Solid polymer electrolyte(SPE) shows great potential for all-solid-state batteries because of the inherent safety and flexibility;however, the unfavourable Li+deposition and large thickness hamper its development and ...Solid polymer electrolyte(SPE) shows great potential for all-solid-state batteries because of the inherent safety and flexibility;however, the unfavourable Li+deposition and large thickness hamper its development and application. Herein, a laminar MXene functional layer-thin SPE layer-cathode integration(MXene-PEO-LFP) is designed and fabricated. The MXene functional layer formed by stacking rigid MXene nanosheets imparts higher compressive strength relative to PEO electrolyte layer. And the abundant negatively-charged groups on MXene functional layer effectively repel anions and attract cations to adjust the charge distribution behavior at electrolyte–anode interface. Furthermore,the functional layer with rich lithiophilic groups and outstanding electronic conductivity results in low Li nucleation overpotential and nucleation energy barrier. In consequence, the cell assembled with MXene-PEO-LFP, where the PEO electrolyte layer is only 12 μm, much thinner than most solid electrolytes, exhibits uniform, dendrite-free Li+deposition and excellent cycling stability. High capacity(142.8 mAh g-1), stable operation of 140 cycles(capacity decay per cycle, 0.065%), and low polarization potential(0.5 C) are obtained in this Li|MXene-PEO-LFP cell,which is superior to most PEO-based electrolytes under identical condition. This integrated design may provide a strategy for the large-scale application of thin polymer electrolytes in all-solid-state battery.展开更多
Polyethylene oxide(PEO)-based solid polymer electrolytes(SPEs)with good electrochemical stability and excellent Li salt solubility are considered as one of the most promising SPEs for solid-state lithium metal batteri...Polyethylene oxide(PEO)-based solid polymer electrolytes(SPEs)with good electrochemical stability and excellent Li salt solubility are considered as one of the most promising SPEs for solid-state lithium metal batteries(SSLMBs).However,PEO-based SPEs suffer from low ionic conductivity at room temperature and high interfacial resistance with the electrodes due to poor interfacial contact,seriously hindering their practical applications.As an emerging technology,in-situ polymerization process has been widely used in PEO-based SPEs because it can effectively increase Li-ion transport at the interface and improve the interfacial contact between the electrolyte and electrodes.Herein,we review recent advances in design and fabrication of in-situ polymerized PEO-based SPEs to realize enhanced performance in LMBs.The merits and current challenges of various SPEs,as well as their stabilizing strategies are presented.Furthermore,various in-situ polymerization methods(such as free radical polymerization,cationic polymerization,anionic polymerization)for the preparation of PEO-based SPEs are summarized.In addition,the application of in-situ polymerization technology in PEO-based SPEs for adjustment of the functional units and addition of different functional filler materials was systematically discussed to explore the design concepts,methods and working mechanisms.Finally,the challenges and future prospects of in-situ polymerized PEO-based SPEs for SSLMBs are also proposed.展开更多
Biodegradable magnesium(Mg) and its alloy show huge potential as temporary bone substitute due to the favorable biocompatibility and mechanical compatibility. However, one issue deserves attention is the too fast degr...Biodegradable magnesium(Mg) and its alloy show huge potential as temporary bone substitute due to the favorable biocompatibility and mechanical compatibility. However, one issue deserves attention is the too fast degradation. In this work, mesoporous bioglass(MBG)with high pore volume(0.59 cc/g) and huge specific surface area(110.78 m^(2)/g) was synthesized using improved sol-gel method, and introduced into Mg-based composite via laser additive manufacturing. Immersion tests showed that the incorporated MBG served as powerful adsorption sites, which promoted the in-situ deposition of apatite by successively adsorbing Ca2+and HPO42-. Such dense apatite film acted as an efficient protection layer and enhanced the corrosion resistance of Mg matrix, which was proved by the electrochemical impedance spectroscopy measurements. Thereby, Mg based composite showed a significantly decreased degradation rate of 0.31 mm/year. Furthermore,MBG also improved the mechanical properties as well as cell behavior. This work highlighted the advantages of MBG in the fabrication of Mg-based implant with enhanced overall performance for orthopedic application.展开更多
Using pyromellitic dianhydride (PMDA) and 4,4’ diaminodiphenyl ether (ODA) as monomer materials, polyimide thin films have been prepared onto glass substrate by vapor deposition polymerization under a vacuum of 2.666...Using pyromellitic dianhydride (PMDA) and 4,4’ diaminodiphenyl ether (ODA) as monomer materials, polyimide thin films have been prepared onto glass substrate by vapor deposition polymerization under a vacuum of 2.666×10 -3 Pa and thermal curing of polyamic acid film in a vacuum at temperature of 150~200 ℃ for 60 min. In this process, the polymerization can be carried out through controlling the stoichiometric ratio, heating time and deposition ratio of the two monomers. The composition, the structure and properties of the polyimide films are investigated with IR spectrum, XRD, and SEM methods. The results show that the polyimide films by vapor deposition polymerization have good electrical properties and thermal stability. Therefore, the vapor deposition polymerization process is considered as a possible method of polymerization for other polymers.展开更多
Biodegradable poly (D,L-lactide) (PLA)/carboxyl-functionalized multi-walled carbon nanotubes (c-MWCNTs) composites were achieved via in-situ polymerization. These as-prepared composite materials were characteriz...Biodegradable poly (D,L-lactide) (PLA)/carboxyl-functionalized multi-walled carbon nanotubes (c-MWCNTs) composites were achieved via in-situ polymerization. These as-prepared composite materials were characterized with FT-IR, XRD, TG, DSC, SEM, and high insulation resistance meter. The results demonstrate that the multi-walled carbon nanotube was carboxyl functionalized, which improved the collection between c-MWCNTs and PLA, and further realized the graft copolymerization of c-MWCNTs and PLA. There is a higher glass transition temperature and a lower pyrolysis temperature of PLA/c-MWCNTs composites than pure PLA. The c-MWCNTs gave a better dispersion than unmodified MWCNTs in the PLA matrix, and an even coating of PLA on the surface of c-MWCNTs was obtained, which increased the interfacial interaction. High insulation resistance analysis showed that the addition of c-MWCNTs increased the electric conductivity, and c-MWCNTs performed against the large dielectric coefficient and electrostatic state of PLA. These results demonstrated that c-MWCNTs modified PLA composites were beneficial for potential application in the development of heat-resisting and conductivity plastic engineering.展开更多
The concentration difference in the near-surface region of lithium metal is the main cause of lithium dendrite growth.Resolving this issue will be key to achieving high-performance lithium metal batteries(LMBs).Herein...The concentration difference in the near-surface region of lithium metal is the main cause of lithium dendrite growth.Resolving this issue will be key to achieving high-performance lithium metal batteries(LMBs).Herein,we construct a lithium nitrate(LiNO_(3))-implanted electroactiveβphase polyvinylidene fluoride-co-hexafluoropropylene(PVDF-HFP)crystalline polymorph layer(PHL).The electronegatively charged polymer chains attain lithium ions on the surface to form lithium-ion charged channels.These channels act as reservoirs to sustainably release Li ions to recompense the ionic flux of electrolytes,decreasing the growth of lithium dendrites.The stretched molecular channels can also accelerate the transport of Li ions.The combined effects enable a high Coulombic efficiency of 97.0%for 250 cycles in lithium(Li)||copper(Cu)cell and a stable symmetric plating/stripping behavior over 2000 h at 3 mA cm^(-2)with ultrahigh Li utilization of 50%.Furthermore,the full cell coupled with PHL-Cu@Li anode and Li Fe PO_(4) cathode exhibits long-term cycle stability with high-capacity retention of 95.9%after 900 cycles.Impressively,the full cell paired with LiNi_(0.87)Co_(0.1)Mn_(0.03)O_(2)maintains a discharge capacity of 170.0 mAh g^(-1)with a capacity retention of 84.3%after 100 cycles even under harsh condition of ultralow N/P ratio of 0.83.This facile strategy will widen the potential application of LiNO_(3)in ester-based electrolyte for practical high-voltage LMBs.展开更多
The function of solid electrolytes and the composition of solid electrolyte interphase(SEI)are highly significant for inhibiting the growth of Li dendrites.Herein,we report an in-situ interfacial passivation combined ...The function of solid electrolytes and the composition of solid electrolyte interphase(SEI)are highly significant for inhibiting the growth of Li dendrites.Herein,we report an in-situ interfacial passivation combined with self-adaptability strategy to reinforce Li_(0.33)La_(0.557)TiO_(3)(LLTO)-based solid-state batteries.Specifically,a functional SEI enriched with LiF/Li_(3)PO_(4) is formed by in-situ electrochemical conversion,which is greatly beneficial to improving interface compatibility and enhancing ion transport.While the polarized dielectric BaTiO_(3)-polyamic acid(BTO-PAA,BP)film greatly improves the Li-ion transport kinetics and homogenizes the Li deposition.As expected,the resulting electrolyte offers considerable ionic conductivity at room temperature(4.3 x 10~(-4)S cm^(-1))and appreciable electrochemical decomposition voltage(5.23 V)after electrochemical passivation.For Li-LiFePO_(4) batteries,it shows a high specific capacity of 153 mA h g^(-1)at 0.2C after 100 cycles and a long-term durability of 115 mA h g^(-1)at 1.0 C after 800 cycles.Additionally,a stable Li plating/stripping can be achieved for more than 900 h at 0.5 mA cm^(-2).The stabilization mechanisms are elucidated by ex-situ XRD,ex-situ XPS,and ex-situ FTIR techniques,and the corresponding results reveal that the interfacial passivation combined with polarization effect is an effective strategy for improving the electrochemical performance.The present study provides a deeper insight into the dynamic adjustment of electrode-electrolyte interfacial for solid-state lithium batteries.展开更多
In this work, the wafer bowing during growth can be in-situ measured by a reflectivity mapping method in the 3×2 Thomas Swan close coupled showerhead metal organic chemical vapor deposition(MOCVD) system. The r...In this work, the wafer bowing during growth can be in-situ measured by a reflectivity mapping method in the 3×2 Thomas Swan close coupled showerhead metal organic chemical vapor deposition(MOCVD) system. The reflectivity mapping method is usually used to measure the film thickness and growth rate. The wafer bowing caused by stresses(tensile and compressive) during the epitaxial growth leads to a temperature variation at different positions on the wafer, and the lower growth temperature leads to a faster growth rate and vice versa. Therefore, the wafer bowing can be measured by analyzing the discrepancy of growth rates at different positions on the wafer. Furthermore, the wafer bowings were confirmed by the ex-situ wafer bowing measurement. High-resistivity and low-resistivity Si substrates were used for epitaxial growth. In comparison with low-resistivity Si substrate, Ga N grown on high-resistivity substrate shows a larger wafer bowing caused by the highly compressive stress introduced by compositionally graded Al Ga N buffer layer. This transition of wafer bowing can be clearly in-situ measured by using the reflectivity mapping method.展开更多
The continuous evolution of chip manufacturing demands the development of materials with ultra-low dielectric constants.With advantageous dielectric and mechanical properties,initiated chemical vapor deposited(iCVD)po...The continuous evolution of chip manufacturing demands the development of materials with ultra-low dielectric constants.With advantageous dielectric and mechanical properties,initiated chemical vapor deposited(iCVD)poly(1,3,5-trimethyl-1,3,5-trivinyl cyclotrisiloxane)(pV3D3)emerges as a promising candidate.However,previous works have not explored etching for this cyclosiloxane polymer thin film,which is indispensable for potential applications to the back-end-of-line fabrication.Here,we developed an etching process utilizing O2/Ar remote plasma for cyclic removal of iCVD pV3D3 thin film at sub-nanometer scale.We employed in-situ quartz crystal microbalance to investigate the process parameters including the plasma power,plasma duration and O2 flow rate.X-ray photoelectron spectroscopy and cross-sectional microscopy reveal the formation of an oxidized skin layer during the etching process.This skin layer further substantiates an etching mechanism driven by surface oxidation and sputtering.Additionally,this oxidized skin layer leads to improved elastic modulus and hardness and acts as a barrier layer for protecting the bottom cyclosiloxane polymer from further oxidation.展开更多
The Jianbeigou gold deposit is a typical lode gold deposit in the Qinling metallogenic belt, located on the southern margin of the North China Craton. Three stages of the hydrothermal process can be distinguished, inc...The Jianbeigou gold deposit is a typical lode gold deposit in the Qinling metallogenic belt, located on the southern margin of the North China Craton. Three stages of the hydrothermal process can be distinguished, including the quartz ± pyrite, quartz-polymetallic sulfide, and quartz-carbonate ± pyrite stages. From the early to late stages, the homogenization temperatures of primary fluid inclusions are 281–362°C, 227–331°C, and 149–261°C, respectively. The corresponding salinities estimated for these fluids are 3.9–9.9 wt%, 0.4–9.4 wt%, and 0.7–7.2 wt% Na Cl equiv. Combined with laser Raman spectroscopy data, the ore-forming fluid belongs to a H_(2)O-CO_(2)-Na Cl ± CH_4 system with medium–low temperature and salinity. The δ~(18)Ofluid and δD values for the quartz veins are-1.0‰ to 6.0‰ and-105‰ to-84‰, respectively, which indicates that the ore-forming fluid is of mixed source, mainly derived from magma, with a contribution from meteoric water. Pyrite has been identified into three generations based on mineral paragenetic sequencing, including Py1, Py2, and Py3. The pyrites have δ~(34)S sulfur isotopic compositions from three stages between 3.7‰ and 8.4‰, indicating that sulfur mainly originated from magma. Te, Bi, Sb, and Cu contents in pyrite were all high and showed a strong correlation with Au concentrations. Native gold and the Au-Ag-Bi telluride minerals were formed concurrently, and the As concentration was low and decoupled from the Au content. Therefore, Te, Bi, Sb and other low-melting point chalcophile elements play an important role for gold mineralization in arsenic-deficient ore-forming fluid. Combined with the geological setting, evolution of pyrite, and ore-fluids geochemistry, we propose that the Jianbeigou deposit can be classified as a magmatic–hydrothermal lode gold deposit. Gold mineralization on the southern margin of the North China Craton is related to Early Cretaceous magmatism and formed in an extensional setting.展开更多
Polypropylene/montmorillonite (PP/MMT)nanocomposites were prepared by in-situ polymerization using aMMT/MgCl_2/TiCl_4-EB Ziegler-Natta catalyst activated by triethylaluminum(TEA). The enlarged layer spacing of MMT was...Polypropylene/montmorillonite (PP/MMT)nanocomposites were prepared by in-situ polymerization using aMMT/MgCl_2/TiCl_4-EB Ziegler-Natta catalyst activated by triethylaluminum(TEA). The enlarged layer spacing of MMT wasconfirmed by X-ray wide angle diffraction (WAXD), demonstrating that MMT were intercalated by the catalyst components.X-ray photoelectron spectrometry (XPS) analysis proved that TiCl_4 was mainly supported on MgCl_2 instead of on the surfaceof MMT The exfoliated structure of MMT layers in the PP matrix of PP/MMT composites was demonstrated by WAXDpatterns and transmission electron microscopy (TEM) observation. The higher glass transition temperature and higher storage modulus of the PP/MMT composites in comparison with pure PP were revealed by dynamic mechanical analysis (DMA).展开更多
Polysulfonamide/zinc oxide(PSA/ZnO) nanocomposite films with w(ZnO)=0.5% were prepared by in-situ polymerization based on 4,4′-diaminodiphenylsulfone and terephthaloyl chloride in the common solvent N,N-Dimethylaceta...Polysulfonamide/zinc oxide(PSA/ZnO) nanocomposite films with w(ZnO)=0.5% were prepared by in-situ polymerization based on 4,4′-diaminodiphenylsulfone and terephthaloyl chloride in the common solvent N,N-Dimethylacetamide(DMAc). Atomic force microscopy (AFM) was employed to observe the microstructure of the composite film. The thermal property was investigated by TGA and mechanical property was characterized by DXLL-1000 electromechanical material testing machine. The results showed that the breaking strength of the film containing 0.5% ZnO was great enhanced. The average size of ZnO particles was below 100 nm. The introduction of ZnO as nano filler in PSA react as UV shield effect and make the composite mechanical property improved.展开更多
Conductive polymer composites based on crystalline polymer matrix have been prepared by using an in-situ polymerization process of pyrrole in amorphous poly (ethylene terephthalate) (PET) film. The DSC and WAXD me...Conductive polymer composites based on crystalline polymer matrix have been prepared by using an in-situ polymerization process of pyrrole in amorphous poly (ethylene terephthalate) (PET) film. The DSC and WAXD measurement and SEM observation show that liquid-induced crystallization of PET matrix has occurred during the preparation of composite films. Depending upon the equilibrium degree of swelling and crystallinity, the limited depth of penetration of pyrrole molecules results in a skin-core structure of the composite film. The skin layer containing charge transfer intercalated polypyrrole has a surface resistance of 3.5×10;Ω. Rigid and heat-resistant polypyrrole molecules formed in PET film increase the tensile modulus and, especially, the rigidity of PET at elevated temperatures. However, they decrease the tensile strength and elongation at break, and impair the thermal ductility of PET.展开更多
Using the langasite crystal microbalance (LCM), the trends in film thickness produced by means of the chemical vapor deposition using trichlorosilane gas, monomethylsilane gas and their mixed gas were observed at 600?...Using the langasite crystal microbalance (LCM), the trends in film thickness produced by means of the chemical vapor deposition using trichlorosilane gas, monomethylsilane gas and their mixed gas were observed at 600?C and evaluated by comparison with the information from a transmission electron microscope (TEM). The crystalline silicon film thickness from trichlorosilane gas was comparable to that of an amorphous silicon carbide film from monomethylsilane gas. The film obtained from the gas mixture was amorphous and was the thinnest in this study. Because the thickness trend obtained by the LCM agreed with that by the TEM, the LCM is shown to be a convenient evaluation tool for the behavior of various film deposition.展开更多
Using Cu-phthalocyanine(CuPc),4,4’-diaminodiphenyl ether and pyromellitic dianhydride as monomer materials, polyimide(PI) thin films doped-CuPc have been prepared onto glass substrate by vapor phase co-deposition...Using Cu-phthalocyanine(CuPc),4,4’-diaminodiphenyl ether and pyromellitic dianhydride as monomer materials, polyimide(PI) thin films doped-CuPc have been prepared onto glass substrate by vapor phase co-deposition polymerization under a vacuum of 2×10-3Pa and thermal curing of polyamic acid film in at temperature of 150-200℃ for 60min. In this process, the polymerization can be carried out through controlling the stoichiometric ratio, heating time and deposition rates of the three monomers. IR spectrum identifies the designed chemical structure of the polymer. The absorption of polyimide doped-CuPc is very intense in vis-range and near-infrared by UV-Vis spectrum. And, the PI films doped-CuPc polymerized by vapor phase deposition have uniformity, fine thermal stability and good nonlinear optical properties, and the third-order optical nonlinear susceptibility χ(3) with degenerate four-wave mixing can be 1.984×10-9ESU.展开更多
A kind of new nano composite with ultraviolet (UV) ray resistance and high temperature stability was prepared by in-situ polymerization in low temperature. Polysulfonamide (PSA) was synthesized with 4, 4'-diamin...A kind of new nano composite with ultraviolet (UV) ray resistance and high temperature stability was prepared by in-situ polymerization in low temperature. Polysulfonamide (PSA) was synthesized with 4, 4'-diaminodiphenyl sulfone (DDS) and terephthaloyl chloride (TPC) in the common solvent N, N-Dimethyl- -acetamide (DMAc). Nano filler is a certain nano titanium oxide modified by silicon oxide (TMS), which plays the role of UV resistance additives. Properties of the novel composite materials were characterized by Atomic Force microscopy (AFM), thermal gravimetric Analysis (TGA) and Ultraviolet Spectroscopy. AFM had showed the sizes and distributions of TMS particles in the nanocomposite. Ultraviolet Spectroscopy for the nanocomposites showed a large absorption in UV band. TGA showed the decomposition temperature was increased over ten degrees with 0.5% wt TMS for this nanocomposite compared with pure PSA.展开更多
This study shows the preparation of a TiO2 coated Pt/C(TiO2/Pt/C) by atomic layer deposition(ALD),and the examination of the possibility for TiO2/Pt/C to be used as a durable cathode catalyst in polymer electrolyt...This study shows the preparation of a TiO2 coated Pt/C(TiO2/Pt/C) by atomic layer deposition(ALD),and the examination of the possibility for TiO2/Pt/C to be used as a durable cathode catalyst in polymer electrolyte fuel cells(PEFCs). Cyclic voltammetry results revealed that TiO2/Pt/C catalyst which has 2 nm protective layer showed similar activity for the oxygen reduction reaction compared to Pt/C catalysts and they also had good durability. TiO2/Pt/C prepared by 10 ALD cycles degraded 70% after 2000 Accelerated degradation test, while Pt/C corroded 92% in the same conditions. TiO2 ultrathin layer by ALD is able to achieve a good balance between the durability and activity, leading to TiO2/Pt/C as a promising cathode catalyst for PEFCs. The mechanism of the TiO2 protective layer used to prevent the degradation of Pt/C is discussed.展开更多
The Dachang tin-polymetallic district, Guangxi,China, is one of the largest tin ore fields in the world. Both cassiterite-sulfide and Zn–Cu skarn mineralization are hosted in the Mid-Upper Devonian carbonate-rich sed...The Dachang tin-polymetallic district, Guangxi,China, is one of the largest tin ore fields in the world. Both cassiterite-sulfide and Zn–Cu skarn mineralization are hosted in the Mid-Upper Devonian carbonate-rich sediments adjacent to the underlying Cretaceous Longxianggai granite(91–97 Ma). The Lamo Zn–Cu deposit is a typical skarn deposit in the district and occurs at the contact zone between the Upper Devonian limestone and the granite.The ore minerals mainly consist of sphalerite, arsenopyrite,pyrrhotite, galena, chalcopyrite, and minor molybdenite.However, the age of mineralization and source of the metals are not well constrained. In this study, we use the molybdenite Re–Os dating method and in-situ Pb isotopes of sulfides from the Lamo deposit for the first time in order to directly determine the age of mineralization and the tracing source of metals. Six molybdenite samples yielded a more accurate Re–Os isochron age of 90.0 ± 1.1 Ma(MSWD = 0.72), which is much younger than the reported garnet Sm–Nd isochron age of 95 ± 11 Ma and quartz fluid inclusions Rb–Sr isochron age of 99 ± 6 Ma. This age is also interpreted as the age of Zn–Cu skarn mineralization in the Dachang district. Further, in this study we found that in-situ Pb isotopes of sulfides from the Lamo deposit and feldspars in the district's biotite granite and granitic porphyry dikes have a narrow range and an overlap of Pb isotopic compositions(^(206) Pb/^(204) Pb =18.417–18.594,^(207) Pb/^(204) Pb = 15.641–15.746, and^(208) Pb/^(204) Pb = 38.791–39.073), suggesting that the metals were mainly sourced from Cretaceous granitic magma.展开更多
The Southern Great Xing’an Range (SGXR) which forms part of the eastern segment of the Central Asian Orogenic Belt (CAOB) is known as one of the most important Cu-Mo-Pb-Zn-Ag-Au metallogenic belts in China,hosting a ...The Southern Great Xing’an Range (SGXR) which forms part of the eastern segment of the Central Asian Orogenic Belt (CAOB) is known as one of the most important Cu-Mo-Pb-Zn-Ag-Au metallogenic belts in China,hosting a number of porphyry Mo (Cu),skarn Fe (Sn),epithermal Au-Ag,and hydrothermal veintype Ag-Pb-Zn ore deposits.Here we investigate the Bianjiadayuan hydrothermal vein-type Ag-Pb-Zn ore deposit in the southern part of the SGXR.Porphyry Sn ±Cu ± Mo mineralization is also developed to the west of the Ag-Pb-Zn veins in the ore field.We identify a five-stage mineralization process based on field and petrologic studies including (i) the early porphyry mineralization stage,(ii) main porphyry mineralization stage,(iii) transition mineralization stage,(iv) vein-type mineralization stage and (v) late mineralization stage.Pyrite is the predominant sulfide mineral in all stages except in the late mineralization stage,and we identify corresponding four types of pyrites: Py1 is medium-grained subhedral to euhedral occurring in the early barren quartz vein;Py2 is medium- to fine-grained euhedral pyrite mainly coexisting with molybdenite,chalcopyrite,minor sphalerite and galena;Py3 is fine-grained,subhedral to irregular pyrite and displays cataclastic textures with micro-fractures;Py4 occurs as euhedral microcrystals and forms irregularly shaped aggregate with sphalerite and galena.LA-ICP-MS trace element analyses of pyrite show that Cu,Pb,Zn,Ag,Sn,Cd and Sb are partitioned into pyrite as structurally bound metals or mineral micro/nano-inclusions,whereas Co,Ni,As and Se enter the lattice via isomorphism in all types of pyrite.The Cu,Zn,Ag,Cd concentrations gradually increase from Py1 to Py4,which we correlate with cooling and mixing of ore-forming fluid with meteoric water.Py2 contains the highest contents of Co,Ni,Se,Te and Bi,suggesting high temperature conditions for the porphyry mineralization stage.Ratios of Co/Ni (0.03-10.79,average 2.13) and sulphur isotope composition of sulfide indicate typical hydrothermal origin for pyrites.The δ^34SCDT values of Py1 (0.42‰-1.61‰,average 1.16‰),Py2 (-1.23‰ to 0.82‰,average 0.35‰),Py3 (-0.36‰ to 2.47‰,average 0.97‰),Py4 (2.51‰-3.72‰,average 3.06‰),and other sulfides are consistent with those of typical porphyry deposit (-5‰ to 5‰),indicating that the Pb-Zn polymetallic mineralization in the Bianjiadayuan deposit is genetically linked to the Yanshanian (JurassiceCretaceous) magmatic-hydrothermal events.Variations of d34S values are ascribed to the changes in physical and chemical conditions during the evolution and migration of the ore-forming fluid.We propose that the high Sn content of pyrite in the Bianjiadayuan hydrothermal vein-type PbeZn polymetallic deposit can be used as a possible pathfinder to prospect for Sn mineralization in the surrounding area or deeper level of the ore field in this region.展开更多
Three-dimensional porous poly-lactic acid(PLA) scaffold was fabricated using fused deposition modeling(FDM) method including 30%, 50% and 70% nominal porosity. Study of phases in initial polymeric material and printed...Three-dimensional porous poly-lactic acid(PLA) scaffold was fabricated using fused deposition modeling(FDM) method including 30%, 50% and 70% nominal porosity. Study of phases in initial polymeric material and printed scaffolds was done by X-ray diffraction(XRD), and no significant phase difference was observed due to the manufacturing process, and the poly-lactic acid retains its crystalline properties. The results of the mechanical properties evaluation by the compression test show that the mechanical properties of the scaffold have decreased significantly with increasing the porosity of scaffold. The microstructure of scaffolds were studied by scanning electron microscope(SEM), showing that the pores had a regular arrangement and their morphology changed with porosity change. The mechanical properties of the poly-lactic acid scaffolds printed using fused deposition modeling, can be adapted to the surrounding tissue, by porosity change.展开更多
基金This work is supported by National Natural Science Founda-tion of China(U2004199)National Key Research and Devel-opment Program of China(2018YFD0200606)+1 种基金China Postdoctoral Science Foundation(2021T140615),Natural Sci-enceFoundationofHenanProvince(212300410285)Young Talent Support Project of Henan Province(2021HYTP028).
文摘Solid polymer electrolyte(SPE) shows great potential for all-solid-state batteries because of the inherent safety and flexibility;however, the unfavourable Li+deposition and large thickness hamper its development and application. Herein, a laminar MXene functional layer-thin SPE layer-cathode integration(MXene-PEO-LFP) is designed and fabricated. The MXene functional layer formed by stacking rigid MXene nanosheets imparts higher compressive strength relative to PEO electrolyte layer. And the abundant negatively-charged groups on MXene functional layer effectively repel anions and attract cations to adjust the charge distribution behavior at electrolyte–anode interface. Furthermore,the functional layer with rich lithiophilic groups and outstanding electronic conductivity results in low Li nucleation overpotential and nucleation energy barrier. In consequence, the cell assembled with MXene-PEO-LFP, where the PEO electrolyte layer is only 12 μm, much thinner than most solid electrolytes, exhibits uniform, dendrite-free Li+deposition and excellent cycling stability. High capacity(142.8 mAh g-1), stable operation of 140 cycles(capacity decay per cycle, 0.065%), and low polarization potential(0.5 C) are obtained in this Li|MXene-PEO-LFP cell,which is superior to most PEO-based electrolytes under identical condition. This integrated design may provide a strategy for the large-scale application of thin polymer electrolytes in all-solid-state battery.
基金This work was supported by the Major Science and Technology Projects of Henan Province(221100230200)the National Key Research and Development Program of China(2020YFB1713500)Open Fund of State Key Laboratory of Advanced Refractories(No.SKLAR202210).
文摘Polyethylene oxide(PEO)-based solid polymer electrolytes(SPEs)with good electrochemical stability and excellent Li salt solubility are considered as one of the most promising SPEs for solid-state lithium metal batteries(SSLMBs).However,PEO-based SPEs suffer from low ionic conductivity at room temperature and high interfacial resistance with the electrodes due to poor interfacial contact,seriously hindering their practical applications.As an emerging technology,in-situ polymerization process has been widely used in PEO-based SPEs because it can effectively increase Li-ion transport at the interface and improve the interfacial contact between the electrolyte and electrodes.Herein,we review recent advances in design and fabrication of in-situ polymerized PEO-based SPEs to realize enhanced performance in LMBs.The merits and current challenges of various SPEs,as well as their stabilizing strategies are presented.Furthermore,various in-situ polymerization methods(such as free radical polymerization,cationic polymerization,anionic polymerization)for the preparation of PEO-based SPEs are summarized.In addition,the application of in-situ polymerization technology in PEO-based SPEs for adjustment of the functional units and addition of different functional filler materials was systematically discussed to explore the design concepts,methods and working mechanisms.Finally,the challenges and future prospects of in-situ polymerized PEO-based SPEs for SSLMBs are also proposed.
基金National Natural Science Foundation of China (51935014,52165043, 82072084, 81871498)Jiang Xi Provincial Natural Science Foundation of China (20192ACB20005,2020ACB214004)+6 种基金The Provincial Key R&D Projects of Jiangxi (20201BBE51012)Guangdong Province Higher Vocational Colleges&Schools Pearl River Scholar Funded Scheme (2018)Shenzhen Science and Technology Plan Project (JCYJ20170817112445033)Innovation Team Project on University of Guangdong Province(2018GKCXTD001)Technology Innovation Platform Project of Shenzhen Institute of Information Technology 2020(PT2020E002)China Postdoctoral Science Foundation(2020M682114)Open Research Fund of Jiangsu Key Laboratory of Precision and Micro-Manufacturing Technology。
文摘Biodegradable magnesium(Mg) and its alloy show huge potential as temporary bone substitute due to the favorable biocompatibility and mechanical compatibility. However, one issue deserves attention is the too fast degradation. In this work, mesoporous bioglass(MBG)with high pore volume(0.59 cc/g) and huge specific surface area(110.78 m^(2)/g) was synthesized using improved sol-gel method, and introduced into Mg-based composite via laser additive manufacturing. Immersion tests showed that the incorporated MBG served as powerful adsorption sites, which promoted the in-situ deposition of apatite by successively adsorbing Ca2+and HPO42-. Such dense apatite film acted as an efficient protection layer and enhanced the corrosion resistance of Mg matrix, which was proved by the electrochemical impedance spectroscopy measurements. Thereby, Mg based composite showed a significantly decreased degradation rate of 0.31 mm/year. Furthermore,MBG also improved the mechanical properties as well as cell behavior. This work highlighted the advantages of MBG in the fabrication of Mg-based implant with enhanced overall performance for orthopedic application.
文摘Using pyromellitic dianhydride (PMDA) and 4,4’ diaminodiphenyl ether (ODA) as monomer materials, polyimide thin films have been prepared onto glass substrate by vapor deposition polymerization under a vacuum of 2.666×10 -3 Pa and thermal curing of polyamic acid film in a vacuum at temperature of 150~200 ℃ for 60 min. In this process, the polymerization can be carried out through controlling the stoichiometric ratio, heating time and deposition ratio of the two monomers. The composition, the structure and properties of the polyimide films are investigated with IR spectrum, XRD, and SEM methods. The results show that the polyimide films by vapor deposition polymerization have good electrical properties and thermal stability. Therefore, the vapor deposition polymerization process is considered as a possible method of polymerization for other polymers.
基金Projects(21107032,51073072)supported by the National Natural Science Foundation of ChinaProjects(Y406469,Y4110555,Y4100745)supported by Natural Science Foundation of Zhejiang Province,ChinaProjects(2011AY1048-5,2011AY1030)supported by the Science Foundation of Jiaxing Science and Technology Bureau,China
文摘Biodegradable poly (D,L-lactide) (PLA)/carboxyl-functionalized multi-walled carbon nanotubes (c-MWCNTs) composites were achieved via in-situ polymerization. These as-prepared composite materials were characterized with FT-IR, XRD, TG, DSC, SEM, and high insulation resistance meter. The results demonstrate that the multi-walled carbon nanotube was carboxyl functionalized, which improved the collection between c-MWCNTs and PLA, and further realized the graft copolymerization of c-MWCNTs and PLA. There is a higher glass transition temperature and a lower pyrolysis temperature of PLA/c-MWCNTs composites than pure PLA. The c-MWCNTs gave a better dispersion than unmodified MWCNTs in the PLA matrix, and an even coating of PLA on the surface of c-MWCNTs was obtained, which increased the interfacial interaction. High insulation resistance analysis showed that the addition of c-MWCNTs increased the electric conductivity, and c-MWCNTs performed against the large dielectric coefficient and electrostatic state of PLA. These results demonstrated that c-MWCNTs modified PLA composites were beneficial for potential application in the development of heat-resisting and conductivity plastic engineering.
基金the financial support from the National Natural Science Foundation of China(Nos.22205191 and 52002346)the Science and Technology Innovation Program of Hunan Province(No.2021RC3109)+1 种基金the Natural Science Foundation of Hunan Province,China(No.2022JJ40446)Guangxi Key Laboratory of Low Carbon Energy Material(No.2020GXKLLCEM01)。
文摘The concentration difference in the near-surface region of lithium metal is the main cause of lithium dendrite growth.Resolving this issue will be key to achieving high-performance lithium metal batteries(LMBs).Herein,we construct a lithium nitrate(LiNO_(3))-implanted electroactiveβphase polyvinylidene fluoride-co-hexafluoropropylene(PVDF-HFP)crystalline polymorph layer(PHL).The electronegatively charged polymer chains attain lithium ions on the surface to form lithium-ion charged channels.These channels act as reservoirs to sustainably release Li ions to recompense the ionic flux of electrolytes,decreasing the growth of lithium dendrites.The stretched molecular channels can also accelerate the transport of Li ions.The combined effects enable a high Coulombic efficiency of 97.0%for 250 cycles in lithium(Li)||copper(Cu)cell and a stable symmetric plating/stripping behavior over 2000 h at 3 mA cm^(-2)with ultrahigh Li utilization of 50%.Furthermore,the full cell coupled with PHL-Cu@Li anode and Li Fe PO_(4) cathode exhibits long-term cycle stability with high-capacity retention of 95.9%after 900 cycles.Impressively,the full cell paired with LiNi_(0.87)Co_(0.1)Mn_(0.03)O_(2)maintains a discharge capacity of 170.0 mAh g^(-1)with a capacity retention of 84.3%after 100 cycles even under harsh condition of ultralow N/P ratio of 0.83.This facile strategy will widen the potential application of LiNO_(3)in ester-based electrolyte for practical high-voltage LMBs.
基金financially supported by the National Natural Science Foundation of China (51971080)the Shenzhen Bureau of Science,Technology and Innovation Commission (GXWD20201230155427003-20200730151200003 and JSGG20200914113601003)。
文摘The function of solid electrolytes and the composition of solid electrolyte interphase(SEI)are highly significant for inhibiting the growth of Li dendrites.Herein,we report an in-situ interfacial passivation combined with self-adaptability strategy to reinforce Li_(0.33)La_(0.557)TiO_(3)(LLTO)-based solid-state batteries.Specifically,a functional SEI enriched with LiF/Li_(3)PO_(4) is formed by in-situ electrochemical conversion,which is greatly beneficial to improving interface compatibility and enhancing ion transport.While the polarized dielectric BaTiO_(3)-polyamic acid(BTO-PAA,BP)film greatly improves the Li-ion transport kinetics and homogenizes the Li deposition.As expected,the resulting electrolyte offers considerable ionic conductivity at room temperature(4.3 x 10~(-4)S cm^(-1))and appreciable electrochemical decomposition voltage(5.23 V)after electrochemical passivation.For Li-LiFePO_(4) batteries,it shows a high specific capacity of 153 mA h g^(-1)at 0.2C after 100 cycles and a long-term durability of 115 mA h g^(-1)at 1.0 C after 800 cycles.Additionally,a stable Li plating/stripping can be achieved for more than 900 h at 0.5 mA cm^(-2).The stabilization mechanisms are elucidated by ex-situ XRD,ex-situ XPS,and ex-situ FTIR techniques,and the corresponding results reveal that the interfacial passivation combined with polarization effect is an effective strategy for improving the electrochemical performance.The present study provides a deeper insight into the dynamic adjustment of electrode-electrolyte interfacial for solid-state lithium batteries.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.61274039 and 51177175)the National Basic Research Program of China(Grant No.2011CB301903)+5 种基金the Ph.D.Programs Foundation of Ministry of Education of China(Grant No.20110171110021)the International Science and Technology Collaboration Program of China(Grant No.2012DFG52260)the International Science and Technology Collaboration Program of Guangdong Province,China(Grant No.2013B051000041)the Science and Technology Plan of Guangdong Province,China(Grant No.2013B010401013)the National High Technology Research and Development Program of China(Grant No.2014AA032606)the Opened Fund of the State Key Laboratory on Integrated Optoelectronics,China(Grant No.IOSKL2014KF17)
文摘In this work, the wafer bowing during growth can be in-situ measured by a reflectivity mapping method in the 3×2 Thomas Swan close coupled showerhead metal organic chemical vapor deposition(MOCVD) system. The reflectivity mapping method is usually used to measure the film thickness and growth rate. The wafer bowing caused by stresses(tensile and compressive) during the epitaxial growth leads to a temperature variation at different positions on the wafer, and the lower growth temperature leads to a faster growth rate and vice versa. Therefore, the wafer bowing can be measured by analyzing the discrepancy of growth rates at different positions on the wafer. Furthermore, the wafer bowings were confirmed by the ex-situ wafer bowing measurement. High-resistivity and low-resistivity Si substrates were used for epitaxial growth. In comparison with low-resistivity Si substrate, Ga N grown on high-resistivity substrate shows a larger wafer bowing caused by the highly compressive stress introduced by compositionally graded Al Ga N buffer layer. This transition of wafer bowing can be clearly in-situ measured by using the reflectivity mapping method.
基金the funding from the National Natural Science Foundation of China(22178301 and 21938011)the grant from the Science&Technology Department of Zhejiang Province(2023C01182)+3 种基金the funding from the Natural Science Foundation of Zhejiang Province(LR21B060003)supported by the Fundamental Research Funds for the Central Universities(226-2024-00023)Shanxi Institute of Zhejiang University for New Materials and Chemical Industry(2022SZ-TD005)Quzhou Science and Technology Program(2021NC02).
文摘The continuous evolution of chip manufacturing demands the development of materials with ultra-low dielectric constants.With advantageous dielectric and mechanical properties,initiated chemical vapor deposited(iCVD)poly(1,3,5-trimethyl-1,3,5-trivinyl cyclotrisiloxane)(pV3D3)emerges as a promising candidate.However,previous works have not explored etching for this cyclosiloxane polymer thin film,which is indispensable for potential applications to the back-end-of-line fabrication.Here,we developed an etching process utilizing O2/Ar remote plasma for cyclic removal of iCVD pV3D3 thin film at sub-nanometer scale.We employed in-situ quartz crystal microbalance to investigate the process parameters including the plasma power,plasma duration and O2 flow rate.X-ray photoelectron spectroscopy and cross-sectional microscopy reveal the formation of an oxidized skin layer during the etching process.This skin layer further substantiates an etching mechanism driven by surface oxidation and sputtering.Additionally,this oxidized skin layer leads to improved elastic modulus and hardness and acts as a barrier layer for protecting the bottom cyclosiloxane polymer from further oxidation.
基金jointed supported by National Key Research and Development Program of China (Grant No. 2021YFC2901704)the National Natural Science Foundation of China (Grant No. 41930430)the State Key Laboratory of Lithospheric Evolution, IGGCAS (Grant No. SKL-Z201905)。
文摘The Jianbeigou gold deposit is a typical lode gold deposit in the Qinling metallogenic belt, located on the southern margin of the North China Craton. Three stages of the hydrothermal process can be distinguished, including the quartz ± pyrite, quartz-polymetallic sulfide, and quartz-carbonate ± pyrite stages. From the early to late stages, the homogenization temperatures of primary fluid inclusions are 281–362°C, 227–331°C, and 149–261°C, respectively. The corresponding salinities estimated for these fluids are 3.9–9.9 wt%, 0.4–9.4 wt%, and 0.7–7.2 wt% Na Cl equiv. Combined with laser Raman spectroscopy data, the ore-forming fluid belongs to a H_(2)O-CO_(2)-Na Cl ± CH_4 system with medium–low temperature and salinity. The δ~(18)Ofluid and δD values for the quartz veins are-1.0‰ to 6.0‰ and-105‰ to-84‰, respectively, which indicates that the ore-forming fluid is of mixed source, mainly derived from magma, with a contribution from meteoric water. Pyrite has been identified into three generations based on mineral paragenetic sequencing, including Py1, Py2, and Py3. The pyrites have δ~(34)S sulfur isotopic compositions from three stages between 3.7‰ and 8.4‰, indicating that sulfur mainly originated from magma. Te, Bi, Sb, and Cu contents in pyrite were all high and showed a strong correlation with Au concentrations. Native gold and the Au-Ag-Bi telluride minerals were formed concurrently, and the As concentration was low and decoupled from the Au content. Therefore, Te, Bi, Sb and other low-melting point chalcophile elements play an important role for gold mineralization in arsenic-deficient ore-forming fluid. Combined with the geological setting, evolution of pyrite, and ore-fluids geochemistry, we propose that the Jianbeigou deposit can be classified as a magmatic–hydrothermal lode gold deposit. Gold mineralization on the southern margin of the North China Craton is related to Early Cretaceous magmatism and formed in an extensional setting.
文摘Polypropylene/montmorillonite (PP/MMT)nanocomposites were prepared by in-situ polymerization using aMMT/MgCl_2/TiCl_4-EB Ziegler-Natta catalyst activated by triethylaluminum(TEA). The enlarged layer spacing of MMT wasconfirmed by X-ray wide angle diffraction (WAXD), demonstrating that MMT were intercalated by the catalyst components.X-ray photoelectron spectrometry (XPS) analysis proved that TiCl_4 was mainly supported on MgCl_2 instead of on the surfaceof MMT The exfoliated structure of MMT layers in the PP matrix of PP/MMT composites was demonstrated by WAXDpatterns and transmission electron microscopy (TEM) observation. The higher glass transition temperature and higher storage modulus of the PP/MMT composites in comparison with pure PP were revealed by dynamic mechanical analysis (DMA).
基金Education Commission of Shanghai (No04AB19)Science and Technology Commission of Shanghai Municipal Government(Nano Founds No 0452NM051)
文摘Polysulfonamide/zinc oxide(PSA/ZnO) nanocomposite films with w(ZnO)=0.5% were prepared by in-situ polymerization based on 4,4′-diaminodiphenylsulfone and terephthaloyl chloride in the common solvent N,N-Dimethylacetamide(DMAc). Atomic force microscopy (AFM) was employed to observe the microstructure of the composite film. The thermal property was investigated by TGA and mechanical property was characterized by DXLL-1000 electromechanical material testing machine. The results showed that the breaking strength of the film containing 0.5% ZnO was great enhanced. The average size of ZnO particles was below 100 nm. The introduction of ZnO as nano filler in PSA react as UV shield effect and make the composite mechanical property improved.
文摘Conductive polymer composites based on crystalline polymer matrix have been prepared by using an in-situ polymerization process of pyrrole in amorphous poly (ethylene terephthalate) (PET) film. The DSC and WAXD measurement and SEM observation show that liquid-induced crystallization of PET matrix has occurred during the preparation of composite films. Depending upon the equilibrium degree of swelling and crystallinity, the limited depth of penetration of pyrrole molecules results in a skin-core structure of the composite film. The skin layer containing charge transfer intercalated polypyrrole has a surface resistance of 3.5×10;Ω. Rigid and heat-resistant polypyrrole molecules formed in PET film increase the tensile modulus and, especially, the rigidity of PET at elevated temperatures. However, they decrease the tensile strength and elongation at break, and impair the thermal ductility of PET.
文摘Using the langasite crystal microbalance (LCM), the trends in film thickness produced by means of the chemical vapor deposition using trichlorosilane gas, monomethylsilane gas and their mixed gas were observed at 600?C and evaluated by comparison with the information from a transmission electron microscope (TEM). The crystalline silicon film thickness from trichlorosilane gas was comparable to that of an amorphous silicon carbide film from monomethylsilane gas. The film obtained from the gas mixture was amorphous and was the thinnest in this study. Because the thickness trend obtained by the LCM agreed with that by the TEM, the LCM is shown to be a convenient evaluation tool for the behavior of various film deposition.
基金Natural Science Foundation of Shaanxi Province ( 2004CS110005 ) Research Foundation of Northwestern Polytechnical University
文摘Using Cu-phthalocyanine(CuPc),4,4’-diaminodiphenyl ether and pyromellitic dianhydride as monomer materials, polyimide(PI) thin films doped-CuPc have been prepared onto glass substrate by vapor phase co-deposition polymerization under a vacuum of 2×10-3Pa and thermal curing of polyamic acid film in at temperature of 150-200℃ for 60min. In this process, the polymerization can be carried out through controlling the stoichiometric ratio, heating time and deposition rates of the three monomers. IR spectrum identifies the designed chemical structure of the polymer. The absorption of polyimide doped-CuPc is very intense in vis-range and near-infrared by UV-Vis spectrum. And, the PI films doped-CuPc polymerized by vapor phase deposition have uniformity, fine thermal stability and good nonlinear optical properties, and the third-order optical nonlinear susceptibility χ(3) with degenerate four-wave mixing can be 1.984×10-9ESU.
文摘A kind of new nano composite with ultraviolet (UV) ray resistance and high temperature stability was prepared by in-situ polymerization in low temperature. Polysulfonamide (PSA) was synthesized with 4, 4'-diaminodiphenyl sulfone (DDS) and terephthaloyl chloride (TPC) in the common solvent N, N-Dimethyl- -acetamide (DMAc). Nano filler is a certain nano titanium oxide modified by silicon oxide (TMS), which plays the role of UV resistance additives. Properties of the novel composite materials were characterized by Atomic Force microscopy (AFM), thermal gravimetric Analysis (TGA) and Ultraviolet Spectroscopy. AFM had showed the sizes and distributions of TMS particles in the nanocomposite. Ultraviolet Spectroscopy for the nanocomposites showed a large absorption in UV band. TGA showed the decomposition temperature was increased over ten degrees with 0.5% wt TMS for this nanocomposite compared with pure PSA.
基金supported by the Ministry of Knowledge Economy (MKE, Korea) under the Global Collaborative R&D program supervised by the KIAT (N0000698)
文摘This study shows the preparation of a TiO2 coated Pt/C(TiO2/Pt/C) by atomic layer deposition(ALD),and the examination of the possibility for TiO2/Pt/C to be used as a durable cathode catalyst in polymer electrolyte fuel cells(PEFCs). Cyclic voltammetry results revealed that TiO2/Pt/C catalyst which has 2 nm protective layer showed similar activity for the oxygen reduction reaction compared to Pt/C catalysts and they also had good durability. TiO2/Pt/C prepared by 10 ALD cycles degraded 70% after 2000 Accelerated degradation test, while Pt/C corroded 92% in the same conditions. TiO2 ultrathin layer by ALD is able to achieve a good balance between the durability and activity, leading to TiO2/Pt/C as a promising cathode catalyst for PEFCs. The mechanism of the TiO2 protective layer used to prevent the degradation of Pt/C is discussed.
基金supported by the National Science Foundation of China(Grants Nos.41672080,41772079,41272113)Outstanding Talent Foundation of the Institute of Geochemistry,Chinese Academy of Sciences
文摘The Dachang tin-polymetallic district, Guangxi,China, is one of the largest tin ore fields in the world. Both cassiterite-sulfide and Zn–Cu skarn mineralization are hosted in the Mid-Upper Devonian carbonate-rich sediments adjacent to the underlying Cretaceous Longxianggai granite(91–97 Ma). The Lamo Zn–Cu deposit is a typical skarn deposit in the district and occurs at the contact zone between the Upper Devonian limestone and the granite.The ore minerals mainly consist of sphalerite, arsenopyrite,pyrrhotite, galena, chalcopyrite, and minor molybdenite.However, the age of mineralization and source of the metals are not well constrained. In this study, we use the molybdenite Re–Os dating method and in-situ Pb isotopes of sulfides from the Lamo deposit for the first time in order to directly determine the age of mineralization and the tracing source of metals. Six molybdenite samples yielded a more accurate Re–Os isochron age of 90.0 ± 1.1 Ma(MSWD = 0.72), which is much younger than the reported garnet Sm–Nd isochron age of 95 ± 11 Ma and quartz fluid inclusions Rb–Sr isochron age of 99 ± 6 Ma. This age is also interpreted as the age of Zn–Cu skarn mineralization in the Dachang district. Further, in this study we found that in-situ Pb isotopes of sulfides from the Lamo deposit and feldspars in the district's biotite granite and granitic porphyry dikes have a narrow range and an overlap of Pb isotopic compositions(^(206) Pb/^(204) Pb =18.417–18.594,^(207) Pb/^(204) Pb = 15.641–15.746, and^(208) Pb/^(204) Pb = 38.791–39.073), suggesting that the metals were mainly sourced from Cretaceous granitic magma.
基金financially supported by National Key Research and Development Program of China (2016YFC0600504)Fundamental Research Funds for the Central Universities (2652017218)
文摘The Southern Great Xing’an Range (SGXR) which forms part of the eastern segment of the Central Asian Orogenic Belt (CAOB) is known as one of the most important Cu-Mo-Pb-Zn-Ag-Au metallogenic belts in China,hosting a number of porphyry Mo (Cu),skarn Fe (Sn),epithermal Au-Ag,and hydrothermal veintype Ag-Pb-Zn ore deposits.Here we investigate the Bianjiadayuan hydrothermal vein-type Ag-Pb-Zn ore deposit in the southern part of the SGXR.Porphyry Sn ±Cu ± Mo mineralization is also developed to the west of the Ag-Pb-Zn veins in the ore field.We identify a five-stage mineralization process based on field and petrologic studies including (i) the early porphyry mineralization stage,(ii) main porphyry mineralization stage,(iii) transition mineralization stage,(iv) vein-type mineralization stage and (v) late mineralization stage.Pyrite is the predominant sulfide mineral in all stages except in the late mineralization stage,and we identify corresponding four types of pyrites: Py1 is medium-grained subhedral to euhedral occurring in the early barren quartz vein;Py2 is medium- to fine-grained euhedral pyrite mainly coexisting with molybdenite,chalcopyrite,minor sphalerite and galena;Py3 is fine-grained,subhedral to irregular pyrite and displays cataclastic textures with micro-fractures;Py4 occurs as euhedral microcrystals and forms irregularly shaped aggregate with sphalerite and galena.LA-ICP-MS trace element analyses of pyrite show that Cu,Pb,Zn,Ag,Sn,Cd and Sb are partitioned into pyrite as structurally bound metals or mineral micro/nano-inclusions,whereas Co,Ni,As and Se enter the lattice via isomorphism in all types of pyrite.The Cu,Zn,Ag,Cd concentrations gradually increase from Py1 to Py4,which we correlate with cooling and mixing of ore-forming fluid with meteoric water.Py2 contains the highest contents of Co,Ni,Se,Te and Bi,suggesting high temperature conditions for the porphyry mineralization stage.Ratios of Co/Ni (0.03-10.79,average 2.13) and sulphur isotope composition of sulfide indicate typical hydrothermal origin for pyrites.The δ^34SCDT values of Py1 (0.42‰-1.61‰,average 1.16‰),Py2 (-1.23‰ to 0.82‰,average 0.35‰),Py3 (-0.36‰ to 2.47‰,average 0.97‰),Py4 (2.51‰-3.72‰,average 3.06‰),and other sulfides are consistent with those of typical porphyry deposit (-5‰ to 5‰),indicating that the Pb-Zn polymetallic mineralization in the Bianjiadayuan deposit is genetically linked to the Yanshanian (JurassiceCretaceous) magmatic-hydrothermal events.Variations of d34S values are ascribed to the changes in physical and chemical conditions during the evolution and migration of the ore-forming fluid.We propose that the high Sn content of pyrite in the Bianjiadayuan hydrothermal vein-type PbeZn polymetallic deposit can be used as a possible pathfinder to prospect for Sn mineralization in the surrounding area or deeper level of the ore field in this region.
文摘Three-dimensional porous poly-lactic acid(PLA) scaffold was fabricated using fused deposition modeling(FDM) method including 30%, 50% and 70% nominal porosity. Study of phases in initial polymeric material and printed scaffolds was done by X-ray diffraction(XRD), and no significant phase difference was observed due to the manufacturing process, and the poly-lactic acid retains its crystalline properties. The results of the mechanical properties evaluation by the compression test show that the mechanical properties of the scaffold have decreased significantly with increasing the porosity of scaffold. The microstructure of scaffolds were studied by scanning electron microscope(SEM), showing that the pores had a regular arrangement and their morphology changed with porosity change. The mechanical properties of the poly-lactic acid scaffolds printed using fused deposition modeling, can be adapted to the surrounding tissue, by porosity change.