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1.
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2.
The nanometer MnO2 has outstanding electrochemical performance theoretically, but it is not suitable for actual utilization, which may result in capacity decrease and resource waste. In this study we have utilized the characterizations of the nanometer material, synthesized a type of nanometer α-MnO2 through KMnO4 and KNO3 with hydrothermal method, and mixed the products into micron electrolytic manganese dioxide （EMD） to enhance the electrochemical performance of the electrode.The cyclic voltammogram and galvanostatical discharge measurements of the samples were investigated. It is found that the 50﹪ nanometer MnO2 mixed electrode has the best electrochemical performance. The electrochemical performance improvement mechanism of the sample nanometer MnO2 mixed into micron EMD was discussed. With the existence of electrolyte, the nanometer MnO2 particles filled into the interspaces of the micron EMD particles, the mass and charge transfer conditions of the electrode reaction were improved, and the electrode polarization was diminished.  相似文献   

3.
The phase state of fluid in the H2O-NaF-Na2SO4 system in the presence of silicates (quartz and albite) was experimentally explored using the method of synthetic fluid inclusions in quartz at 700°C and pressures of 1 and 2 kbar. Parallel experiments were conducted under identical conditions with either two silicates (quartz and albite) or quartz only. The presence of albite affects heterogeneous fluid equilibria both at different pressures and at different solution compositions. This indicates high solubilities of silicates in a saltwater fluid containing NaF and Na2SO4. The absence of inclusions homogenizing to a gas phase in the experimental products provides compelling evidence that liquid-liquid rather than liquid-vapor equilibria are characteristic of the H2O-SiO2-NaF-Na2SO4 and H2O-SiO2-NaF-Na2SO4-NaAlSi3O2 systems in the heterogeneous region. It can be concluded that critical equilibria in saturated solutions can exist in these systems. In addition, it was shown that the phase diagrams of these systems are complicated by the formation of immiscible liquids in the presence of vapor. This allowed us to conclude that there are two critical curves describing equilibria with two different salts. Fluids containing two salts (NaF and Na2SO4) are similar to fluids containing only one of these salts: (a) two liquids are in equilibrium under the parameters of the upper heterogeneous region, (b) each of them can in turn undergo unmixing at decreasing temperature and pressure, and (c) owing to chemical interaction between silicate and fluid components, a glassy phase can be formed and trapped in inclusions.  相似文献   

4.
An integrated lithofacies analysis of the Middle-Upper Bathonian petroleum horizon J2 in the northeastern part of the latitudinal Ob’ region was carried out. The new data were used to supplement and refine the available data. The recognized lithofacies and their associations clearly mark off the boundaries of reconstructed sedimentation conditions. A petrographical study of the silt-sandy rocks of the horizon was carried out with a detailed calculation of their grain size and petrographic compositions. Grain size coefficients were analyzed with the use of genetic, dynamic, and dynamogenetic diagrams. The new data permitted a considerable refinement of the reconstructed sedimentation conditions of the horizon. It has been found that the transgressive change of sedimentation conditions is reflected in regular changes in some characteristics of the studied sediments: a decrease in the total number and thickness of coal interbeds, an increase in the degree of sediment bioturbation, a change of ichnofossils, and an increase in the amount of pyrite. More detailed paleogeographical schemes have been constructed for the formation of the lower (continental), middle (transitional), and upper (littoral marine) parts of the horizon. They provide a better understanding of the regularities of development of the Middle-Late Bathonian sedimentary basin in the study area.  相似文献   

5.
The launch of the Spektrum-Roentgen-Gamma (SRG) international orbiting astrophysical observatory is planned for the near future. It is planned tomaneuver SRGinto the vicinity of the L2 libration point of the Sun–Earth system, where it will be kept in a quasi-stable orbit. The spacecraft orbit must be maintained in order to carry out the scientific program of the project, which requires obtaining information about the current parameters of its motion. With the aim of developing methods for making optical measurements and estimating the required volume of measurement data and their accuracy, observations of the Gaia spacecraft, which is located in the vicinity of L2, were made at the Sayan Observatory in 2014–2015. The results of observations of the Gaia spacecraft on the 1.6-m infrared telescope of the Sayan Observatory are presented. The measured brightness of the spacecraft was 20.7–22m, which is close to the limiting magnitude of the telescope. The accuracy of these astrometric measurements was about one arcsecond. Possibilities for obtaining accurate astrometric data for the SRG spacecraft in orbit in the vicinity of L2 are discussed, as well as the required observing conditions and the volume of measurement data required for adequate prediction of the spacecraft motion.  相似文献   

6.
The evolution of nephelinitic melts in equilibrium with mica-bearing liquidus assemblages and melting relations have been studied on two silica-undersaturated joins of the KAlSiO4– Mg2SiO4– Ca2SiO4– SiO2– F system at atmospheric pressure by quench runs in sealed platinum capsules. Fluorine has been added to the batch compositions by the direct exchange of fluorine for oxygen (2F− = O2−). The first join is the pseudo-ternary Forsterite – Diopside – KAlSiO3F2 system. Forsterite, diopside, F-phlogopite and leucite crystallisation fields and a fluoride-silicate liquid immiscibility solvus are present on the liquidus surface of the join. Sub-liquidus and sub-solidus phases include akermanite, cuspidine, spinel, fluorite and some other minor fluorine phases. The second system is the pseudo-binary Akermanite – F-phlogopite join that intersects the Forsterite – Diopside – KAlSiO3F2 join. Akermanite, forsterite, diopside, F-phlogopite, leucite and cuspidine are found to crystallise on the join. Forsterite (fo) and leucite (lc) are related to F-phlogopite (phl) by a reaction with the fluorine-bearing liquid: fo + lc + l = phl, and the reaction proceeds until forsterite or leucite are completely consumed. The reaction temperature and resulting phase association depend on batch composition. Thus, leucite is not stable in the sub-solidus of the Akermanite – F-phlogopite join, but is preserved in a part of the Forsterite – Diopside – KAlSiO3F2 system where forsterite reacts out, or does not crystallise at all. The phlogopite-in reaction has an important effect on the composition of the coexisting liquid. The liquids initially saturated in forsterite evolve to extremely Ca rich, larnite-normative residuals. The experimental data show that larnite-normative melilitolites can crystallise from evolved melilititic melts generated from “normal” melanephelinitic parental magmas with no normative larnite. The evolution towards melilitites requires fractionation of phlogopite-bearing assemblages under volatile pressure. Received: 3 June 1997 / Accepted: 5 January 1998  相似文献   

7.
正1 Introduction Lithium resources are widely distributed in the oilfield brine from the Nanyishan district in the Qaidam Basin(Fan et al.,2007).The investigation of the thermodynamics and phase diagram of the brine system is valuable in providing the theoretic foundation and scientific guidance in the comprehensive exploitation of the mixture salts effectively.Comprehensive  相似文献   

8.
Facies analysis combined with sequence stratigraphic interpretation of the Upper Permian carbonate (Ca2) of NE Germany (i.e. northern basin margin of the Southern Permian Basin) confirm the existence of a rimmed platform with a steep and tectonically structured slope. The karstified A1 platform is overlain by deposits of a thin transgressive systems tract (TST) and a thick highstand systems tract (HST) which shows two larger-scale regressive shallowing-upwards cycles (4th order) with typical stacking patterns of small-scale cycles (5th order). The TST consists of bitumen-rich mudstones with reworked clasts of anhydrite and early cemented wacke- to grainstones, and it shows two, probably 5th-order, deepening-upwards cycles. The first larger-scale shallowing-up cycle on the Ca2 platform (4th-order) is dominated by aggradation of the bar and shoal deposits, whereas the second one is dominated by progradation. The tops of both cycles are characterised by erosional and exposure surfaces. Various types of small-scale shallowing-upwards cycles (5th-order) are observed in the bar, in the intertidal and in the algal-dominated supratidal environment, showing pronounced transgressive boundaries. On the slope and in the basin, equally thick TST and HST are observed. These incorporate carbonate turbidites which indicate "highstand shedding" from the platform. Various orders of relative sea-level variations are discussed. Controlling factors include tectonics, climate, and eustatic processes. A combined carbonate and evaporite sequence was found on the upper Ca2 slope, which may indicate a Ca2-lowstand systems wedge.  相似文献   

9.
The polymorphic relations for Mg3(PO4)2 and Mg2PO4OH have been determined by reversed experiments in the temperature-pressure (T-P) range 500–1100 °C, 2–30 kbar. The phase transition between the low-pressure phase farringtonite and Mg3(PO4)2-II, the Mg analogue of sarcopside, is very pressure dependent and was tightly bracketed between 625 °C, 7 kbar and 850 °C, 9 kbar. The high-temperature, high-pressure polymorph, Mg3(PO4)2-III, is stable above 1050 °C at 10 kbar and above 900 °C at 30 kbar. The low-pressure stability of farringtonite is in keeping with its occurrence in meteorites. The presence of iron stabilizes the sarcopside-type phase towards lower P. From the five Mg2PO4OH polymorphs only althausite, holtedahlite, β-Mg2PO4OH (the hydroxyl analogue of wagnerite) and ɛ-Mg2PO4OH were encountered. Relatively speaking, holtedahlite is the low-temperature phase (<600 °C), ɛ-Mg2PO4OH the high-temperature, low-pressure phase and β-Mg2PO4OH the high-temperature, high-pressure phase, with an intervening stability field for althausite which extends from about 3 kbar at 500 °C to about 12 kbar at 800 °C. Althausite and holtedahlite are to be expected in F-free natural systems under most geological conditions; however, wagnerite is the most common Mg-phosphate mineral, implying that fluorine has a major effect in stabilizing the wagnerite structure. Coexisting althausite and holtedahlite from Modum, S. Norway, show that minor fluorine is strongly partitioned into althausite (KD F/OH≈ 4) and that holtedahlite may incorporate up to 4 wt% SiO2. Synthetic phosphoellenbergerite has a composition close to (Mg0.9□0.1)2Mg12P8O38H8.4. It is a high-pressure phase, which breaks down to Mg2PO4OH + Mg3(PO4)2 + H2O below 8.5 kbar at 650 °C, 22.5 kbar at 900 °C and 30 kbar at 975 °C. The stability field of the phosphate end-member of the ellenbergerite series extends therefore to much lower P and higher T than that of the silicate end-members (stable above 27 kbar and below ca. 725 °C). Thus the Si/P ratio of intermediate members of the series has a great barometric potential, especially in the Si-buffering assemblage with clinochlore + talc + kyanite + rutile + H2O. Application to zoned ellenbergerite crystals included in the Dora-Maira pyrope megablasts, western Alps, reveals that growth zoning is preserved at T as high as 700–725 °C. However, the record of attainment of the highest T and/or of decreasing P through P-rich rims (1 to 2 Si pfu) is only possible in the presence of an additional phosphate phase (OH-bearing or even OH-dominant wagnerite in these rocks), otherwise the trace amounts of P in the system remain sequestered in the core of Si-rich crystals (5 to 8 Si pfu) and can no longer react. Received: 7 April 1995 / Accepted: 12 November 1997  相似文献   

10.
In this paper, the behaviors of aqueous zinc sorption by hydroxyapatite in the co-existence of Pb^2＋, Cd^2＋ and Cu^2＋ are investigated, the effects of Pb^2＋, Cd^2＋ and Cu^2＋ on the sorption of Zn^2＋ are discussed, and the hydroxyapatite sorption capabilities for Pb^2＋, Cd^2＋, Cu^2＋ and Zn^2＋ are compared. The experimental results show that the Zn^2＋ removal efficiency decreases gradually with the increase of the Cd^2＋ concentration of the solution, and there is no sorption preference between Cd^2＋ and Zn^2＋. On the other hand, the Zn^2＋ removal efficiency rapidly decreases rapidly with the increase of the Cu^2＋ concentration of the solution, and there is a clear sorption preference between Cu^2＋ and Zn^2＋. It is noticed that the Zn^2＋ removal efficiency is hardly changed with the variance of Pb^2＋ concentration because the removal mechanisms for these two ions are totally different. It is concluded that the adsorption affinities of the heavy metals for the hydroxyapatite follows this sequence： pb^2＋〉 Cu^2＋〉 Cd^2＋〉 Zn^2＋.  相似文献   

11.
To elaborate physicochemical models for the origin of crystalline rocks, experimental studies of the field of high-alumina assemblages of the system CaO–MgO–Al2O3–SiO2 were carried out at 10–30 kbar and 1250–1535 °C. We have determined the phase relations between the melt (L) and An, Sp, Cpx, Cor, and Ga, the slope of the rays of the monovariant reactions An + Sp = Cpx + Cor + (Ga) and L = Cpx +Ga + Cor + Sp, the position of the nonvariant point (An, Sp, Cpx, Cor, Ga, L), and the compositions of phases participating in these reactions. Based on a topological analysis of the studied segment of the system CaO–MgO–Al2O3–SiO2, we have substantiated that “eclogitization” must follow the reaction Opx + An + Sp = Cpx + Ga. A fundamental continuous series of eutectic monovariant equilibria was observed: L = Cpx + Opx + Fo + An, L = Cpx + Opx + An + Sp, L = Cpx (+ Ga) + An + Sp, and L = Cpx + Cor (+ Ga) + An. A change in the melt composition in this series of eutectic reactions depending on pressure must reflect the most likely magma genesis trend in nature. Comparision of the composition fields in which the above series of reactions is observed with the composition fields of the rocks of magmatic formations showed that this series is most similar to the alkali-earth series of rocks. The mineralogical compositions of cumulates and phenocrysts found in the effusive and dike varieties of these rocks correspond to unique sets of subsolidus phase associations and individual subsolidus phases crystallizing in this fundamental eutectic series.  相似文献   

12.
《Applied Geochemistry》2002,17(10):1305-1312
The effect of different drying conditions on the stability of NaNd(CO3)·6H2O and NaEu(CO3)·6H2O and the identity of the decomposition product have been investigated. The rate of decomposition and the nature of the altered phases are dependant on the drying conditions used. When the phases are oven dried at 120 °C, the decomposition is immediate and the phase completely alters to Nd2(CO3)3 or Eu2(CO3)3 respectively. Under less severe drying conditions, the Na rare earth carbonate phases alter to Nd2(CO3)3·8H2O and Eu2(CO3)3·8H2O over a period of 24–48 h, but they can be kept indefinitely in a water saturated environment. The implications for using Nd and Eu as actinide analogues are discussed.  相似文献   

13.
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14.
In situ high-temperature synchrotron radiation powder diffraction patterns were taken from room temperature to T = 740°C from synthetic feldspars along the join CaAl2Si2O8–SrAl2Si2O8 (An–SrF). Three samples of composition An95SrF5, An90SrF10 and An85SrF15 were investigated, and the evolution of cell parameters with T was determined by Rietveld analysis of powder X-ray diffraction patterns. The high-temperature $P\bar 1{\text{-}}I\bar 1$ phase transition, previously observed with T c = 241°C in anorthite, was found in An95SrF5, An90SrF10 and An85SrF15 feldspars at T c = 233(5)°, 195(2)° and 174(2)°C respectively. The transition was revealed by the disappearance of critical reflections and variations in the rate of change of cell parameters with temperature. A significant, although small (between 0.0025 and 0.0012 at room temperature), spontaneous strain could be measured, allowing the thermodynamic behaviour of the transition to be modelled. A second-order trend for An90SrF10 and An85SrF15 [β = 0.504(7) and 0.505(7) respectively] or nearly second-order for An95SrF5[β = 0.458(4)] was observed in contrast with tricritical behaviour of end member anorthite. An extrapolation of the T c versus composition to room temperature indicates that the critical composition for the $P\bar 1$ phase is An60SrF40.  相似文献   

15.
The type and kinetics of metamorphic CO2-producing processes in metacarbonate rocks is of importance to understand the nature and magnitude of orogenic CO2 cycle. This paper focuses on CO2 production by garnet-forming reactions occurring in calc-silicate rocks. Phase equilibria in the CaO–FeO–Al2O3–SiO2–CO2–H2O (CFAS–CO2–H2O) system are investigated using P–T phase diagrams at fixed fluid composition, isobaric T–X(CO2) phase diagram sections and phase diagram projections in which fluid composition is unconstrained. The relevance of the CFAS–CO2–H2O garnet-bearing equilibria during metamorphic evolution of calc-silicate rocks is discussed in the light of the observed microstructures and measured mineral compositions in two representative samples of calc-silicate rocks from eastern Nepal Himalaya. The results of this study demonstrate that calc-silicate rocks may act as a significant CO2 source during prograde heating and/or early decompression. However, if the system remains closed, fluid–rock interactions may induce hydration of the calc-silicate assemblages and the in situ precipitation of graphite. The interplay between these two contrasting processes (production of CO2-rich fluids vs. carbon sequestration through graphite precipitation) must be considered when dealing with a global estimate of the role exerted by decarbonation processes on the orogenic CO2 cycle.  相似文献   

16.
 An in situ high-pressure (HP) X-ray diffraction investigation of synthetic diopside and of the Ca0.8Mg1.2Si2O6 clinopyroxene (Di80En20) was performed up to respectively P=40.8 and 15.1 GPa, using high brilliance synchrotron radiation. The compression of the cell parameters is markedly anisotropic, with βb ⋙ βc > βa > βasinβ for any pressure range and for both diopside and Di80En20. The compressibility along the crystallographic axes decreases significantly with pressure and is higher in Di80En20 than in diopside. The β cell parameter decreases as well with pressure, at a higher rate in Di80En20. The cell volume decreases at almost the same rate for the two compositions, since in diopside a higher compression along a* occurs. A change in the mechanism of deformation at P higher than about 5–10 GPa is suggested for both compositions from the analysis of the strain induced by compression. In diopside at lower pressures, the deformation mainly occurs, at a similar rate, along the b axis and at a direction 145° from the c axis on the (0 1 0) plane. At higher pressures, instead, the deformation occurs mostly along the b axis. In Di80En20 the orientation of the strain axes is the same as in diopside. The substitution of Ca with Mg in the M2 site induces at a given pressure a higher deformation on (0 1 0) with respect to diopside, but a similar change in the compressional behaviour is found. Changes in the M2 polyhedron with pressure can explain the above compressional behaviour. A third-order Birch-Murnaghan equation of state was fit to the retrieved volumes, with K=105.1(9) GPa, K′=6.8(1) for diopside and K=107.3(1.4) GPa, K′=5.7(3) for Di80En20; the same equation can be applied for any pressure range. The elasticity of diopside is therefore not significantly affected by Mg substitution into the M2 site, in contrast to the significant stiffening occurring for Ca substitution into Mg-rich orthopyroxenes. Received: 3 January 2000 / Accepted: 21 May 2000  相似文献   

17.
The incorporation of hydrogen in enstatite in a hydrous system containing various amounts of NaCl was investigated at 25 kbar. The hydrogen content in enstatite shows a clear negative correlation to the NaCl-concentration in the system. The most favourable explanation is the reduction of water fugacity due to dilution. Other reasons for the limited hydrogen incorporation at high NaCl levels, such as a significant influence of Na+ on the defect chemistry or an exchange between OH- and Cl−in enstatite, appear much less important. A partition coefficient D Na En/Fluid = 0.0013 could be determined, demonstrating that Na is less incompatible in enstatite than H. The new results support the idea that dissolved components have to be considered when the total hydrogen storage capacity in nominally anhydrous minerals is estimated, especially in geological settings with high levels of halogens, such as subduction zones.  相似文献   

18.
 One of the main uncertainties in mineralogical models of the Earth's lower mantle is the nature of the aluminous mineral: it is not clear whether Al forms its own minerals or is mainly contained in (Mg,Fe)SiO3-perovskite. This question is very important, since it is known that if Al were mainly hosted by perovskite, it would radically change Fe/Mg-partitioning and phase equilibria between mantle minerals, and also alter many physical and chemical properties of perovskite, which is currently believed to comprise ca. 70% of the volume of the lower mantle. This, in turn, would require us to reconsider many of our geochemical and geophysical models for the lower mantle. This work considers the possibility of a V3O5-type structured modification of Al2SiO5 to be the main host of Al in the lower mantle, as proposed by previous workers. We report ab initio calculations, based on density functional theory within the generalised gradient approximation (GGA) with plane wave basis set and nonlocal pseudopotentials. We consider polymorphs of Al2SiO5 (kyanite, andalusite, sillimanite, and hypothetical V3O5-like and pseudobrookite-like phases), SiO2 (stishovite, quartz) and Al2O3 (corundum). Computational conditions (e.g., plane-wave energy cutoff, Brillouin zone sampling) were carefully chosen in order to reproduce small energy changes associated with phase transitions between the Al2SiO5 polymorphs. Good agreement of crystal structures, bulk moduli, atomisation energies and the phase diagram of Al2SiO5 with experimental data was found. Strong disagreement between the calculated lattice parameters and density of V3O5-like phase of Al2SiO5 and experimental values, assigned to it by previous workers, suggests that a V3O5-structured phase of Al2SiO5 was never observed experimentally. In addition, we found that the most stable high-pressure assembly in Al2SiO5 system is corundum+stishovite, and the value of the transition pressure at T = O K (113 kbar) is in excellent agreement with experimental estimates (95–150 kbar). We explain the instability of octahedrally coordinated silicates of Al to decomposition on the basis of Pauling's second rule. Received: 18 May 1999 / Accepted: 5 November 1999  相似文献   

19.
This work aims to quantify sulfate ion concentrations in the system Na2SO4-H2O using Raman micro-spectroscopy.Raman spectra of sodium sulfate solutions with known concentrations were collected at ambient temperature（293 K） and in the 500 cm1-4000 cm-1 spectral region.The results indicate that the intensity of the SO42- band increases with increasing concentrations of sulfate ion.A linear correlation was found between the concentration of SO42-（c） and parameter I1,which represents the ratio of the area of the SO42- band to that of the O-H stretching band of water（As/Aw）:I1=-0.00102+0.01538 c.Furthermore,we deconvoluted the O-H stretching band of water(2800 cm-1-3800 cm-1) at 3232 and 3430 cm-1 into two sub-Gaussian bands,and then defined Raman intensity of the two sub-bands as ABi(3232 cm-1) and AB2(3430 cm-1),defined the full width of half maximum（FWHM） of the two sub-bands as WB1(3232 cm-1) and WB2(3430 cm-1).A linear correlation between the concentration of SO42-（c） and parameter I2,which represents the ratio of Raman intensity of SO42-（As）(in 981 cm-1) to(AB1+AB2),was also established:I2=-0.0111+0.3653 c.However,no correlations were found between concentration of SO42-（c） and FWHM ratios,which includes the ratio of FWHM of SO42-（Ws） to WB1 WB2 and WB1+B2(the sum of WB1 and WB2),suggesting that FWHM is not suitable for quantitative studies of sulfate solutions with Raman spectroscopy.A comparison of Raman spectroscopic studies of mixed Na2SO4 and NaCI solutions with a constant SO42- concentration and variable CI- concentrations suggest that the I\ parameter is affected by CI-,whereas the I2 parameter was not.Therefore,even if the solution is not purely Na2SO4-H2O,SO42- concentrations can still be calculated from the Raman spectra if the H2O band is deconvoluted into two sub-bands,making this method potentially applicable to analysis of natural fluid inclusions.  相似文献   

20.
In order to determine the mechanisms of formation and properties of natural hydrosilicate liquids (HSLs), which are formed during the transition from magmatic to hydrothermal mineral formation in granitic pegmatites and rare-metal granites, the formation of HSLs was experimentally studied in the Na2O-SiO2-H2O, Na2O-Al2O3-SiO2-H2O, and Na2O-K2O-Li2O-Al2O3-SiO2-H2O systems at 600°C and 1.5 kbar. It was shown that the sequential extension of composition does not suppress HSL formation in the systems and expands the stability field of this phase. However, HSLs formed in extended chemical systems have different structure and properties: the addition of alumina induces some compression of the structure of the silicate framework of HSLs, which results in a decrease in water content in this phase and probably hinders the reversibility of its dehydration. It was demonstrated that HSL can be formed by the coagulation of silica present in a silica-oversaturated alkaline aqueous fluid. It was supposed that the HSL formed during this process has a finely dispersed structure. It was argued that anomalous enrichment in some elements in natural HSLs can be due to their sorption by the extensively developed surface of HSL at the moment of its formation.  相似文献   

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