (ZnO), silver (Ag) and titanium dioxide (TiO₂) nanoparticles (NPs), are three of the most widely manufactured NPs, while composite NPs have gained popularity due to their enhanced properties. NP release in environmental matrices increases chances of bioavailability and subsequent impact on human health. The current study focuses on manufacturing, characterization and cyto-genotoxic assessment of Ag, ZnO/Ag, TiO₂ and TiO₂/Ag NPs with and without humic acids (HAs), aiming for a holistic approach that leads to a comprehensive profile of said NPs. It entails (a) the synthesis of the aforementioned NPs via single-nozzle Flame Spray Pyrolysis (SN-FSP); (b) the characterization of NPs (in powder form and in dispersion media) using Powder X-ray Diffraction (PXRD), Transmission Electron Microscopy (TEM) and Dynamic Light Scattering (DLS); and (c) the assessment of their genotoxicity and cytotoxicity against human lymphocytes in presence of two HAs, thus simulating actual environmental conditions, and without HAs, through the cytokinesis block micronucleus assay (CBMN) with cytochalasin-B. No genotoxicity was observed in any case, whereas cytotoxicity induction varied depending on the NP and the presence or absence of the two HAs. Therefore, it is indispensable to evaluate the toxic profile of NPs considering different environmental scenarios, while conducting an integrated characterization of NPs. Full article

High-altitude mine wastelands in Southwest China present formidable challenges for ecological rehabilitation due to extreme climatic stressors and multi-element contamination. Ecological restoration is closely related to soil environment. However, the mechanism by which parent material-induced heterogeneity governs spontaneous vegetation succession is still poorly understood. We established 36 plots (216 quadrats) to investigate the soil physical and chemical properties and vegetation restoration of propylite, porphyry and siltstone in the Xifanping Copper Mine, Sichuan Province. Furthermore, fifteen metal/metalloid elements (Au, Ag, Mo, W, Cu, Pb, Zn, Hg, As, U, Se, Cr, Sn, Ti, Total Fe₂O₃), soil pollution and vegetation structure were evaluated. The study area exhibited severe composite pollution (mean Nemerow integrated pollution index = 8.09), primarily driven by Au, Ag, Mo, W, and Cu. Vegetation surveys identified 34 vascular plant species from 12 families. Propylite-derived substrates supported significantly higher species richness, Shannon–Wiener diversity, and soil organic matter than porphyry and siltstone. Redundancy analysis (RDA) identified soil organic matter (SOM) and bulk density (BD) as dominant environmental filters, with SOM explaining 14.03% of community variance (p < 0.01). Two native pioneers, Potentilla supina and Cynoglossum wallichii, were identified as specialized uranium (U) accumulators with bioconcentration factors of 13.39 and 4.49, respectively. Lithological inheritance dictates early successional trajectories by influencing edaphic structure and nutrient bioavailability. The identified U-accumulating species provide a valuable genetic resource for implementing Assisted Natural Regeneration (ANR) and developing sustainable phytoremediation strategies in contaminated alpine ecosystems. Full article

The six platinum group elements (PGE) are among the rarest elements in the upper continental crust of the earth. Higher values of PGE have been detected in the upper mantle and in chondrite meteorites. The PGE are siderophile and chalcophile elements and are divided into the following: (1) the Ir subgroup (IPGE) = Os, Ir, and Ru and (2) the Pd subgroup (PPGE) = Rh, Pt, and Pd. The IPGE are more refractory and less chalcophile than the PPGE. High concentrations of PGE led, in rare cases, to the formation of mineral deposits. The PGE are carried in discrete phases, the platinum group minerals (PGM), and are included as trace elements into the structure of base metal sulphides (BM), such as pentlandite, chalcopyrite, pyrite, and pyrrhotite. Similarly to PGE, the PGM are also divided into two main groups, i.e., IPGM composed of Os, Ir, and Ru and PPGM containing Rh, Pt, and Pd. The PGM occur both in mafic and ultramafic rocks and are mainly hosted in stratiform reefs, sulphide-rich lenses, and placer deposits. Presently, there are only 169 valid PGM that represent about 2.7% of all 6176 minerals discovered so far. However, 496 PGM are listed among the valid species that have not yet been officially accepted, while a further 641 are considered as invalid or discredited species. The main reason for the incomplete characterization of PGM resides in their mode of occurrence, i.e., as grains in composite aggregates of a few microns in size, which makes it difficult to determine their crystallography. Among the PGM officially accepted by the IMA, only 13 (8%) were discovered before 1958, the year when the IMA was established. The highest number of PGM was discovered between 1970 and 1979, and 99 PGM have been accepted from 1980 until now. Of the 169 PGM accepted by the IMA, 44% are named in honour of a person, typically a scientist or geologist, and 31% are named after their discovery localities. The nomenclature of 25% of the PGM is based on their chemical composition and/or their physical properties. PGM have been discovered in 25 countries throughout the world, with 64 from Russia, 17 from Canada and South Africa (each), 15 from China, 12 from the USA, 8 from Brazil, 6 from Japan, 5 from Congo, 3 from Finland and Germany (each), 2 from the Dominican Republic, Greenland, Malaysia, and Papua New Guinea each, and only 1 from Argentine, Australia, Bulgaria, Colombia, Czech Republic, England, Ethiopia, Guyana, Mexico, Serbia, and Tanzania each. Most PGM phases contain Pd (82 phases, 48% of all accepted PGM), followed, in decreasing order of abundances, by those of Pt 35 phases (21%), Rh 23 phases (14%), Ir 18 phases (11%), Ru 7 phases (4%), and Os 4 phases (2%). The six PGE forming the PGM are bonded to other elements such as Fe, Ni, Cu, S, As, Te, Bi, Sb, Se, Sn, Hg, Ag, Zn, Si, Pb, Ge, In, Mo, and O. Thirty-two percent of the 169 valid PGM crystallize in the cubic system, 17% are orthorhombic, 16% hexagonal, 14% tetragonal, 11% trigonal, 3% monoclinic, and only 1% triclinic. Some PGM are members of a solid-solution series, which may be complete or contain a miscibility gap, providing information concerning the chemical and physical environment in which the mineral was formed. The refractory IPGM precipitate principally in primitive, high-temperature, mantle-hosted rocks such as podiform and layered chromitites. Being more chalcophile, PPGE are preferentially collected and concentrated in an immiscible sulphide liquid, and, under appropriate conditions, the PPGM can precipitate in a thermal range of about 900–300 °C in the presence of fluids and a progressive increase of oxygen fugacity (fO₂). Thus, a great number of Pt and Pd minerals have been described in Ni-Cu sulphide deposits. Two main genetic models have been proposed for the formation of PGM nuggets: (1) Detrital PGM represent magmatic grains that were mechanically liberated from their primary source by weathering and erosion with or without minor alteration processes, and (2) PGM reprecipitated in the supergene environment through a complex process that comprises solubility, the leaching of PGE from the primary PGM, and variation in Eh-pH and microbial activity. These two models do not exclude each other, and alluvial deposits may contain contributions from both processes. Full article

The corrosion behaviors of newly developed solder alloys with excellent mechanical properties, Sn-2.5 Ag-1.0 Bi-0.8 Cu-0.05 Ni (SABC25108N) and Sn-1.5 Bi-0.75 Cu-0.065 Ni (SBC15075N), are analyzed to supplement the corrosion behavior of the limited corrosion data in Pb- and Zn-free solder compositions. A potentiodynamic polarization test is conducted on these compositions in a NaCl electrolyte solution, the results of which are compared with those of conventional Sn-3.0 (wt%) Ag-0.5Cu and Sn-1.2Ag-0.5Cu-0.05Ni alloys. The results indicate that SBC15075N exhibits the lowest corrosion potential and highest corrosion current density, thus signifying the lowest corrosion resistance. By contrast, SABC25108N exhibits the lowest corrosion current density and highest corrosion resistance. Notably, SABC25108N shows a slower corrosion progression in the active state and exhibits the longest passive state. The difference in corrosion resistance is affected more significantly by the formation and distribution of the Ag₃Sn intermetallic compound phase owing to the high Ag content instead of by the presence of Bi or Ni. This uniform dispersion of Ag₃Sn IMC phases in the SABC25108N alloy effectively suppressed corrosion propagation along the grain boundaries and reduced the formation of corrosion products, such as Sn₃O(OH)₂Cl₂, thereby enhancing the overall corrosion resistance. These findings provide valuable insights into the optimal design of solder alloys and highlight the importance of incorporating sufficient Ag content into multicomponent compositions to improve corrosion resistance. Full article

Unlike municipal solid waste bottom ash (MSWBA), fly ash (MSWFA) is landfilled due to its toxicity. However, MSWFA may also be a source of elements. Ash samples collected from a Portuguese MSW incinerator from different locations and over six months were analyzed. Their geochemical composition was normalized to the upper continental crust (UCC) and compared since metal enrichment may be used as an indicator for potential recovery. The potential recovery economic viability was also assessed for metals K, Sb, Cu, Pb, and Zn, considering the ore cut-off grade and minimum industrial grade (MIG) from Chinese geological and mineral industry standards. Compared to the global samples, only the Baghouse 1 FA size fraction’s coarse fraction showed a slight enrichment (1- to 5-fold) in Bi, Nb, and Zr. After wet sieving, most trace elements were enriched in all fractions, but Sb, Bi, Pb, Zn, Ag, As, Cd, Sn, Se, and Hg were depleted in the coarse fractions and enriched in the fine ones. For Baghouse 1 samples collected over 6 months, the normalization to the UCC showed enrichment of Zn and Pb between 10× and 50×, Zr, Cu, In, and Se between 50× and 100×, and Ag, Mn, Cd, Sb, and Bi at more than 100×. Over six months, the Baghouse 1 FA soluble fraction ranged between 21 wt.% and 30 wt.%, and its precipitates comprised 27% CaO, 6% Na₂O, and 9% K₂O. The K concentration in the MSWFA was above the cut-off and the MIG, and K could be concentrated in precipitates via simple washing. Full article

Ag-based electrical contact materials are essential in low-voltage devices such as relays, switches, circuit breakers, and contactors. Historically, Ag-CdO composites have been preferred due to their superior electrical and thermal conductivities, resistance to arcing, and mechanical strength. However, the toxicity of Cd has led to increased restrictions on its use. With the aim of contributing to the development of a new environment-friendly, Ag-Zn₂SnO₄-based electrical contact material, the kinetics of the hot mechanochemical oxidation of a Ag-Sn-Zn solid solution obtained by mechanical alloying were investigated. The results indicated that the proposed synthesis route produces Ag-based composites with a homogeneous distribution of nanoscale Zn₂SnO₄ precipitates, which is unattainable through conventional material processing methods. This kinetic study established that the mechanochemical oxidation of the Ag-Sn-Zn solid solution follows the Johnson–Mehl–Avrami–Kolmogorov model. An analysis of the microstructure and the relationship between the activation energy “Ea” and the Avrami exponent “n” from experimental data fitting suggests that the primary mechanism for the oxidation of the Ag-Sn-Zn solid solution during the hot mechanochemical process is related to the three-dimensional oxide growth being limited by oxygen diffusion after its immediate initial nucleation. Full article

Intermetallic compounds (IMCs) growth can simultaneously bring about low-resistance electrical pathways and drastically reduce joint lifetime. Recently, incorporated trace nanoparticles into the free-Pb solder were found to promote the performance of the solder joints. Sn3Ag0.9Zn (SAZ) nano-composite solders were developed by doping 0.5 wt.% Al₂O₃ nanoparticles into the SAZ solder. The IMCs formation and growth behavior at the interfacial reactions between the SAZ-0.5Al₂O₃ nano-composite solder and the Cu substrate during soldering at temperatures ranging from 250 to 325 °C for 30 min were investigated. The results showed that after the addition of Al₂O₃ nanoparticles into the SAZ solder, the elongated-type IMCs layer changed into a prism-type IMCs layer, and Ag₃Sn nanoparticles were absorbed on the grain surface of the interfacial Cu₆Sn₅ phase, effectively suppressing the growth of the IMCs layers. The activation energies (Q) for the IMCs layers (Cu₆Sn₅ + Cu₃Sn) were determined to be 36.4 and 39.1 kJ/mol for the SAZ/Cu and SAZ-Al₂O₃/Cu solders, respectively. Full article

The Baoshan Cu-Pb-Zn deposit is situated at the intersection of the Qin-Hang Cu polymetallic and Nanling W-Sn polymetallic metallogenic belts. The age, lithology, petrogenesis, and tectonic setting of granodiorite porphyry within the deposit remain subjects of debate. Additionally, there is a lack of comparative studies with the W-Sn-related granites in the region. This study conducted whole-rock major and trace element analysis, Sr-Nd isotope analysis, and zircon U-Pb dating on the Baoshan granodiorite porphyry. The zircon U-Pb age of the granodiorite porphyry is 162 ± 1 Ma. The whole-rock SiO₂ and K₂O contents range from 65.87 to 68.21 wt.% and 3.42 to 5.62 wt.%, respectively, indicating that the granodiorite porphyry belongs to high-potassium calc-alkaline I-type granite. The granodiorite porphyry is characterized by enrichment in LREE and depletion in HREE (LREE/HREE ratio = 6.2–21.2). The samples of granodiorite porphyry generally exhibit weak negative Eu anomalies or no Eu anomalies (δEu = 0.62–1.04, mean = 0.82). The (⁸⁷Sr/⁸⁶Sr)_i and ε_Nd(t) values are 0.707717–0.709506 and −7.54 to −4.87, respectively. The whole-rock geochemical composition and Sr-Nd isotopic values indicate that the magma originated from the partial melting of the Mesoproterozoic ancient crust and Neoproterozoic mafic juvenile lower crust, with the addition of high oxygen fugacity and water-rich lithospheric mantle melts. The source of the granodiorite porphyry in the Baoshan deposit is significantly different from the crust-derived metapelite source of the W-Sn-related granite in the area, indicating that different magma sources might be the main reason for the co-spatial and nearly contemporaneous development of Cu-Pb-Zn and W-Sn mineralization in the southern Hunan region. Full article

Due to the continuous miniaturization and high current-carrying demands in the field of integrated circuits, as well as the desire to save space and improve computational capabilities, there is a constant drive to reduce the size of integrated circuits. However, highly integrated circuits also bring about challenges such as high current density and excessive Joule heating, leading to a series of reliability issues caused by electromigration. Therefore, the service reliability of integrated circuits has always been a concern. Sn-based solders are widely recognized in the industry due to their availability, minimal technical issues during operation, and good compatibility with traditional solders. However, solders that are mostly Sn-based, such as SAC305 and SnZn, have a high melting point for sophisticated electronic circuits. When Bi is added, the melting point of the solder decreases but may also lead to problems related to electromigration reliability. This article reviews the general principles of electromigration in SnBi solder joints on Cu substrates with current flow, as well as the phenomena of whisker formation, voids/cracks, phase separation, and resistance increase caused by atomic migration due to electromigration. Furthermore, it explores methods to enhance the reliability of solder joint by additives including Fe, Ni, Ag, Zn, Co, RA (rare earth element), GNSs (graphene nanosheets), FNS (Fullerene) and Al₂O₃. Additionally, modifying the crystal orientation within the solder joint or introducing stress to the joint can also improve its reliability to some extent without changing the composition conditions. The corresponding mechanisms of reliability enhancement are also compared and discussed among the literature. Full article

The Pusangguo deposit (1.42 Mt @ 1.42% Cu, 0.14 Mt @ 1.82% Zn, 0.08 Mt @ 1.01% Pb, and 285.8 t Co @ 140 g/t Co) is the first Co-rich Cu-Zn-Pb skarn deposit discovered in the Gangdese metallogenic belt. However, the trace and minor element geochemistry of the sulfides in this deposit has not been studied, limiting further understanding of elements’ occurrence and mineralization. Here, we identified four ore stages, and two types of sphalerites (SpI and SpII) and pyrites (PyI and PyII), in this deposit. In this study, LA-ICP-MS in-situ trace element analyses were conducted on sphalerite and pyrite, to obtain their chemical compositions, elemental substitution mechanisms, and mineralization physicochemical conditions. The results indicate that two types of sphalerites are generally more enriched with Co than pyrite. SpI has higher concentrations of Co, Cr, Cu, Ag, and As compared to SpII. Both types of sphalerite have very low contents of Sn, Ge, and Ga. PyII has higher contents of most trace elements, such as Co, Ni, Mn, Zn, Cu, As, Sn, Se, Pb, Ag, and Bi, compared to PyI. Both types of pyrite are poor in Mn, Ga, Ge, and Cd, but enriched in As, Co, and Ni. The Mn, Fe, Co, and Cd in sphalerite, and Co, Ni, and Mn in pyrite are generally lattice-bound, while Cu, As, Ag, and Sb are usually present in both micro-inclusions and coupled substitution. Significant elemental correlations in sphalerite indicate the possible substitution mechanisms 2Fe²⁺ + Ga²⁺ ↔ 3Zn²⁺, 2Fe²⁺ + Ge⁴⁺ ↔ 4Zn²⁺, and (Sb³⁺, Sn³⁺) + (Cu⁺, Ag⁺) ↔ 2Zn²⁺. The correlation trends between trace elements in pyrite suggest the coupled substitution mechanisms of (Tl⁺ + Cu⁺ + Ag⁺) + (As³⁺ + Sb³⁺) ↔ 2Zn²⁺ and As³⁺ + Cu⁺ ↔ 2Zn²⁺. The mineralization temperature at Pusangguo, as determined by the GGIMFis sphalerite geothermometer, is 237–345 °C (avg. 307 °C), consistent with the high Zn/Cd ratio (avg. 203), low Ga/In (avg. 0.06), and high In/Ge (avg. 15.9) in sphalerite, and high Co/Ni ratio (avg. 24) in pyrite. These results indicate that the ore-forming fluid was high-temperature, with a low sulfur fugacity (fS₂) (10^−13.4 to 10^−8.3) and low oxygen fugacity (fO₂). The high temperature, and low sulfur fugacity and oxygen fugacity of the ore-forming fluid, and the fluid-mixing process, jointly controlled the sulfide precipitation, which caused the formation of the Pusangguo deposit. Full article

The Qiandongshan–Dongtangzi large Pb-Zn deposit is located in the Fengxian–Taibai (abbr. Fengtai) polymetallic orefield. The ore bodies primarily occur within and around the contact surface between the limestone of the Gudaoling Formation and the phyllite of the Xinghongpu Formation, which are clearly controlled by anticline and specific lithohorizon. Magmatic rocks are well developed in the mining area, consisting mainly of granitoid plutons and mafic–felsic dikes. Previous metallogenic geochronology studies have yielded a narrow range of ages between 226 and 211 Ma, overlapped by the extensive magmatism during the Late Triassic period in this region. The ω(Co)/ω(Ni) ratio of pyrite in lead–zinc ore ranges from 4.44 to 15.57 (avg. 8.56), implying that its genesis is probably related to volcanic and magmatic-hydrothermal fluids. The δD and δ¹⁸O values (ranging from −94.2‰ to −82‰, and 18.89‰ to 20.72‰, respectively,) of the ore-bearing quartz indicate that the fluids were perhaps derived from a magmatic source. The δ³⁴S values of ore-related sulfides display a relatively narrow range of 4.29‰ to 9.63‰ and less than 10‰, resembling those of magmatic-hydrothermal origin Pb-Zn deposits. The Pb isotopic composition of the sulfides from the Qiandongshan–Dongtangzi Pb-Zn deposit (with ²⁰⁶Pb/²⁰⁴Pb ratios of 18.06 to 18.14, the ²⁰⁷Pb/²⁰⁴Pb ratios of 15.61 to 15.71, and ²⁰⁸Pb/²⁰⁴Pb ratios of 38.15 to 38.50) is similar to that of the Late Triassic Xiba granite pluton, suggesting that they share the same Pb source. The contents of W, Mo, As, Sb, Hg, Bi, Cd, and other elements associated with magmatic-hydrothermal fluids are high in lead–zinc ores, and the contents of Sn, W, Co, and Ni are also enriched in sphalerite. The contents of trace elements and rare earth elements in the ore are similar to those in the Xiba granite pluton, and they maybe propose a magmatic-hydrothermal origin as well. As a result of this information, the Qiandongshan–Dongtangzi large Pb-Zn deposit may be classified as a magmatic hydrothermal stratabound type, with the Si/Ca contact area being the ore-forming structural plane. Thus, a mineralization model has been proposed based on a comparative analysis of the geological and geochemical properties of the lead–zinc deposit in the Fengtai orefield. It is considered that the secondary anticlines developed on both wings of the Qiandongshan–Dongtangzi composite anticline are the favorable sites for Pb-Zn deposition. Accordingly, the Si/Ca plane and secondary anticline are the major ore-controlling factors and prospecting targets. The verification project was first set up on the north wing of the composite anticline, and thick lead–zinc ore bodies were found in all verification boreholes, accumulating successful experience for deep exploration of lead–zinc deposits in this region. Full article

This study investigated the synthesis of Ag-SnO₂-ZnO by powder metallurgy methods and their subsequent electrical contact behavior. The pieces of Ag-SnO₂-ZnO were prepared by ball milling and hot pressing. The arc erosion behavior of the material was evaluated using homemade equipment. The microstructure and phase evolution of the materials were investigated through X-ray diffraction, energy-dispersive spectroscopy and scanning electron microscopy. The results showed that, although the mass loss of the Ag-SnO₂-ZnO composite (9.08 mg) during the electrical contact test was higher than that of the commercial Ag-CdO (1.42 mg), its electrical conductivity remained constant (26.9 ± 1.5% IACS). This fact would be related to the reaction of Zn₂SnO₄’s formation on the material’s surface via electric arc. This reaction would play an important role in controlling the surface segregation and subsequent loss of electrical conductivity of this type of composite, thus enabling the development of a new electrical contact material to replace the non-environmentally friendly Ag-CdO composite. Full article

To explore the source of Pb in Bronze Age artefacts from the Central Plains (Zhongyuan) in China, we investigated non-ferrous minerals from the Qingyuan archaeological site in Yuanqu County near the Zhongtiao Mountains. Fragments of smelting slag from the Erlitou cultural layer were collected. The smelting slag was investigated by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and lead isotope analysis. The SEM and EDS results confirmed that the slag contained Pb, Pb–As, and Cu–Pb–Sn inclusions and non-metal impurities such as low-Zn spinels. The XRD results signified that the bulk of the slag comprised Fe–Mn–Si phases. The chemical state of Pb was mainly Pb–O with some metallic Pb, as identified by XPS. The theoretical melting point was calculated using FactSage7.1 based on the composition and phase characterisation. The calculated temperature was 1100–1200 °C, which agreed well with the actual melting point of 1114–1354 °C. The slag composition and inclusion phases indicated that Pb–Zn–O ores with Mn and As were added during reduction smelting in Qingyuan. The raw materials of smelting included crude Pb with minor amounts of Cu, As, and Sn. Lead isotope analysis revealed that the lead materials produced in Qingyuan were likely transferred to Yanshi City in the Shang Dynasty. The findings of this study provide significant clues for exploring lead mineral production in the Central Plains during the Early Bronze Age. Full article

Kesterite Cu₂ZnSnS₄ (CZTS) thin films using various 1,8-diiodooctane (DIO) polymer additive concentrations were fabricated by the electrochemical deposition method. The optical, electrical, morphological, and structural properties of the CZTS thin films synthesized using different concentrations of 5 mg/mL, 10 mg/mL, 15 mg/mL, and 20 mg/mL were investigated using different techniques. Cyclic voltammetry exhibited three cathodic peaks at −0.15 V, −0.54 V, and −0.73 V, corresponding to the reduction of Cu²⁺, Sn²⁺, Sn²⁺, and Zn²⁺ metal ions, respectively. The analysis of the X-ray diffraction (XRD) pattern indicated the formation of the pure kesterite crystal structure, and the Raman spectra showed pure CZTS with the A1 mode of vibration. Field emission scanning electron microscopy (FE-SEM) indicated that the films are well grown, with compact, crack-free, and uniform deposition and a grain size of approximately 4 µm. For sample DIO-20 mg/mL, the elemental composition of the CZTS thin film was modified to Cu:Zn:Sn: and S = 24.2:13.3:12.3:50.2, which indicates a zinc-rich and copper-poor composition. The X-ray photoelectron spectroscopy (XPS) results confirmed the existence of Cu, Sn, Zn, and S elements and revealed the element oxidation states. The electrochemical deposition synthesis increased the absorption of the CZTS film to more than 10⁴ cm⁻¹ with a band gap between 1.62 eV and 1.51 eV. Finally, the photovoltaic properties of glass/CZTS/CdS/n-ZnO/aluminum-doped zinc oxide (AZO)/Ag solar cells were investigated. The best-performing photovoltaic device, with a DIO concentration of 20 mg/mL, had a short-circuit current density of 16.44 mA/cm², an open-circuit voltage of 0.465 V, and a fill factor of 64.3%, providing a conversion efficiency of 4.82%. Full article