High-Pressure Preparation of High-Density Cu_2ZnSnS_4 Materials

High-density Cu2ZnSnS4 （CZTS） materials are prepared via the mechanical alloying and high pressure sintering method using Cu2S, ZnS and SnS2 as the raw materials. The morphological, structural, compositional and electrical properties of the materials are investigated by using x-ray diffraction, scanning electron microscopy, and energy dispersive x-ray spectroscopy, as well as by the Raman scattering and the Hall EFfect measurements. The CZTS synthesized under 5 GPa and 800℃ shows a p-type conductivity, with a resistivity of 9.69 × 10^-2 Ω.cm and a carrier concentration of 1.45 × 10^20 cm-3. It is contributed to by the large grains in the materials reducing the grain boundaries, thus effectively reducing the recombination of the charge carriers.

Electrolyte additive enhances the electrochemical performance of Cu for rechargeable Cu//Zn batteries

Cu-based cathodes in aqueous batteries become very attractive in view of high theoretical capacity,moderate operation voltage and rich reserves of raw materials.However,their applications are obstructed by serious side reactions.The side reaction mainly arises from the spontaneous formation of Cu_(2)O,which occupies the electrode surface and lowers the reaction reversibility.Here,Na_(2)EDTA is introduced to address these issues.Both experimental results and theoretical calculations indicate that the Na_(2)EDTA reshapes the solvation structure of Cu^(2+)and modifies the electrode/electrolyte interface.Therefore,the redox potential of Cu^(2+)/Cu_(2)O is reduced and the surface of Cu is protected from H2O,thereby inhibiting the formation of Cu_(2)O.Meanwhile,the change in the solvation structure reduces the electrostatic repulsion between Cu^(2+)and the cathode,leading to high local concentration and benefiting uniform deposition.The results shed light on the applications of rechargeable Cu-based batteries.

First-Principles Electronic Structure of Cu^(+) Luminescence Centers in Cu-Doped ZnS

The electronic structures of various Cu^(+) luminescence centers in wurtzite ZnS are studied by using first-principles linear muffin-tin-orbital method combining atomic sphere approximation.The results for ZnS:Cu:Cl and ZnS:Cu:Al show that Cu acceptor states are anomalously deep(beyond 2.7eV above the top of valence band)and located near the bottom of conduction band in these two cases.On the other hand,the results for ZnS:Cu with sulfur vacancies manifest that the Cu+center is an associated center,whose Cu d-like states are situated above the top of valence band.

Lithium/Silver-Doped Cu_2ZnSnS_4 with Tunable Band Gaps and Phase Structures: a First-Principles Study

Doping is an effective approach for improving the photovoltaic performance of Cu2 ZnSnS4（CZTS）. The doping by substitution of Cu atoms in CZTS with Li and Ag atoms is investigated using density functional theory. The results show that the band gaps of Li（2 x）Cu2（1-x）ZnSnS4 and Ag（2 x）Cu2（1-x）ZnSnS4 can be tuned in the ranges of 1.30-3.43 and 1.30-1.63 eV, respectively. The calculation also reveals a phase transition from kesterite to wurtzite-kesterite for Li（2 x）Cu2（1-x）ZnSnS4 as x is larger than 0.9. The tunable band gaps of Li（2 x）Cu2（1-x）ZnSnS4 and Ag（2 x）Cu2（1-x） ZnSnS4 make them beneficial for achieving band-gap-graded solar cells.

Synthesis of Cu_2ZnSnS_4 thin film from mixed solution of Cu_2SnS_3 nanoparticles and Zn ions

The Cu2ZnSnS4 thin film was prepared by a facile solution method without vacuum environment and toxic substance. The formation mechanism of the film was studied by transmission electron microscopy (TEM), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), and Raman scattering measurements. Through cyclic voltammetry and photo-electricity tests, the electrocatalytic activity of the prepared film as the counter electrode of dye-sensitizedsolar cell was also studied. The results show that the mixed precursor solution mainly consists of Cu2SnS3 nanoparticles and Zn ions.After 550 °C annealing process on the precursor film prepared from the mixed solution, Cu2ZnSnS4 thin film is obtained. Besides, itis found that the prepared Cu2ZnSnS4 thin film has the electrocatalytic activity toward the redox reaction of I3?/I? and the dye-sensitized solar cell with the prepared Cu2ZnSnS4 thin film as the counter electrode achieves the efficiency of 1.09%.

Geology, geochronology and geochemistry of large Duobaoshan Cu-Mo-Au orefield in NE China: Magma genesis and regional tectonic implications

Duobaoshan is the largest porphyry-related Cu-Mo-Au orefield in northeastern(NE)Asia,and hosts a number of large-medium porphyry Cu(PCDs),epithermal Au and Fe-Cu skarn deposits.Formation ages of these deposits,from the oldest(Ordovician)to youngest(Jurassic),have spanned across over 300 Ma.No similar orefields of such size and geological complexity are found in NE Asia,which reflects its metallogenic uniqueness in forming and preserving porphyry-related deposits.In this study,we explore the actual number and timing of magmatic/mineralization phases,their respective magma genesis,fertility,and regional tectonic connection,together with the preservation of PCDs.We present new data on the magmatic/mineralization ages(LA-ICP-MS zircon U-Pb,pyrite and molybdenite Re-Os dating),whole-rock geochemistry,and zircon trace element compositions on four representative deposits in the Duobaoshan orefield,i.e.,Duobaoshan PCD,Tongshan PCD,Sankuanggou Fe-Cu skarn,and Zhengguang epithermal Au deposits,and compiled published ones from these and other mineral occurrences in the orefield.In terms of geochronology,we have newly summarized seven magmatic phases in the orefield:(1)Middle-Late Cambrian(506-491 Ma),(2)Early and Middle Ordovician(485-471 Ma and~462 Ma),(3)Late Ordovician(450-447 Ma),(4)Early Carboniferous and Late-Carboniferous to Early Permian(351-345 and 323-291 Ma),(5)Middle-Late Triassic(244-223 Ma),(6)Early-Middle and Late Jurassic(178-168 Ma and~150 Ma),and(7)Early Cretaceous(~112 Ma).Three of these seven major magmatic phases were coeval with ore formation,including(1)Early Ordovician(485-473 Ma)porphyry-type Cu-Mo-(Au),(2)Early-Middle Triassic(246-229 Ma)porphyry-related epithermal Au-(Cu-Mo),and(3)Early Jurassic(177-173 Ma)Fe-Cu skarn mineralization.Some deposits in the orefield,notably Tongshan and Zhengguang,were likely formed by more than one mineralization events.In terms of geochemistry,ore-causative granitoids in the orefield exhibit adakite-like or adakite-normal arc transitional signatures,but those forming the porphyry-/epithermal-type Cu-Mo-Au mineralization are largely confined to the former.The varying but high Sr/Y,Sm/Yb and La/Yb ratios suggest that the ore-forming magmas were mainly crustal sourced and formed at different depths(clinopyroxene-/amphibole-/garnet-stability fields).The adakite-like suites may have formed by partial melting of the thickened lower crust at 35-40 km(for the Early Ordovician arc)and>40 km(for the Middle-Late Triassic arc)depths.The Early Jurassic Fe-Cu skarn orecausative granitoids show an adakitic-normal arc transitional geochemical affinity.These granitoids were likely formed by partial melting of the juvenile lower crust(35-40 km depth),and subsequently modified by assimilation and fractional crystallization(AFC)processes.In light of the geological,geochronological and geochemical information,we proposed the following tectonometallogenic model for the Duobaoshan orefield.The Ordovician Duobaoshan may have been in a continental arc setting during the subduction of the Paleo-Asian Ocean,and formed the porphyry-related deposits at Duobaoshan,Tongshan and Zhengguang.Subduction may have ceased in the latest Ordovician,and the regional tectonics passed into long subsidence and extension till the latest Carboniferous.This extensional tectonic regime and the Silurian terrestrial-shallow marine sedimentation had likely buried and preserved the Ordovician Duobaoshan magmatic-hydrothermal system.The south-dipping Mongol-Okhotsk Ocean subduction from north of the orefield had generated the Middle-Late Triassic continental arc magmatism and the associated Tongshan PCD and Zhengguang epithermal Au mineralization(which superimposed on the Ordovician PCD system).The Middle Jurassic closure of Mongol-Okhotsk Ocean in the northwestern Amuria block(Erguna terrane),and the accompanying Siberia-Amuria collision,may have placed the Paleo-Pacific subduction system in NE China(including the orefield)under compression,and formed the granodiorite-tonalite and Fe-Cu skarn deposits at Sankuanggou and Xiaoduobaoshan.From the Middle Jurassic,the consecutive accretion of Paleo-Pacific arc terranes(e.g.,Sikhote-Alin and Nadanhada)onto the NE Asian continental margin may have gradually distant the Duobaoshan orefield from the subduction front,and consequently arc-type magmatism and the related mineralization faded.The minor Late Jurassic and Cretaceous unmineralized magmatism in the orefield may have triggered mainly by the far-field extension led by the post-collisional(Siberia-Amuria)gravitational collapse and/or Paleo-Pacific backarc-basin opening.

Microwave-assisted One-pot Synthesis ofYellow Cu： ZnSe/ZnS Quantum Dots UsingSelenium Dioxide Containing Copper Impurity

CuZnSe/ZnS core/shell quantum dots exhibiting yellow fluorescent emission were synthesized in aqueous phase via a one-potmicrowave irradiation approach, where glutathione （GSH） as stabilizer and selenium dioxide （SeO2） containing Cu as seleniumsource, respectively. The QDs obtained at the optimal conditions without any post-treatment present high crystallinity, which wasconfirmed by transmission electron microscopy （TEM） and high resolution transmission electron microscopy （HRTEM）. Thecore/shell structure was confirmed by X-ray photoelectron spectra （XPS） and Powder X-ray diffraction （XRD）. The binding ofGSH on the surface of QDs through thiol ligands was proved by the characterization of Fourier Transform Infrared Spectroscopy（FTIR）, suggesting the biocompatibility of the obtained QDs.

6种固化剂对土壤Pb Cd Cu Zn的固化效果

通过在重金属污染土壤中分别施加沸石、石灰石、硅藻土、羟基磷灰石、膨润土和海泡石6种固化剂,研究了这6种固化剂对土壤中Pb、Cd、Cu、Zn的固化效果,筛选出几种效果较好的固化剂。实验结果表明:沸石、石灰石和羟基磷灰石均能够有效地降低土壤中交换态Pb、Cd的含量,并且明显减少了土壤中Pb、Cd的毒性浸出量,其中沸石最多降低土壤中交换态Pb、Cd含量分别达到48.7%和56.2%,减少土壤中Pb、Cd的毒性浸出量达到37.1%和30.1%;沸石、石灰石均能够有效降低土壤中交换态Cu的含量,降低量分别高达68.1%和85.2%,膨润土能有效减少土壤中Cu的毒性浸出量,减少量最高达到66.51%;石灰石对土壤中Zn有着良好的固化效果。

不同品种水稻糙米对Cd Cu Zn积累特性的研究

以酸性矿山废水污染的含有多种重金属的农田土壤为供试土壤,通过盆栽实验,研究不同水稻品种,不同类型、不同遗传背景水稻糙米重金属Cd、Cu、Zn的积累差异。结果表明,供试水稻糙米Cd含量为0.006～0.092mg·kg-1,最高值和最低值相差15倍;Cu含量为6.712～27.117mg·kg-1,最高值和最低值相差4倍;Zn含量为28.390～43.296mg·kg-1,最高值和最低值相差不到1倍。常规稻和杂交稻糙米的Cd、Cu、Zn含量差异不明显。三系杂交稻的糙米Cd、Cu含量极显著高于二系杂交稻,而二系杂交稻糙米中Zn含量则显著高于三系杂交稻。不同遗传背景水稻品种糙米Cd、Cu、Zn含量也存在明显差异。相关分析结果表明,糙米中Cu、Cd含量间呈极显著正相关,Cu、Zn含量之间存在显著负相关,而Cd、Zn含量间的相关性不明显。

盐胁迫下花花柴 miR398 对 Cu/Zn 超氧化物歧化酶基因的调控研究

植物miRNA能够参与盐胁迫下基因表达的调控。在盐胁迫条件下盐生植物花花柴miR398（KcmiR398）呈现显著性差异表达，为了探讨rniR398的靶基因及其对靶基因的调控方式，通过生物信息学分析（http：／／plant—grn．noble．Org／psRNATarget／），预测KcmiR398的靶基因分别为Cu／Zn超氧化物歧化酶（SOD）基因CSDl和CSD2。利用RACE技术从花花柴中克隆到CSDl和CSD2基因全长序列，分别命名为KcCSDl和KcCSD2。qRTPCR结果表明：（1）KcmiR398在盐胁迫的花花柴茎中上调表达，在新叶中下调表达；KcCSDl在盐胁迫的老叶中上调表达，而在老茎和根中下调表达；KcCSD2在盐胁迫的老茎和根中上调表达。（2）300mmol／I，NaCl胁迫24~48h，KcmiR398与对照无显著差异；KcCSDl的表达为对照的3倍以上，而KcCSD2的表达没有显著差异。研究表明，花花柴的KcmiR398和KcCSDl、KcCSD2有组织差异性表达，盐胁迫可以影响KcmiR398和KcCSDl、KcCSD2基因的表达以适应盐胁迫产生的氧化危害。

Influence of different phosphates on adsorption and leaching of Cu and Zn in red soil

Batch and soil column experiments were conducted to evaluate the influence of KH2PO4, （NH4）H2PO4and Ca（H2PO4）2on the adsorption and leaching characteristics of Cu and Zn in red soil. The results show that all the three phosphates can greatly improve the adsorption capacity of red soil for Cu and Zn, and the effect of different phosphates on Cu and Zn adsorption follows the order of Ca（H2PO4）2〉KH2PO4〉（NH4）H2PO4. The addition of phosphate has little effect on the mobility of Cu. Ca（H2PO4）2and （NH4）H2PO4 show a strong ability in immobilizing Zn while the immobilization ability of KH2PO4 is much weaker. All the three phosphates are helpful for modifying the partitioning of Cu and Zn from the non-residual phase to the residual phase; however, they could also enhance the contents of Cu and Zn associated with exchangeable and carbonates fractions.

Microstructure evolution and thermal expansion of Cu-Zn alloy after high pressure heat treatment

The thermal expansion coefficients of Cu-Zn alloy before and after high pressure treatment were measured by thermal expansion instrument in the temperature range of 25？700 ℃,and the microstructure and phase transformation of the alloy were examined by optical microscope,X-ray diffractometer（XRD） and differential scanning calorimeter（DSC）.Based on the experimental results,the effects of high pressure treatment on the microstructure and thermal expansion of Cu-Zn alloy were investigated.The results show that the high pressure treatment can refine the grain and increase the thermal expansion coefficient of the Cu-Zn alloy,resulting in that the thermal expansion coefficient exhibits a high peak value on the α-T curve,and the peak value decreases with increasing the pressure.

Experimental Study of the Distribution of Au and Cu in Aqueous Vapor Phase at High Temperatures and Its Role on Ore-forming Transportation

This study focuses on experiments of Au and Cu dissolved in vapor phase in hydrothermal fluids. Experiments prove that Au and Cu can re-distribute in vapor phase and liquid phase during separation of Au- and Cu-bearing supercritical fluids to vapor and liquid phases. These experimental results can illustrate some ore geneses, where boiling phenomena of ore fluids were found. Au- and Cubearing NaHCO3-HCl solutions were heated up to more than 350℃ in the main vessel, and then passed through a phase separator in a temperature range from 250℃ to 300℃, separated into vapor and liquid phases. We collected and analyzed the liquid and vapor samples separately, and found that Au and Cu dissolved and distributed in vapor phase. In some cases, the concentrations of Au and Cu in vapor are higher than those in liquid phase. Those experiments are used to interpret field observations of fluid inclusion data of some Au and Cu deposits, and demonstrate that some Au and Cu ore deposits are derived from metals transportation in vapor phase.

Microstructure and properties of Cu/Al joints brazed with Zn-Al filler metals

The mechanical properties and microstructural distribution of the Cu/A1 brazing joints formed by torch-brazing with different Zn-A1 filler metals were investigated. The microstructure of the Zn-A1 alloys was studied by optical microscopy and scanning electron microscopy, and the phase constitution of the Cu/A1 joints was analyzed by energy dispersion spectrometry. The results show that the spreading area of the Zn-A1 filler metals on the Cu and A1 substrates increases as the A1 content increases. The mechanical results indicate that the shear strength reaches a peak value of 88 MPa when A1 and Cu are brazed with Zn-15AI filler metal. Microhardness levels from HV122 to HV515 were produced in the three brazing seam regions corresponding to various microstructure features. The Zn- and Al-rich phases exist in the middle brazing seam regions. However, two interface layers, CuZn3 and A12Cu are formed on the Cu side when the A1 content in the filler metals is 2% and more than 15%, respectively. The relationship between intermetallic compounds on Cu side and Zn-xA1 filler metals was investigated.

Petrogenesis and Tectonic Significance of the Three-Period Porphyries from the Daruoluolong Cu(Au) Deposit, Tibet, China

Objective The Daruoluolong deposit is the first high-grade Cu(Au)deposit discovered in the middle section of the Bangonghu-Nujiang(herein after referred to as Ban-Nu)metallogenic belt,which has not been documented about previously.This deposit is located in Shuanghu County of northern Tibet,and its geotectonic position belongs to the

^40Ar/^39Ar and Rb-Sr Ages of the Tiegelongnan Porphyry Cu-(Au)Deposit in the Bangong Co-Nujiang Metallogenic Belt of Tibet,China:Implication for Generation of Super-Large Deposit

The Tiegelongnan deposit is a newly discovered super-large porphyry-epithermal Cu-（Au） deposit in the western part of the Bangong Co-Nujiang metallogenic belt, Tibet（China）. Field geology and geochronology indicate that the porphyry mineralization was closely related to the Early Cretaceous intermediate-felsic intrusions（ca. 123–120 Ma）. Various epithermal ore and gangue mineral types were discovered in the middle-shallow part of the orebody, indicating the presence of epithermal mineralization at Tiegelongnan. Potassic, propylitic, phyllic and advanced argillic alteration zones were identified. 40Ar/39Ar dating of hydrothermal biotite（potassic zone）, sericite（phyllic zone）, and alunite（advanced argillic zone） in/around the ore-bearing granodiorite porphyry yielded 121.1±0.6 Ma（1σ）, 120.8±0.7 Ma（1σ） and 117.9±1.6 Ma（1σ）, respectively. Five hydrothermal mineralization stages were identified, of which the Stage IV pyrite was Rb-Sr dated to be 117.5±1.8 Ma（2σ）, representing the end of epithermal mineralization. Field geology and geochronology suggest that both the epithermal and porphyry mineralization belong to the same magmatic-hydrothermal system. The Tiegelongnan super-large Cu-（Au） deposit may have undergone a prolonged magmatichydrothermal evolution, with the major mineralization event occurring at ca.120–117Ma.

Gapped Spin-1/2 Spinon Excitations in a New Kagome Quantum Spin Liquid Compound Cu_3Zn(OH)_6FBr

We report a new kagome quantum spin liquid candidate CuaZn（OH）6FBr, which does not experience any phase transition down to 50inK, more than three orders lower than the antiferromagnetic Curie-Weiss temperature （-200 K）. A clear gap opening at low temperature is observed in the uniform spin susceptibility obtained from 19F nuclear magnetic resonance measurements. We observe the characteristic magnetic field dependence of the gap as expected for fractionalized spin-1/2 spinon excitations. Our experimental results provide firm evidence for spin fractionalization in a topologically ordered spin system, resembling charge fraetionalization in the fractional quantum Hall state.

The Characteristics of Ore-Controlling Structure in Baoshan Cu-Pb-Zn Polymetallic Deposit,Hunan Province

The Baoshan Cu-Pb-Zn polymetallic deposit is lied in the central Nanling mineralization zone,and belongs to the junction area of the Chenzhou-Linwu fault zone and the Leiyang-Linwu fault zone.It is a significant part of Nanling polymetallic deposit belt.The outcropping stratas consist of upper Devonian Shetianqiao,Xikuangshan Formation,Lower Carboniferous Menggong’ao,Shidengzi,Ceshui,and Zimenqiao Formation.Igneous rocks in the Baoshan ore area mainly comprise granodiorite porphyry.Furthermore,the radio isotopic age ranges from 123 Ma to 183 Ma,belonging to the early to middle Yanshanian.

多晶 CuZnAl 合金马氏体变体群结构及其生长过程研究

利用金相动态观察及Ｘ－射线衍射研究了多晶Ｃｕ－１８．５２Ｚｎ－６．３７Ａｌ合金Ｍ１８Ｒ马氏体变体群组态及其生长过程。多晶Ｃｕ－Ｚｎ－Ａｌ合金一个晶粒内多以一个变体群为主。每群由Ａ、Ｂ、Ｃ、Ｄ四个变体组成，形成ＡＣ型矛头状、ＡＢ平行及ＡＤ分叉型三种组态。变体群形成过程中，马氏体变体的消长及变体内小孪晶结构的形成等动力学特征反映了马氏体的热弹性及相变应力、应变自调节。在相变热循环中，变体群内形成大量非常稳定的残留马氏体。