The rapid development of novel energy materials has led to a sustained surge in the global demand for fluorine.Fluorite is the primary source of fluorine globally and is increasingly being exploited.The estimated annu...The rapid development of novel energy materials has led to a sustained surge in the global demand for fluorine.Fluorite is the primary source of fluorine globally and is increasingly being exploited.The estimated annual production of fluorite worldwide is approximately 8 million tons,with an additional 5 million tons of fluorite tailings.This accumulation not only consumes land resources,but also contributes to dust generation and F-percolation,leading to water and air contamination.This paper comprehensively reviews the utilization methods of fluorite tailings,including the flotation recovery of quartz and fluorite,the preparation of cement mineralizing agents,and the preparation of concrete mineral additives,autoclaved lime sand brick,and glass-ceramics.Furthermore,potential future applications and research directions are proposed,including the comprehensive recovery of valuable minerals,auxiliary cementitious materials preparation,and the functionalization of glass-ceramics.This study can serve as a reference for expediting the utilization of fluorite tailings,promoting the development of tailing-free mines,and establishing sustainable development strategies.展开更多
The increasing global demand for clean and potable water underscores the need for advanced pollutant remediation technologies in wastewater,such as the degradation of azo dyes,which are known to be harmful to human he...The increasing global demand for clean and potable water underscores the need for advanced pollutant remediation technologies in wastewater,such as the degradation of azo dyes,which are known to be harmful to human health.To address this issue,heterogeneous photocatalysis emerges as a promising strategy for breaking down recalcitrant molecules.However,efforts are required to develop efficient and stable photocatalysts capable of operating under visible light.This study explores the photocatalytic potential of Fe-doped RE_(2)Zr_(2)O_(7-δ)(RE=Pr,Sm,Nd,Y)compositions,synthesized through the microwaveassisted solvothermal method,for the degradation of methylene blue.Characterizations,such as X-ray diffraction(XRD)and Raman spectroscopy,reveal the obtention of single-phase ordered pyrochlore for RE=Pr,Sm and Nd or defect fluorite structures for Y.Photocatalytic tests under visible light demonstrate efficient dye degradation for all Fe-doped samples,Y_(2)Zr_(1.9)Fe_(0.1)O_(6.95)(YZF)defect fluorite being the one that exhibits the highest efficiency.Radical scavenging experiments identify hydroxyl radicals as key contributors to the degradation process,along with photoinduced holes.These materials exhibit minimal leaching of iron ions,confirming their stability,and the best material,YZF,demonstrates effective reusability.The results highlight the potential of Fe-doped RE_(2)Zr_(2)O_(7)compositions as an efficient alternative for application as photocatalysts for the degradation of azo dyes under visible light.展开更多
Flotation separation of calcite from fluorite is a challenge on low-grade fluorite flotation that limits the recovery and purity of fluorite concentrate.A new acid leaching–flotation process for fluorite is proposed ...Flotation separation of calcite from fluorite is a challenge on low-grade fluorite flotation that limits the recovery and purity of fluorite concentrate.A new acid leaching–flotation process for fluorite is proposed in this work.This innovative process raised the fluor-ite’s grade to 97.26wt%while producing nanoscale calcium carbonate from its leachate,which contained plenty of calcium ions.On the production of nanoscale calcium carbonate,the impacts of concentration,temperature,and titration rate were examined.By modifying the process conditions and utilizing crystal conditioning agents,calcite-type and amorphous calcium carbonates with corresponding particle sizes of 1.823 and 1.511μm were produced.The influence of the impurity ions Mn^(2+),Mg^(2+),and Fe^(3+)was demonstrated to reduce the particle size of nanoscale calcium carbonate and make crystal shape easier to manage in the fluorite leach solution system compared with the calcium chloride solution.The combination of the acid leaching–flotation process and the nanoscale calcium carbonate preparation method improved the grade of fluorite while recovering calcite resources,thus presenting a novel idea for the effective and clean usage of low-quality fluorite resources with embedded microfine particles.展开更多
Anisotropic surface broken bond densities of six different surfaces of calcite and three surfaces of fluorite were calculated. In terms of the calculated results, the commonly exposed surfaces of the two minerals were...Anisotropic surface broken bond densities of six different surfaces of calcite and three surfaces of fluorite were calculated. In terms of the calculated results, the commonly exposed surfaces of the two minerals were predicted and the relations between surface broken bonds densities and surface energies were analyzed. Then the anisotropic wettability of the commonly exposed surfaces was studied by means of contact angle measurement. The calculation results show that the （101^-4）, （213^-4）and （01 1^-8）surfaces for calcite and （111） for fluorite are the most commonly exposed surfaces and there is a good rectilinear relation between surface broken bond density and surface energy with correlation of determination （R^2） of 0.9613 and 0.9969, respectively. The anisotropic wettability of different surfaces after immersing in distilled water and sodium oleate solutions at different concentrations can be explained by anisotropic surface broken bond densities and active Ca sites densities, respectively.展开更多
Round Top Mountain in Hudspeth County, west Texas, USA is a surface-exposed rhyolite intrusion enriched in Y and heavy rare earth elements （HREEs）, as well as Nb, Ta, Be, Li, F, Sn, Rb, Th, and U. The massive tonnag...Round Top Mountain in Hudspeth County, west Texas, USA is a surface-exposed rhyolite intrusion enriched in Y and heavy rare earth elements （HREEs）, as well as Nb, Ta, Be, Li, F, Sn, Rb, Th, and U. The massive tonnage, estimated at well over 1 billion tons, of the deposit makes it a target for recovery of valuable yttrium and HREEs （YHREEs）, and possibly other scarce ele-ments. Because of the extremely fine grain size of the mineralized rhyolite matrix, it has not been clear which minerals host the YHREEs and in what proportions. REE-bearing minerals reported in the deposit included bastn？site-Ce, Y-bearing fluorite, xeno-time-Y, zircon, aeschynite-Ce, a Ca-Th-Pb fluoride, and possibly ancylite-La and cerianite-Ce. Extended X-ray absorption fine struc-ture （EXAFS） indicated that virtually all of the yttrium, a proxy for the HREEs, resided in a coordination in the fluorite-type crystal structure, rather than those in the structures of bastn？site-Ce and xenotime-Y. The YREE grade of the Round Top deposit was just over 0.05%, with 72%of this consisting of YHREEs. This grade was in the range of the South China ionic clay deposits that supply essentially all of the world’s YHREEs. Because the host Y-bearing fluorite is soluble in dilute sulfuric acid at room temperature, a heap leaching of the deposit appeared feasible, aided by the fact that 90%-95%of the rock consists of unreactive and insoluble feld-spars and quartz. The absence of overburden, remarkable consistency of mineralization grade throughout the massive rhyolite, prox-imity （a few km） to a US interstate highway, major rail systems and gas and electricity, temperate climate, and stable political location in the world’s largest economy all enhanced the potential economic appeal of Round Top.展开更多
The demand for fluorite resource is increasing rapidly as most fluorite deposits on Earth’s surface have been exhausted.The newly discovered fluorite deposits in Inner Mongolia are hosted by Permian metamorphosed san...The demand for fluorite resource is increasing rapidly as most fluorite deposits on Earth’s surface have been exhausted.The newly discovered fluorite deposits in Inner Mongolia are hosted by Permian metamorphosed sandy slate,intermediate-acid intrusive rocks and Cretaceous volcanic sedimentary rocks.The ore bodies are strictly controlled by faults and buried by cover rocks.The feasibility and effectiveness of multi-techniques for prospecting concealed fluorite ore bodies are evaluated,and 10 anomalies are delineated.On the basis of geological features and effectiveness of different methods,the optimum combinations of ore prospecting techniques are proposed for the exploration of zonal type and burial type concealed fluorite ore bodies.Based on comprehensive researches,an integrated exploration model is proposed:(i)select key prospecting targets based on geological backgrounds,regional geochemical anomalies of F and Ca,and remote sensing images;(ii)identify the spatial distribution of low resistivity anomaly and ore-controlling structure from geophysical survey;(iii)evaluate the mineralization potential in fault zone based on F and Ca anomalies in key sections selected from low resistivity anomaly zones;and(iv)evaluate the mineralization potential and reveal the spatial distribution of fluorite ore bodies and ore-controlling faults based on integrated geophysical and geochemical anomalies.The integrated exploration model is verified to be a powerful tool for prospecting concealed fluorite ore bodies in coverage area.展开更多
For the first time, fluid-melt inclusions are found in fluorite of the Huanggangliang skarn iron-tin deposit (HSID). The fluorite was formed in the main stage of mineralization, named the hydro-skarnization stage. The...For the first time, fluid-melt inclusions are found in fluorite of the Huanggangliang skarn iron-tin deposit (HSID). The fluorite was formed in the main stage of mineralization, named the hydro-skarnization stage. The inclusions contain various components such as Fe, Mg and Cr from deep sources. The melts of primary inclusions are mainly Ca- and F-rich and those of secondary inclusions tend to become Si-rich. During this evolution process, the melts and iron daughter minerals decreased and even vanished. These facts reveal that the evolution of the primary mineralizing fluids and the differentiation of the fluids and melts are the main factors leading to the deposition of Fe, Sn and other elements. This discovery confirms the magmatic genesis of the HSID and has filled in the gaps in the research of magmatogenic skarn deposits and furnished new methods for such research. Furthermore, it has enlarged the scope of the research on fluid inclusions.展开更多
The mechanism of phthalic acid,a dicarboxylic acid collector,in flotation separation of fluorite and rare earth(RE)was studied in this paper.The experimental data of flotation show that phthalic acid,as the collector,...The mechanism of phthalic acid,a dicarboxylic acid collector,in flotation separation of fluorite and rare earth(RE)was studied in this paper.The experimental data of flotation show that phthalic acid,as the collector,can realize highly efficient separation of fluorite and rare earth under weakly acidic conditions.The adsorption mechanism of phthalic acid on the surface of fluorite and bastnaesite was analyzed in this paper by means of the zeta potential measurement,the Fourier transform infrared(FT-IR),the X-ray photoelectron spectroscopy(XPS)and the stability constant measurement of active metal ion and phthalic acid coo rdination complex.According to the zeta potential testing results,the surfaces of fluorite adsorb the collector phthalate ion with negative charge under weakly acidic conditions which,in turn,increases its electronegativity and results in the motion of its potential.After the reaction between phthalic acid and fluorite ores under weakly acidic conditions,the peak of the fluorite ores is found to have significant changes in the FT-IR results,indicating strong chemical adsorption on the surfaces of phthalic acid and fluorite ores.According to the XPS analysis,the peak of benzene ring of phthalic acid is as high as 2%on the surface of fluorite,while no obvious characteristic peak of benzene ring is found on the surface of bastnaesite.According to the pH potentiometric titration results,the stability constant Ktotal of calcium phthalate complex within the acid range is higher than the stability constant K’total of cerium phthalate complex,indicating that the complex generated between phthalic acid and Ca^(2+)is more stable than the complex generated between phthalic acid and Ce^(3+).The possible reason is that Ca^(2+),with the highest reticular density,plays a prevailing role in the octahedron structure of fluorite amidst the acidic media.As the active point of flotation,Ca^(2+)works with the carboxyl groups of the collector phthalic acid(-C=O-)to form polycyclic calcium phthalate complex.展开更多
The co-reduction roasting and grinding-magnetic separation of seaside titanomagnetite and blast furnace dust was investigated with and without fluorite addition at a reduction roasting temperature of 1250°C for 6...The co-reduction roasting and grinding-magnetic separation of seaside titanomagnetite and blast furnace dust was investigated with and without fluorite addition at a reduction roasting temperature of 1250°C for 60 min, a grinding fineness of-43 μm accounting for 69.02 wt% of the total, and a low-intensity magnetic field strength of 151 kA/m. The mineral composition, microstructure, and state of the roasted products were analyzed, and the concentrations of CO and CO_2 were analyzed in the co-reduction roasting. Better results were achieved with a small fluorite dosage(≤4 wt%) in the process of co-reduction. In addition, F^- was found to reduce the melting point and viscosity of the slag phase because of the high content of aluminate and silicate minerals in the blast furnace dust. The low moisture content of the blast furnace dust and calcic minerals inhibited the hydrolysis of CaF_2 and the loss of F^-. Compared with the blast furnace dust from Chengdeng, the blast furnace dusts from Jiugang and Jinxin inhibited the diffusion of F-when used as reducing agents, leading to weaker effects of fluorite.展开更多
The surface properties of fluorite are often affected by dissolved gangue species(e.g.,calcite)during the flotation process.Microflotation testing with and without the addition of calcite supernatant was conducted usi...The surface properties of fluorite are often affected by dissolved gangue species(e.g.,calcite)during the flotation process.Microflotation testing with and without the addition of calcite supernatant was conducted using octanohydroxamic acid(OHA)as the collector.The results revealed that dissolved calcite species significantly affected the flotation behavior of fluorite.Fourier transform infrared spectra confirmed that the decrease in flotation recovery was linked to lower OHA adsorption.Solution chemistry analysis indicated that CaCO_(3) and Ca^(2+)from the calcite supernatant were the most favorably adsorbed species,and X-ray photoelectron spectroscopy analysis confirmed the surface adsorption of calcite species.Density functional theory simulations provided a detailed analysis of the multidentate adsorption configuration of OHA,which was the most favorable for adsorption on the fluorite surface.The adsorption energy calculation showed that the calcite dissolved species were more stably adsorbed on the fluorite surface than OHA.The pre-adsorption of calcite dissolved species hindered the adsorption of OHA due to electrostatic repulsion.展开更多
High-temperature solid-state electrolyte is a key component of several important electrochemical devices,such as oxygen sensors for automobile exhaust control,solid oxide fuel cells(SOFCs) for power generation,and sol...High-temperature solid-state electrolyte is a key component of several important electrochemical devices,such as oxygen sensors for automobile exhaust control,solid oxide fuel cells(SOFCs) for power generation,and solid oxide electrolysis cells for H_(2) production from water electrolysis or CO_(2) electrochemical reduction to value-added chemicals.In particular,internal diffusion of protons or oxygen ions is a fundamental and crucial issue in the research of SOFCs,hypothetically based on either oxygen-ionconducting electrolytes or proton-conducting electrolytes.Up to now,some electrolyte materials based on fluorite or perovskite structure were found to show certain degree of dual-ion transportation capability,while in available electrolyte database,particularly in the field of SOFCs,such dual-ion conductivity was seriously overlooked.Actually,few concerns arising to the simultaneous proton and oxygen-ion conductivities in electrolyte of SOFCs inevitably induce various inadequate and confusing results in literature.Understanding dual-ion transportation behavior in electrolyte is indisputably of great importance to explain some unusual fuel cell performance as reported in literature and enrich the knowledge of solid state ionics.On the other hand,exploration of novel dual-ion conducting electrolytes will benefit the development of SOFCs.In this review,we provide a comprehensive summary of the understanding of dual-ion transportation in solid electrolyte and recent advances of dual-ion conducting SOFCs.The oxygen ion and proton conduction mechanisms at elevated temperature inside oxide-based electrolyte materials are first introduced,and then(mixed) oxygen ion and proton conduction behaviors of fluorite and perovskite-type oxides are discussed.Following on,recent advances in the development of dual-ion conducting SOFCs based on fluorite and perovskite-type single-phase or composite electrolytes,are reviewed.Finally,the challenges in the development of dual-ion conducting SOFCs are discussed and future prospects are proposed.展开更多
A series of compositionally complex fluorite oxides(CCFOs)were prepared by ball milling the mixture of ZrO_(2),HfO_(2),Y_(2)O_(3),La_(2)O_(3),and Pr_(6)O_(11)followed by conventional solid-state sintering.Both XRD and...A series of compositionally complex fluorite oxides(CCFOs)were prepared by ball milling the mixture of ZrO_(2),HfO_(2),Y_(2)O_(3),La_(2)O_(3),and Pr_(6)O_(11)followed by conventional solid-state sintering.Both XRD and TG-DSC results demonstrated that single-phase(Zr_(0.2)Hf_(0.2)Pr_(0.2)Y_(0.2)La_(0.2))O_(2-)δwas formed at 1400°C.Elements in bulk ceramic were uniformly distributed without evident accumulation according to SEM-EDS pictures.TEM results revealed that polycrystalline ceramic powder was assignable to cubic Fm-3m fluorite structure.The electrical conductivity(σ)was measured via EIS technology and activation energy(E_(a))of CCFOs was calculated in Arrhenius plots.In the temperature range of 300-750°C,CCFOs preserved the same conduction mechanism and(Zr_(0.1667)Hf_(0.1667)Pr_(0.1667)Y_(0.25)La_(0.25))O_(2-)δpossessed higherσand lower E_(a) than other high entropy fluorite oxides which is related to the incorporation of Pr element or the connection of cation-V_(o) complex.展开更多
Fluorite is one of the main gangue minerals in the Maoniuping REE deposit, Sichuan Province, China. Fluorite with different colors occurs not only within various orebodies, but also in wallrocks of the orefield. Based...Fluorite is one of the main gangue minerals in the Maoniuping REE deposit, Sichuan Province, China. Fluorite with different colors occurs not only within various orebodies, but also in wallrocks of the orefield. Based on REE geochemistry, fluorite in the orefleld can be classified as the LREE-rich, LREE-flat and LREE-depleted types. The three types of fluorite formed at different stages from the same hydrothermal fluid source, with the LREE-rich fluorite forming at the relatively early stage, the LREE-flat fluorite in the middle, and the LREE-depleted fluorite at the latest stage. Various lines of evidence demonstrate that the variation of the REE contents of fluorite shows no relation to the color. The mineralization of the Maouiuping REE deposit is associated spatially and temporally with carbonatite-syenite magmatism and the ore-forming fluids are mainly derived from carbonatite and syenite melts.展开更多
Up to now, there were no systematic studies of geochemistry and isotopic age for the Yixian （义县） fluorite deposit, western Liaoning （辽宁） Province, China. Based on the analysis of metallogenic geological settin...Up to now, there were no systematic studies of geochemistry and isotopic age for the Yixian （义县） fluorite deposit, western Liaoning （辽宁） Province, China. Based on the analysis of metallogenic geological setting, we studied the REE, Rb-Sr and Sm-Nd isotopes. The chondrite-normalized REE patterns of fluorite are characterized by moderate LREE depletion （LREE/HREE=0.95-3.57, （La/Yb）N=0.08-2.84） and enrichment of Sr （146×10^-6-596×10^-6） and moderately positive Eu anomalies （δEu=1.10-1.34）, which are similar to those of the host Mesoproterozoic carbonate rocks. The fluorite display （^87Sr/^86Sr）t=-0.708 5, （^143Nd/^144Nd）t=-0.511 785, and δNd（t）=-12.8, which are similar to those of the host Mesoproterozoic carbonate rocks and volcanic rocks of Middle Jurassic Lanqi （蓝旗） Formation. The REE and Sr-Nd isotope geochemistry suggest that the source of the ore-forming material may be the volcanic rocks of Lanqi Formation and host carbonate rocks. The Sm-Nd isochron age of 154±14 Ma （MSWD=0.23） indicates that the Yixian fluorite mineralization nearly corresponds to the period of Lanqi Formation. Based on the integrated geological and geochemical studies, coupled with previous studies, we suggest that Yixian fluorite deposit formed in the extension setting of postcoilisional stage and may be attributed to the partial melting of ancient basaltic rocks in the lower crust induced by underplating of basic magma and to the reaction between the F-rich ore-forming fluids and the host carbonate rocks.展开更多
Fluorite mineralization occurs along fractures and cracks of Middle Eocene and Pliocene limestones and marls in the north and northeast of the P?hrenk region (?i?ekdagi, Kirsehir). Tb/Ca – Tb/La and Y/Ho ratios were ...Fluorite mineralization occurs along fractures and cracks of Middle Eocene and Pliocene limestones and marls in the north and northeast of the P?hrenk region (?i?ekdagi, Kirsehir). Tb/Ca – Tb/La and Y/Ho ratios were obtained from REE contents of fluorites which have revealed that mineralization is of hydrothermal type. Negative Ce anomalies and positive Eu anomalies reflect that hydrothermal solutions once had high oxygen fugacity. Fluid inclusion studies indicate that homogenization temperatures of mineralization varied between 90°C and 200°C, and hydrothermal solutions are composed of NaCl + KCl + MgCl2 + H2O. In addition, salinity measurements show that hydrothermal solutions were mixed with meteoric or rock formation water. Geologic setting, REE geochemistry and fluid inclusion studies suggest that mineralization was deposited from a solution generated by mixing of magmatic and meteoric water under epithermal conditions.展开更多
Fluorite is one of the important mineral raw materials in the industry.In China,it is mainly distributed in the provinces and regions such as Hunan,Zhejiang,Jiangxi,Inner Mongolia,Fujian,and Henan provinces,boasting h...Fluorite is one of the important mineral raw materials in the industry.In China,it is mainly distributed in the provinces and regions such as Hunan,Zhejiang,Jiangxi,Inner Mongolia,Fujian,and Henan provinces,boasting huge reserves and large numbers of deposits.However,most of the fluorite deposits are on a small or medium scale.The main fluorite deposits in China were studied in this paper.Their geological features and metallogenic regularity were summarized and compared.Meanwhile,based on their main genetic factors including metallogenic fluid sources and main metallogenic geological processes,they were divided into two groups,namely meso-epithermal deposits and magmatic-hydrothermal deposits.Furthermore,based on the prospecting achievements and research progress obtained in fluorite deposits in recent years,prospecting potential predictions were made for the metallogenic prospect areas and major prospecting areas of fluorite in China.This aims to provide a theoretical basis and direction for future fluorite prospecting in China.展开更多
Based on material design idea,we employ a co-precipitation strategy to obtain sinterable Ho_(2)Zr_(2)O_(7) flu-orite particles,successfully leading to novel transparent Ho_(2)Zr_(2)O_(7) ceramics with good optical/mag...Based on material design idea,we employ a co-precipitation strategy to obtain sinterable Ho_(2)Zr_(2)O_(7) flu-orite particles,successfully leading to novel transparent Ho_(2)Zr_(2)O_(7) ceramics with good optical/magneto-optical properties.The resulting precipitation precursor is identified to be hydrated basic carbonate upon calcination at the optimum temperature of 1250℃into near-spherical Ho_(2)Zr_(2)O_(7) nanopowder with an average size of~64 nm and unimodal narrow size distribution.The crystal intrinsic oxygen defect in fluorite ceramic generally exists in the form of F+center.The best bulk specimen achieved in this work exhibits a high refractive index of~2.1 and a high transparency of~74.4%at 1000 nm comparable with the corresponding defect-free single crystal(~76.4%in theory).In the Ho_(2)Zr_(2)O_(7) structure system,the elec-tronic polarizability of O_(2)-anion generally remains constant around 2.2?3 in the visible region and the corresponding optical basicity is approximately 0.9.The developed magneto-optical transparent Ho_(2)Zr_(2)O_(7) ceramic has Verdet constants of-180±3,-157±5,-87±2,-54±2,and-43±2 rad T^(-1) m^(-1) at 515,635,780,980,and 1064 nm,respectively,which are roughly 1.2-fold higher than the commercial TGG crystal.展开更多
In order to fill up the deficiency of the theoretical basis about fluoride formation during Bayan Obo iron concentrate roasting process, the thermodynamic conditions of the interactivity between the components of the ...In order to fill up the deficiency of the theoretical basis about fluoride formation during Bayan Obo iron concentrate roasting process, the thermodynamic conditions of the interactivity between the components of the gangue and calcium fluorite were studied by means of thermodynamic calculation, DTA-TG thermal analysis and XRD characterization. The results revealed that KF, NaF and SiF4 （gaseous） could he,formed during the roasting process, and the tendency of the generation of KF is greater than that of NaF or SiF4 in standard state. Besides, the results of roasting experiments showed that the products of KCaCO3 F and KCaF3 formed in the temperature range of 800-1250 ℃and KF appears when the roasting temperature was higher than 1250 ℃ in K2O-CaF2 system. For the Na2O-CaF2 system, the product of NaF appears at temperature higher than 1050 ℃. The formation reaction of gaseous SiF4 with solid phase CaO · SiO2 in SiO2-CaF2 system took place＂only＇at temperature higher than 1 150 ℃. In the natural potash feldspar-CaF2-CaO system, the fluorination reaction products involved KF at temperature higher than 1 270 ℃ , while in the natural aegirine-CaF2-CaO system, NaF formed at terhperature higher than 980 ℃ during roasting process.展开更多
The Baoshan Cu–Pb–Zn deposit, located in the central part of the Qin–Hang belt in South China, is closely related to the granodiorite-porphyry. However, the characteristics and the source of the ore-forming fluid a...The Baoshan Cu–Pb–Zn deposit, located in the central part of the Qin–Hang belt in South China, is closely related to the granodiorite-porphyry. However, the characteristics and the source of the ore-forming fluid are still ubiquitous. According to the crosscutting relationships between veinlets and their mineral assemblages, three stages of hydrothermal mineralization in this deposit were previously distinguished. In this contribution, two different colored fluorites from the major sulfide mineralization stage are recognized:(1) green fluorites coexisting with Pb–Zn ores;and(2) violet fluorites coexisting with pyrite ores. Y/Ho ratios verify the green fluorites and violet fluorites were co-genetic. The fluorites display elevated(La/Yb)Nratios, which decrease from 1201 to 5710 for green fluorites to 689–1568 for violet fluorites, indicating that they precipitated at the early hydrothermal sulfide stage,and Pb–Zn ores crystallized earlier than pyrite ores. The similar Tb/La ratios of the fluorites also indicate that they precipitated at an early stage within a short time. From the green fluorites to violet fluorites, the total rare earth element(ΣREE)concentrationsdecreasefrom1052–1680 ppm to 148–350 ppm, indicating that the green fluorites precipitated from a more acidic fluid. The Eu/Eu*ratios increase from 0.17 to 0.30 for green fluorites to0.29–0.48 for violet fluorites, and the Ce/Ce* ratios decrease from 1.08–1.13 to 0.93–1.11, suggesting a gradual increase in oxygen fugacity(fO_(2)) and pH value of the mineralization fluid. Though the fluorites display similar REE patterns to the granodiorite-porphyry and limestone,the ΣREE concentrations of the fluorites are significantly higher than those of limestone and the granodiorite-porphyry, suggesting that an important undetected non-magmatic source is involved to provide sufficient REE for fluorites. The most plausible mechanism is fluid mixing between magma fluid and an undetected non-magmatic fluid.展开更多
The Bamianshan fluorite deposit is a super-large one recently discovered in Zhejiang Province of China. This paper presents an analysis of its geological background, orebody and ore characteristics, petrochemical char...The Bamianshan fluorite deposit is a super-large one recently discovered in Zhejiang Province of China. This paper presents an analysis of its geological background, orebody and ore characteristics, petrochemical characteristics of host rocks, rare earth elements （REE） of rocks and ores, fluid inclusions in fluorite and Sm-Nd isotopic features in an effort to study its sedimentary mineralization. The result shows that the super-large Bamianshan fluorite deposit is of hydrothermal sedimentation genesis, deformed by the later hydrothermal fluid. Integrated with host rocks and orebody characteristics, it is inferred that the deposit originates from the Cambrian sedimentary rocks. And the later magmatic activities deformed some orebodies in different degrees, forming steeply dipping vein orebodies in the tectonic belts regionally.展开更多
基金supported by the National Key Research and Development Program of China(No.2023YFC3903901)the Key Research and Development Program of Hubei Province,CHina(No.2022BAA029)the Science and Technology Project of Shaanxi Yanchang Petroleum(Group)Co.,Ltd.,China(No.yc-whlg-2023ky-03).
文摘The rapid development of novel energy materials has led to a sustained surge in the global demand for fluorine.Fluorite is the primary source of fluorine globally and is increasingly being exploited.The estimated annual production of fluorite worldwide is approximately 8 million tons,with an additional 5 million tons of fluorite tailings.This accumulation not only consumes land resources,but also contributes to dust generation and F-percolation,leading to water and air contamination.This paper comprehensively reviews the utilization methods of fluorite tailings,including the flotation recovery of quartz and fluorite,the preparation of cement mineralizing agents,and the preparation of concrete mineral additives,autoclaved lime sand brick,and glass-ceramics.Furthermore,potential future applications and research directions are proposed,including the comprehensive recovery of valuable minerals,auxiliary cementitious materials preparation,and the functionalization of glass-ceramics.This study can serve as a reference for expediting the utilization of fluorite tailings,promoting the development of tailing-free mines,and establishing sustainable development strategies.
基金Project supported by the Spanish Government and the Ministerio de Ciencia e Innovacion(PID2020-116149 GB-I00)Generalitat Valenciana(GRISOLIA/2019/054)the Brazilian National Council for Scientific and Technological Development(306567/2021-0)。
文摘The increasing global demand for clean and potable water underscores the need for advanced pollutant remediation technologies in wastewater,such as the degradation of azo dyes,which are known to be harmful to human health.To address this issue,heterogeneous photocatalysis emerges as a promising strategy for breaking down recalcitrant molecules.However,efforts are required to develop efficient and stable photocatalysts capable of operating under visible light.This study explores the photocatalytic potential of Fe-doped RE_(2)Zr_(2)O_(7-δ)(RE=Pr,Sm,Nd,Y)compositions,synthesized through the microwaveassisted solvothermal method,for the degradation of methylene blue.Characterizations,such as X-ray diffraction(XRD)and Raman spectroscopy,reveal the obtention of single-phase ordered pyrochlore for RE=Pr,Sm and Nd or defect fluorite structures for Y.Photocatalytic tests under visible light demonstrate efficient dye degradation for all Fe-doped samples,Y_(2)Zr_(1.9)Fe_(0.1)O_(6.95)(YZF)defect fluorite being the one that exhibits the highest efficiency.Radical scavenging experiments identify hydroxyl radicals as key contributors to the degradation process,along with photoinduced holes.These materials exhibit minimal leaching of iron ions,confirming their stability,and the best material,YZF,demonstrates effective reusability.The results highlight the potential of Fe-doped RE_(2)Zr_(2)O_(7)compositions as an efficient alternative for application as photocatalysts for the degradation of azo dyes under visible light.
基金supported by the National Key Research Center and Development Program of the 14th Five-Year Plan,China(No.2022YFC2905105)National Natural Science Foundation of China(Nos.52122406 and 52004337)+2 种基金Hunan High-tech Industry Technology Innovation Leading Plan,China(No.2022GK4056)Hunan Innovative Province Construction Special Project,China(No.2020RC3001)Hunan Postgraduate Research and Innovation Project,China(No.CX20220200).
文摘Flotation separation of calcite from fluorite is a challenge on low-grade fluorite flotation that limits the recovery and purity of fluorite concentrate.A new acid leaching–flotation process for fluorite is proposed in this work.This innovative process raised the fluor-ite’s grade to 97.26wt%while producing nanoscale calcium carbonate from its leachate,which contained plenty of calcium ions.On the production of nanoscale calcium carbonate,the impacts of concentration,temperature,and titration rate were examined.By modifying the process conditions and utilizing crystal conditioning agents,calcite-type and amorphous calcium carbonates with corresponding particle sizes of 1.823 and 1.511μm were produced.The influence of the impurity ions Mn^(2+),Mg^(2+),and Fe^(3+)was demonstrated to reduce the particle size of nanoscale calcium carbonate and make crystal shape easier to manage in the fluorite leach solution system compared with the calcium chloride solution.The combination of the acid leaching–flotation process and the nanoscale calcium carbonate preparation method improved the grade of fluorite while recovering calcite resources,thus presenting a novel idea for the effective and clean usage of low-quality fluorite resources with embedded microfine particles.
基金Project (50834006) supported by the National Natural Science Foundation of ChinaProject (CX2011B122) supported by Hunan Provincial Innovation Foundation for PostgraduateProject (2011ybjz045) supported by Graduate Degree Thesis Innovation Foundation of Central South University
文摘Anisotropic surface broken bond densities of six different surfaces of calcite and three surfaces of fluorite were calculated. In terms of the calculated results, the commonly exposed surfaces of the two minerals were predicted and the relations between surface broken bonds densities and surface energies were analyzed. Then the anisotropic wettability of the commonly exposed surfaces was studied by means of contact angle measurement. The calculation results show that the （101^-4）, （213^-4）and （01 1^-8）surfaces for calcite and （111） for fluorite are the most commonly exposed surfaces and there is a good rectilinear relation between surface broken bond density and surface energy with correlation of determination （R^2） of 0.9613 and 0.9969, respectively. The anisotropic wettability of different surfaces after immersing in distilled water and sodium oleate solutions at different concentrations can be explained by anisotropic surface broken bond densities and active Ca sites densities, respectively.
基金Project supported by Research Contracts 26-8211-12 and 26-8211-16 between Texas Rare Earth Resources,Inc.and the University of Texas at El Paso
文摘Round Top Mountain in Hudspeth County, west Texas, USA is a surface-exposed rhyolite intrusion enriched in Y and heavy rare earth elements （HREEs）, as well as Nb, Ta, Be, Li, F, Sn, Rb, Th, and U. The massive tonnage, estimated at well over 1 billion tons, of the deposit makes it a target for recovery of valuable yttrium and HREEs （YHREEs）, and possibly other scarce ele-ments. Because of the extremely fine grain size of the mineralized rhyolite matrix, it has not been clear which minerals host the YHREEs and in what proportions. REE-bearing minerals reported in the deposit included bastn？site-Ce, Y-bearing fluorite, xeno-time-Y, zircon, aeschynite-Ce, a Ca-Th-Pb fluoride, and possibly ancylite-La and cerianite-Ce. Extended X-ray absorption fine struc-ture （EXAFS） indicated that virtually all of the yttrium, a proxy for the HREEs, resided in a coordination in the fluorite-type crystal structure, rather than those in the structures of bastn？site-Ce and xenotime-Y. The YREE grade of the Round Top deposit was just over 0.05%, with 72%of this consisting of YHREEs. This grade was in the range of the South China ionic clay deposits that supply essentially all of the world’s YHREEs. Because the host Y-bearing fluorite is soluble in dilute sulfuric acid at room temperature, a heap leaching of the deposit appeared feasible, aided by the fact that 90%-95%of the rock consists of unreactive and insoluble feld-spars and quartz. The absence of overburden, remarkable consistency of mineralization grade throughout the massive rhyolite, prox-imity （a few km） to a US interstate highway, major rail systems and gas and electricity, temperate climate, and stable political location in the world’s largest economy all enhanced the potential economic appeal of Round Top.
基金supported by the Fundamental Research Funds for the Central Universities(No.2652019191)China Geological Survey(No.1212011120187)the National Natural Science Foundation of China(No.41502347)。
文摘The demand for fluorite resource is increasing rapidly as most fluorite deposits on Earth’s surface have been exhausted.The newly discovered fluorite deposits in Inner Mongolia are hosted by Permian metamorphosed sandy slate,intermediate-acid intrusive rocks and Cretaceous volcanic sedimentary rocks.The ore bodies are strictly controlled by faults and buried by cover rocks.The feasibility and effectiveness of multi-techniques for prospecting concealed fluorite ore bodies are evaluated,and 10 anomalies are delineated.On the basis of geological features and effectiveness of different methods,the optimum combinations of ore prospecting techniques are proposed for the exploration of zonal type and burial type concealed fluorite ore bodies.Based on comprehensive researches,an integrated exploration model is proposed:(i)select key prospecting targets based on geological backgrounds,regional geochemical anomalies of F and Ca,and remote sensing images;(ii)identify the spatial distribution of low resistivity anomaly and ore-controlling structure from geophysical survey;(iii)evaluate the mineralization potential in fault zone based on F and Ca anomalies in key sections selected from low resistivity anomaly zones;and(iv)evaluate the mineralization potential and reveal the spatial distribution of fluorite ore bodies and ore-controlling faults based on integrated geophysical and geochemical anomalies.The integrated exploration model is verified to be a powerful tool for prospecting concealed fluorite ore bodies in coverage area.
文摘For the first time, fluid-melt inclusions are found in fluorite of the Huanggangliang skarn iron-tin deposit (HSID). The fluorite was formed in the main stage of mineralization, named the hydro-skarnization stage. The inclusions contain various components such as Fe, Mg and Cr from deep sources. The melts of primary inclusions are mainly Ca- and F-rich and those of secondary inclusions tend to become Si-rich. During this evolution process, the melts and iron daughter minerals decreased and even vanished. These facts reveal that the evolution of the primary mineralizing fluids and the differentiation of the fluids and melts are the main factors leading to the deposition of Fe, Sn and other elements. This discovery confirms the magmatic genesis of the HSID and has filled in the gaps in the research of magmatogenic skarn deposits and furnished new methods for such research. Furthermore, it has enlarged the scope of the research on fluid inclusions.
基金Project supported by the National Natural Science Foundation of China(51634005,51564042)Inner Mongolia Autonomous Region Natural Science Foundation(2014ZD04.2016ZD05)。
文摘The mechanism of phthalic acid,a dicarboxylic acid collector,in flotation separation of fluorite and rare earth(RE)was studied in this paper.The experimental data of flotation show that phthalic acid,as the collector,can realize highly efficient separation of fluorite and rare earth under weakly acidic conditions.The adsorption mechanism of phthalic acid on the surface of fluorite and bastnaesite was analyzed in this paper by means of the zeta potential measurement,the Fourier transform infrared(FT-IR),the X-ray photoelectron spectroscopy(XPS)and the stability constant measurement of active metal ion and phthalic acid coo rdination complex.According to the zeta potential testing results,the surfaces of fluorite adsorb the collector phthalate ion with negative charge under weakly acidic conditions which,in turn,increases its electronegativity and results in the motion of its potential.After the reaction between phthalic acid and fluorite ores under weakly acidic conditions,the peak of the fluorite ores is found to have significant changes in the FT-IR results,indicating strong chemical adsorption on the surfaces of phthalic acid and fluorite ores.According to the XPS analysis,the peak of benzene ring of phthalic acid is as high as 2%on the surface of fluorite,while no obvious characteristic peak of benzene ring is found on the surface of bastnaesite.According to the pH potentiometric titration results,the stability constant Ktotal of calcium phthalate complex within the acid range is higher than the stability constant K’total of cerium phthalate complex,indicating that the complex generated between phthalic acid and Ca^(2+)is more stable than the complex generated between phthalic acid and Ce^(3+).The possible reason is that Ca^(2+),with the highest reticular density,plays a prevailing role in the octahedron structure of fluorite amidst the acidic media.As the active point of flotation,Ca^(2+)works with the carboxyl groups of the collector phthalic acid(-C=O-)to form polycyclic calcium phthalate complex.
基金financially supported by the National Natural Science Foundation of China (No. 51474018)
文摘The co-reduction roasting and grinding-magnetic separation of seaside titanomagnetite and blast furnace dust was investigated with and without fluorite addition at a reduction roasting temperature of 1250°C for 60 min, a grinding fineness of-43 μm accounting for 69.02 wt% of the total, and a low-intensity magnetic field strength of 151 kA/m. The mineral composition, microstructure, and state of the roasted products were analyzed, and the concentrations of CO and CO_2 were analyzed in the co-reduction roasting. Better results were achieved with a small fluorite dosage(≤4 wt%) in the process of co-reduction. In addition, F^- was found to reduce the melting point and viscosity of the slag phase because of the high content of aluminate and silicate minerals in the blast furnace dust. The low moisture content of the blast furnace dust and calcic minerals inhibited the hydrolysis of CaF_2 and the loss of F^-. Compared with the blast furnace dust from Chengdeng, the blast furnace dusts from Jiugang and Jinxin inhibited the diffusion of F-when used as reducing agents, leading to weaker effects of fluorite.
基金The authors are grateful for the financial supports from the National Natural Science Foundation of China(Nos.51874247,51922091,51904249)Young Elite Scientists Sponsorship Program by CAST,China(No.2018QNRC001)+2 种基金Sichuan Science and Technology Program,China(Nos.2019YFS0453,2018JY0148)Open Research Fund of State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization,China(No.CNMRCUKF2001)Postgraduate Innovation Fund by Southwest University of Science and Technology,China(No.20ycx0027).
文摘The surface properties of fluorite are often affected by dissolved gangue species(e.g.,calcite)during the flotation process.Microflotation testing with and without the addition of calcite supernatant was conducted using octanohydroxamic acid(OHA)as the collector.The results revealed that dissolved calcite species significantly affected the flotation behavior of fluorite.Fourier transform infrared spectra confirmed that the decrease in flotation recovery was linked to lower OHA adsorption.Solution chemistry analysis indicated that CaCO_(3) and Ca^(2+)from the calcite supernatant were the most favorably adsorbed species,and X-ray photoelectron spectroscopy analysis confirmed the surface adsorption of calcite species.Density functional theory simulations provided a detailed analysis of the multidentate adsorption configuration of OHA,which was the most favorable for adsorption on the fluorite surface.The adsorption energy calculation showed that the calcite dissolved species were more stably adsorbed on the fluorite surface than OHA.The pre-adsorption of calcite dissolved species hindered the adsorption of OHA due to electrostatic repulsion.
基金supported by the Australian Research Council Discovery Projects(DP150104365 and DP160104835)the financial support by the China Scholarship Council(201808340038) for his visiting at Curtin University,Australiathe ARC Discovery Early Career Researcher Award(DE180100773)。
文摘High-temperature solid-state electrolyte is a key component of several important electrochemical devices,such as oxygen sensors for automobile exhaust control,solid oxide fuel cells(SOFCs) for power generation,and solid oxide electrolysis cells for H_(2) production from water electrolysis or CO_(2) electrochemical reduction to value-added chemicals.In particular,internal diffusion of protons or oxygen ions is a fundamental and crucial issue in the research of SOFCs,hypothetically based on either oxygen-ionconducting electrolytes or proton-conducting electrolytes.Up to now,some electrolyte materials based on fluorite or perovskite structure were found to show certain degree of dual-ion transportation capability,while in available electrolyte database,particularly in the field of SOFCs,such dual-ion conductivity was seriously overlooked.Actually,few concerns arising to the simultaneous proton and oxygen-ion conductivities in electrolyte of SOFCs inevitably induce various inadequate and confusing results in literature.Understanding dual-ion transportation behavior in electrolyte is indisputably of great importance to explain some unusual fuel cell performance as reported in literature and enrich the knowledge of solid state ionics.On the other hand,exploration of novel dual-ion conducting electrolytes will benefit the development of SOFCs.In this review,we provide a comprehensive summary of the understanding of dual-ion transportation in solid electrolyte and recent advances of dual-ion conducting SOFCs.The oxygen ion and proton conduction mechanisms at elevated temperature inside oxide-based electrolyte materials are first introduced,and then(mixed) oxygen ion and proton conduction behaviors of fluorite and perovskite-type oxides are discussed.Following on,recent advances in the development of dual-ion conducting SOFCs based on fluorite and perovskite-type single-phase or composite electrolytes,are reviewed.Finally,the challenges in the development of dual-ion conducting SOFCs are discussed and future prospects are proposed.
基金supported by National Natural Science Foundation for Young Scientists of China(Grant No.51802213)National Natural Science Foundation of China(Grant Nos.U1710256 and 52072256)Program of Applied Basic Research Program of Shanxi Province(Grant No.201901D211118)。
文摘A series of compositionally complex fluorite oxides(CCFOs)were prepared by ball milling the mixture of ZrO_(2),HfO_(2),Y_(2)O_(3),La_(2)O_(3),and Pr_(6)O_(11)followed by conventional solid-state sintering.Both XRD and TG-DSC results demonstrated that single-phase(Zr_(0.2)Hf_(0.2)Pr_(0.2)Y_(0.2)La_(0.2))O_(2-)δwas formed at 1400°C.Elements in bulk ceramic were uniformly distributed without evident accumulation according to SEM-EDS pictures.TEM results revealed that polycrystalline ceramic powder was assignable to cubic Fm-3m fluorite structure.The electrical conductivity(σ)was measured via EIS technology and activation energy(E_(a))of CCFOs was calculated in Arrhenius plots.In the temperature range of 300-750°C,CCFOs preserved the same conduction mechanism and(Zr_(0.1667)Hf_(0.1667)Pr_(0.1667)Y_(0.25)La_(0.25))O_(2-)δpossessed higherσand lower E_(a) than other high entropy fluorite oxides which is related to the incorporation of Pr element or the connection of cation-V_(o) complex.
文摘Fluorite is one of the main gangue minerals in the Maoniuping REE deposit, Sichuan Province, China. Fluorite with different colors occurs not only within various orebodies, but also in wallrocks of the orefield. Based on REE geochemistry, fluorite in the orefleld can be classified as the LREE-rich, LREE-flat and LREE-depleted types. The three types of fluorite formed at different stages from the same hydrothermal fluid source, with the LREE-rich fluorite forming at the relatively early stage, the LREE-flat fluorite in the middle, and the LREE-depleted fluorite at the latest stage. Various lines of evidence demonstrate that the variation of the REE contents of fluorite shows no relation to the color. The mineralization of the Maouiuping REE deposit is associated spatially and temporally with carbonatite-syenite magmatism and the ore-forming fluids are mainly derived from carbonatite and syenite melts.
基金supported by the Program for Changjiang Scholars and Innovative Research Team in University (PCSIRT)the 111 Project (No.B07011)
文摘Up to now, there were no systematic studies of geochemistry and isotopic age for the Yixian （义县） fluorite deposit, western Liaoning （辽宁） Province, China. Based on the analysis of metallogenic geological setting, we studied the REE, Rb-Sr and Sm-Nd isotopes. The chondrite-normalized REE patterns of fluorite are characterized by moderate LREE depletion （LREE/HREE=0.95-3.57, （La/Yb）N=0.08-2.84） and enrichment of Sr （146×10^-6-596×10^-6） and moderately positive Eu anomalies （δEu=1.10-1.34）, which are similar to those of the host Mesoproterozoic carbonate rocks. The fluorite display （^87Sr/^86Sr）t=-0.708 5, （^143Nd/^144Nd）t=-0.511 785, and δNd（t）=-12.8, which are similar to those of the host Mesoproterozoic carbonate rocks and volcanic rocks of Middle Jurassic Lanqi （蓝旗） Formation. The REE and Sr-Nd isotope geochemistry suggest that the source of the ore-forming material may be the volcanic rocks of Lanqi Formation and host carbonate rocks. The Sm-Nd isochron age of 154±14 Ma （MSWD=0.23） indicates that the Yixian fluorite mineralization nearly corresponds to the period of Lanqi Formation. Based on the integrated geological and geochemical studies, coupled with previous studies, we suggest that Yixian fluorite deposit formed in the extension setting of postcoilisional stage and may be attributed to the partial melting of ancient basaltic rocks in the lower crust induced by underplating of basic magma and to the reaction between the F-rich ore-forming fluids and the host carbonate rocks.
基金carried out within the framework of the“Central Anatolian Fluorite Research Project”supported by General Directorate of Mineral Research and Exploration(MTA).
文摘Fluorite mineralization occurs along fractures and cracks of Middle Eocene and Pliocene limestones and marls in the north and northeast of the P?hrenk region (?i?ekdagi, Kirsehir). Tb/Ca – Tb/La and Y/Ho ratios were obtained from REE contents of fluorites which have revealed that mineralization is of hydrothermal type. Negative Ce anomalies and positive Eu anomalies reflect that hydrothermal solutions once had high oxygen fugacity. Fluid inclusion studies indicate that homogenization temperatures of mineralization varied between 90°C and 200°C, and hydrothermal solutions are composed of NaCl + KCl + MgCl2 + H2O. In addition, salinity measurements show that hydrothermal solutions were mixed with meteoric or rock formation water. Geologic setting, REE geochemistry and fluid inclusion studies suggest that mineralization was deposited from a solution generated by mixing of magmatic and meteoric water under epithermal conditions.
基金funded by Geological Survey Program of China Geological Survey(DD20190816,DD20160057,DD20190606).
文摘Fluorite is one of the important mineral raw materials in the industry.In China,it is mainly distributed in the provinces and regions such as Hunan,Zhejiang,Jiangxi,Inner Mongolia,Fujian,and Henan provinces,boasting huge reserves and large numbers of deposits.However,most of the fluorite deposits are on a small or medium scale.The main fluorite deposits in China were studied in this paper.Their geological features and metallogenic regularity were summarized and compared.Meanwhile,based on their main genetic factors including metallogenic fluid sources and main metallogenic geological processes,they were divided into two groups,namely meso-epithermal deposits and magmatic-hydrothermal deposits.Furthermore,based on the prospecting achievements and research progress obtained in fluorite deposits in recent years,prospecting potential predictions were made for the metallogenic prospect areas and major prospecting areas of fluorite in China.This aims to provide a theoretical basis and direction for future fluorite prospecting in China.
基金supported by the Zhejiang Provincial Natural Science Foundation of China (Grant No.LY23F050007)the Department of Education of Zhejiang Province (No.Y202146207).
文摘Based on material design idea,we employ a co-precipitation strategy to obtain sinterable Ho_(2)Zr_(2)O_(7) flu-orite particles,successfully leading to novel transparent Ho_(2)Zr_(2)O_(7) ceramics with good optical/magneto-optical properties.The resulting precipitation precursor is identified to be hydrated basic carbonate upon calcination at the optimum temperature of 1250℃into near-spherical Ho_(2)Zr_(2)O_(7) nanopowder with an average size of~64 nm and unimodal narrow size distribution.The crystal intrinsic oxygen defect in fluorite ceramic generally exists in the form of F+center.The best bulk specimen achieved in this work exhibits a high refractive index of~2.1 and a high transparency of~74.4%at 1000 nm comparable with the corresponding defect-free single crystal(~76.4%in theory).In the Ho_(2)Zr_(2)O_(7) structure system,the elec-tronic polarizability of O_(2)-anion generally remains constant around 2.2?3 in the visible region and the corresponding optical basicity is approximately 0.9.The developed magneto-optical transparent Ho_(2)Zr_(2)O_(7) ceramic has Verdet constants of-180±3,-157±5,-87±2,-54±2,and-43±2 rad T^(-1) m^(-1) at 515,635,780,980,and 1064 nm,respectively,which are roughly 1.2-fold higher than the commercial TGG crystal.
基金Item Sponsored by National Natural Science Foundation of China(51104088)University Science Research Project of Inner Mongolia of China(NJZZ157)
文摘In order to fill up the deficiency of the theoretical basis about fluoride formation during Bayan Obo iron concentrate roasting process, the thermodynamic conditions of the interactivity between the components of the gangue and calcium fluorite were studied by means of thermodynamic calculation, DTA-TG thermal analysis and XRD characterization. The results revealed that KF, NaF and SiF4 （gaseous） could he,formed during the roasting process, and the tendency of the generation of KF is greater than that of NaF or SiF4 in standard state. Besides, the results of roasting experiments showed that the products of KCaCO3 F and KCaF3 formed in the temperature range of 800-1250 ℃and KF appears when the roasting temperature was higher than 1250 ℃ in K2O-CaF2 system. For the Na2O-CaF2 system, the product of NaF appears at temperature higher than 1050 ℃. The formation reaction of gaseous SiF4 with solid phase CaO · SiO2 in SiO2-CaF2 system took place＂only＇at temperature higher than 1 150 ℃. In the natural potash feldspar-CaF2-CaO system, the fluorination reaction products involved KF at temperature higher than 1 270 ℃ , while in the natural aegirine-CaF2-CaO system, NaF formed at terhperature higher than 980 ℃ during roasting process.
基金financially supported by the National Natural Science Foundation of China(No.42102079)the Natural Science Foundation of Sichuan Province(No.22NSFSC2765)+1 种基金State Key Laboratory of Ore Deposit Geochemistry Key Laboratory Open Project Fund(No.201804)the Southwest University of Science and Technology Doctoral Fund(No.16zx7132)。
文摘The Baoshan Cu–Pb–Zn deposit, located in the central part of the Qin–Hang belt in South China, is closely related to the granodiorite-porphyry. However, the characteristics and the source of the ore-forming fluid are still ubiquitous. According to the crosscutting relationships between veinlets and their mineral assemblages, three stages of hydrothermal mineralization in this deposit were previously distinguished. In this contribution, two different colored fluorites from the major sulfide mineralization stage are recognized:(1) green fluorites coexisting with Pb–Zn ores;and(2) violet fluorites coexisting with pyrite ores. Y/Ho ratios verify the green fluorites and violet fluorites were co-genetic. The fluorites display elevated(La/Yb)Nratios, which decrease from 1201 to 5710 for green fluorites to 689–1568 for violet fluorites, indicating that they precipitated at the early hydrothermal sulfide stage,and Pb–Zn ores crystallized earlier than pyrite ores. The similar Tb/La ratios of the fluorites also indicate that they precipitated at an early stage within a short time. From the green fluorites to violet fluorites, the total rare earth element(ΣREE)concentrationsdecreasefrom1052–1680 ppm to 148–350 ppm, indicating that the green fluorites precipitated from a more acidic fluid. The Eu/Eu*ratios increase from 0.17 to 0.30 for green fluorites to0.29–0.48 for violet fluorites, and the Ce/Ce* ratios decrease from 1.08–1.13 to 0.93–1.11, suggesting a gradual increase in oxygen fugacity(fO_(2)) and pH value of the mineralization fluid. Though the fluorites display similar REE patterns to the granodiorite-porphyry and limestone,the ΣREE concentrations of the fluorites are significantly higher than those of limestone and the granodiorite-porphyry, suggesting that an important undetected non-magmatic source is involved to provide sufficient REE for fluorites. The most plausible mechanism is fluid mixing between magma fluid and an undetected non-magmatic fluid.
基金financially supported by the Excellent Chemical Nonmetal Resource Evaluation Program (Grant 200310300002) from China Geological Survey
文摘The Bamianshan fluorite deposit is a super-large one recently discovered in Zhejiang Province of China. This paper presents an analysis of its geological background, orebody and ore characteristics, petrochemical characteristics of host rocks, rare earth elements （REE） of rocks and ores, fluid inclusions in fluorite and Sm-Nd isotopic features in an effort to study its sedimentary mineralization. The result shows that the super-large Bamianshan fluorite deposit is of hydrothermal sedimentation genesis, deformed by the later hydrothermal fluid. Integrated with host rocks and orebody characteristics, it is inferred that the deposit originates from the Cambrian sedimentary rocks. And the later magmatic activities deformed some orebodies in different degrees, forming steeply dipping vein orebodies in the tectonic belts regionally.
