The structural stability of methane hydrate under pressure at room temperature was examined by both in-situ single-crystal and powder X-ray diffraction techniques on samples with structure types I, II, and H in diamon...The structural stability of methane hydrate under pressure at room temperature was examined by both in-situ single-crystal and powder X-ray diffraction techniques on samples with structure types I, II, and H in diamond-anvil ceils. The diffraction data for types II （slI） and H （sH） were refined to the known structures with space groups Fd3m and P63/mmc, respectively. Upon compression, sl methane hydrate transforms to the sll phase at 120 MPa, and then to the sH phase at 600 MPa. The slI methane hydrate was found to coexist locally with sI phase up to 500 MPa and with sH phase up to 600 MPa. The pure sH structure was found to be stable between 600 and 900 MPa. Methane hydrate decomposes at pressures above 3 GPa to form methane with the orientationally disordered Fm3m structure and ice VII （Pn3m）. The results highlight the role of guest （CH4）-host （H2O） interactions in the stabilization of the hydrate structures under pressure.展开更多
The amount of literature on both melting and thermal conductivity of iron at Earth’s core conditions is overwhelming and the discrepancies are very large.There is a broad range of experimental techniques each of whic...The amount of literature on both melting and thermal conductivity of iron at Earth’s core conditions is overwhelming and the discrepancies are very large.There is a broad range of experimental techniques each of which is flawed to a certain degree,which may explain the discrepancy.In this report,we present new data using a different method for determining the phase behavior and resistivity of iron in the laser-heated diamond cell by measuring the electrical resistance of both solid and liquid iron wires.The experiment avoids some of the major flaws of previous experiments,the most important of which is the detection of the onset of melting.These measurements confirm a shallow melting curve found earlier and the resistivity data imply a trend towards low thermal conductivity in the liquid outer core.展开更多
The lower mantle makes up more than a half of our planet’s volume. Mineralogical and petrological experiments on realistic bulk compositions under high pressure–temperature (P–T) conditions are essential for unders...The lower mantle makes up more than a half of our planet’s volume. Mineralogical and petrological experiments on realistic bulk compositions under high pressure–temperature (P–T) conditions are essential for understanding deep mantle processes. Such high P–T experiments are commonly conducted in a laser-heated diamond anvil cell, producing a multiphase assemblage consisting of 100 nm to submicron crystallite grains. The structures of these lower mantle phases often cannot be preserved upon pressure quenching;thus, in situ characterization is needed. The X-ray diffraction (XRD) pattern of such a multiphase assemblage usually displays a mixture of diffraction spots and rings as a result of the coarse grain size relative to the small X-ray beam size (3–5 lm) available at the synchrotron facilities. Severe peak overlapping from multiple phases renders the powder XRD method inadequate for indexing new phases and minor phases. Consequently, structure determination of new phases in a high P–T multiphase assemblage has been extremely difficult using conventional XRD techniques. Our recent development of multigrain XRD in high-pressure research has enabled the indexation of hundreds of individual crystallite grains simultaneously through the determination of crystallographic orientations for these individual grains. Once indexation is achieved, each grain can be treated as a single crystal. The combined crystallographic information from individual grains can be used to determine the crystal structures of new phases and minor phases simultaneously in a multiphase system. With this new development, we have opened up a new area of crystallography under the high P–T conditions of the deep lower mantle. This paper explains key challenges in studying multiphase systems and demonstrates the unique capabilities of high-pressure multigrain XRD through successful examples of its applications.展开更多
We consider a steady-state(but transient)situation in which a warm dense aggregate is a two-temperature system with equilibrium electrons at temperature T_(e),ions at T_(i),and T_(e)≠T_(i).Such states are achievable ...We consider a steady-state(but transient)situation in which a warm dense aggregate is a two-temperature system with equilibrium electrons at temperature T_(e),ions at T_(i),and T_(e)≠T_(i).Such states are achievable by pump–probe experiments.For warm dense hydrogen in such a twotemperature situation,we investigate nuclear quantum effects(NQEs)on structure and thermodynamic properties,thereby delineating the limitations of ordinary ab initio molecular dynamics.We use path integral molecular dynamics(PIMD)simulations driven by orbital-free density functional theory(OFDFT)calculations with state-of-the-art noninteracting free-energy and exchange-correlation functionals for the explicit temperature dependence.We calibrate the OFDFT calculations against conventional(explicit orbitals)Kohn–Sham DFT.We find that when the ratio of the ionic thermal de Broglie wavelength to the mean interionic distance is larger than about 0.30,the ionic radial distribution function is meaningfully affected by the inclusion of NQEs.Moreover,NQEs induce a substantial increase in both the ionic and electronic pressures.This confirms the importance of NQEs for highly accurate equation-of-state data on highly driven hydrogen.For Te>20 kK,increasing Te in the warm dense hydrogen has slight effects on the ionic radial distribution function and equation of state in the range of densities considered.In addition,we confirm that compared with thermostatted ring-polymer molecular dynamics,the primitive PIMD algorithm overestimates electronic pressures,a consequence of the overly localized ionic description from the primitive scheme.展开更多
Diamond anvil cell techniques have been improved to allow access to the multimegabar ultrahigh-pressure region for exploring novel phenomena in condensedmatter.However,the onlyway to determine crystal structures of ma...Diamond anvil cell techniques have been improved to allow access to the multimegabar ultrahigh-pressure region for exploring novel phenomena in condensedmatter.However,the onlyway to determine crystal structures of materials above 100 GPa,namely,X-ray diffraction(XRD),especially for lowZ materials,remains nontrivial in the ultrahigh-pressure region,even with the availability of brilliant synchrotron X-ray sources.In thiswork,we performa systematic study,choosing hydrogen(the lowest X-ray scatterer)as the subject,to understand how to better perform XRD measurements of low Z materials at multimegabar pressures.The techniques that we have developed have been proved to be effective in measuring the crystal structure of solid hydrogen up to 254GPa at room temperature[C.Ji et al.,Nature 573,558–562(2019)].Wepresent our discoveries and experienceswith regard to several aspects of thiswork,namely,diamond anvil selection,sample configuration for ultrahigh-pressure XRDstudies,XRDdiagnostics for low Z materials,and related issues in data interpretation and pressure calibration.Webelieve that these methods can be readily extended to other low Z materials and can pave the way for studying the crystal structure of hydrogen at higher pressures,eventually testing structural models of metallic hydrogen.展开更多
Polyimide（PI） is a type of important membrane material. A soluble polymer was synthesized from 4,4′-（hexafluoroisopropylidene） diphthalic anhydride（6FDA） and 2,2-bis[4-（4-aminophenoxy） phenyl] hexafluoroprop...Polyimide（PI） is a type of important membrane material. A soluble polymer was synthesized from 4,4′-（hexafluoroisopropylidene） diphthalic anhydride（6FDA） and 2,2-bis[4-（4-aminophenoxy） phenyl] hexafluoropropane（BDAF） by the two-step polymerization method. The polymer was proved to be polyimide 6FDA-BDAF by the Fourier transform infrared（FT-IR）, the 1H-NMR and ^（19）F-NMR spectra. An asymmetric membrane was prepared with the synthesized polyimide 6FDA-BDAF, it was porous in the 50 μm height bulk and dense in a 3–5 μm height surface. The membrane was used to separate n-heptane/thiophene mixtures by pervaporation with sulfur（S） contents from 50 to 900 μg g^（–1）. The total flux was enlarged from 7.96 to 37.61 kg m^（–2） h^（–1） with temperature increasing from 50 to 90°C. The membrane＇s enrichments factor for thiophene were about 3.13 and dependent on the experimental conditions. The experimental results demonstrated that polyimide 6FDA-BDAF would be a potential membrane material for desulfurization and controlled release of the S-containing fertilizer.展开更多
Two kinds of glassy sulfurs are synthesized by thrapid compression method from liquid sulfur at temperatures below and above the X-transition point. The glassy sulfur has different colors and transparencies, depending...Two kinds of glassy sulfurs are synthesized by thrapid compression method from liquid sulfur at temperatures below and above the X-transition point. The glassy sulfur has different colors and transparencies, depending on temperature, which may inherit some structural information from the transition. Raman spectrum studies of these samples show that a large fraction of polymeric chains exist in the glassy sulfur, even in the one solidified from T 〈 Tλ. We find that a higher compression rate instead of a higher temperature of the parent liquid captures more polymeric chains. Pressure-induced glassy sulfur presents high thermal stability compared with temperature quenched glassy sulfur and could transform into liquid sulfur directly without crystallization through an abnormal exothermic melting course. High energy x-ray diffraction is utilized to study the local order of the pressure-induced glassy sulfur.展开更多
We present a large sample of candidate galaxies at z ≈ 7 - 10, selected in the Hubble Ultra Deep Field using the new observations of the Wide Field Camera 3 that was recently installed on the Hubble Space Telescope. ...We present a large sample of candidate galaxies at z ≈ 7 - 10, selected in the Hubble Ultra Deep Field using the new observations of the Wide Field Camera 3 that was recently installed on the Hubble Space Telescope. Our sample is composed of 20 z850-dropouts （four new discoveries）, 15 Y105-dropouts （nine new discoveries） and 20 J125-dropouts （all new discoveries）. The surface densities of the Z850-dropouts are close to what was predicted by earlier studies, however, those of the Y105- and J125-dropouts are quite unexpected. While no Y105- or J125-dropouts have been found at AB ≤ 28.0 mag, their surface densities seem to increase sharply at fainter levels. While some of these candidates seem to be close to foreground galaxies and thus could possibly be gravitationally lensed, the overall surface densities after excluding such cases are still much higher than what would be expected if the luminosity function does not evolve from z ～ 7 to 10. Motivated by such steep increases, we tentatively propose a set of Schechter function parameters to describe the luminosity functions at z ≈8 and 10. As compared to their counterpart at z ≈ 7, here L^＊ decreases by a factor of ～ 6.5 and Ф^＊ increases by a factor of 17-90. Although such parameters are not yet demanded by the existing observations, they are allowed and seem to agree with the data better than other alternatives. If these luminosity functions are still valid beyond our current detection limit, this would imply a sudden emergence of a large number of low-luminosity galaxies when looking back in time to z ≈ 10, which, while seemingly exotic, would naturally fit in the picture of the cosmic hydrogen reionization. These early galaxies could easily account for the ionizing photon budget required by the reionization, and they would imply that the global star formation rate density might start from a very high value at z ≈ 10, rapidly reach the minimum at z≈ 7, and start to rise again towards z ≈ 6. In this scenario, the majority of the stellar mass that the universe assembled through the reionization epoch seems still undetected by current observations at z ≈ 6.展开更多
基金HPSynC is supported as part of EFree,an EnergyFrontier Research Center funded by the U.S.Department of Energy(DOE),Office of Science, Office of Basic Energy Sciences(BES) under Award Number DE-SC0001057HPCAT is supported by CIW,CDAC,UNLV and LLNL through funding from DOE-NNSA,DOE-BES and NSFAPS is supported by DOE-BES,under Contract No.DE-AC02-06CH 11357
文摘The structural stability of methane hydrate under pressure at room temperature was examined by both in-situ single-crystal and powder X-ray diffraction techniques on samples with structure types I, II, and H in diamond-anvil ceils. The diffraction data for types II （slI） and H （sH） were refined to the known structures with space groups Fd3m and P63/mmc, respectively. Upon compression, sl methane hydrate transforms to the sll phase at 120 MPa, and then to the sH phase at 600 MPa. The slI methane hydrate was found to coexist locally with sI phase up to 500 MPa and with sH phase up to 600 MPa. The pure sH structure was found to be stable between 600 and 900 MPa. Methane hydrate decomposes at pressures above 3 GPa to form methane with the orientationally disordered Fm3m structure and ice VII （Pn3m）. The results highlight the role of guest （CH4）-host （H2O） interactions in the stabilization of the hydrate structures under pressure.
基金supported by the National Science Foundation (No. 1248553)
文摘The amount of literature on both melting and thermal conductivity of iron at Earth’s core conditions is overwhelming and the discrepancies are very large.There is a broad range of experimental techniques each of which is flawed to a certain degree,which may explain the discrepancy.In this report,we present new data using a different method for determining the phase behavior and resistivity of iron in the laser-heated diamond cell by measuring the electrical resistance of both solid and liquid iron wires.The experiment avoids some of the major flaws of previous experiments,the most important of which is the detection of the onset of melting.These measurements confirm a shallow melting curve found earlier and the resistivity data imply a trend towards low thermal conductivity in the liquid outer core.
基金the National Natural Science Foundation of China (41574080 and U1530402).
文摘The lower mantle makes up more than a half of our planet’s volume. Mineralogical and petrological experiments on realistic bulk compositions under high pressure–temperature (P–T) conditions are essential for understanding deep mantle processes. Such high P–T experiments are commonly conducted in a laser-heated diamond anvil cell, producing a multiphase assemblage consisting of 100 nm to submicron crystallite grains. The structures of these lower mantle phases often cannot be preserved upon pressure quenching;thus, in situ characterization is needed. The X-ray diffraction (XRD) pattern of such a multiphase assemblage usually displays a mixture of diffraction spots and rings as a result of the coarse grain size relative to the small X-ray beam size (3–5 lm) available at the synchrotron facilities. Severe peak overlapping from multiple phases renders the powder XRD method inadequate for indexing new phases and minor phases. Consequently, structure determination of new phases in a high P–T multiphase assemblage has been extremely difficult using conventional XRD techniques. Our recent development of multigrain XRD in high-pressure research has enabled the indexation of hundreds of individual crystallite grains simultaneously through the determination of crystallographic orientations for these individual grains. Once indexation is achieved, each grain can be treated as a single crystal. The combined crystallographic information from individual grains can be used to determine the crystal structures of new phases and minor phases simultaneously in a multiphase system. With this new development, we have opened up a new area of crystallography under the high P–T conditions of the deep lower mantle. This paper explains key challenges in studying multiphase systems and demonstrates the unique capabilities of high-pressure multigrain XRD through successful examples of its applications.
基金The majority of this work was done while D.K.was a visitor at the University of Florida.He was supported by the Science Challenge Project of China under Grant No.TZ2016001the NSFC under Grant No.11874424+3 种基金the National Key R&D Program of China under Grant No.2017YFA0403200He also acknowledges support by the China Scholarship Council.K.L.(for the majority of the work done while at the University of Florida)S.B.T.were supported by U.S.Department of Energy Grant No.DE-SC0002139Most of the computations were performed on the HiPerGator-II system at the University of Florida.
文摘We consider a steady-state(but transient)situation in which a warm dense aggregate is a two-temperature system with equilibrium electrons at temperature T_(e),ions at T_(i),and T_(e)≠T_(i).Such states are achievable by pump–probe experiments.For warm dense hydrogen in such a twotemperature situation,we investigate nuclear quantum effects(NQEs)on structure and thermodynamic properties,thereby delineating the limitations of ordinary ab initio molecular dynamics.We use path integral molecular dynamics(PIMD)simulations driven by orbital-free density functional theory(OFDFT)calculations with state-of-the-art noninteracting free-energy and exchange-correlation functionals for the explicit temperature dependence.We calibrate the OFDFT calculations against conventional(explicit orbitals)Kohn–Sham DFT.We find that when the ratio of the ionic thermal de Broglie wavelength to the mean interionic distance is larger than about 0.30,the ionic radial distribution function is meaningfully affected by the inclusion of NQEs.Moreover,NQEs induce a substantial increase in both the ionic and electronic pressures.This confirms the importance of NQEs for highly accurate equation-of-state data on highly driven hydrogen.For Te>20 kK,increasing Te in the warm dense hydrogen has slight effects on the ionic radial distribution function and equation of state in the range of densities considered.In addition,we confirm that compared with thermostatted ring-polymer molecular dynamics,the primitive PIMD algorithm overestimates electronic pressures,a consequence of the overly localized ionic description from the primitive scheme.
基金This research was supported by the National Natural Science Foundation of China under Award No.U1930401the Department of Energy(DOE),Office of Basic Energy Science,Division of Materials Sciences and Engineering under Award No.DE-FG02-99ER45775
文摘Diamond anvil cell techniques have been improved to allow access to the multimegabar ultrahigh-pressure region for exploring novel phenomena in condensedmatter.However,the onlyway to determine crystal structures of materials above 100 GPa,namely,X-ray diffraction(XRD),especially for lowZ materials,remains nontrivial in the ultrahigh-pressure region,even with the availability of brilliant synchrotron X-ray sources.In thiswork,we performa systematic study,choosing hydrogen(the lowest X-ray scatterer)as the subject,to understand how to better perform XRD measurements of low Z materials at multimegabar pressures.The techniques that we have developed have been proved to be effective in measuring the crystal structure of solid hydrogen up to 254GPa at room temperature[C.Ji et al.,Nature 573,558–562(2019)].Wepresent our discoveries and experienceswith regard to several aspects of thiswork,namely,diamond anvil selection,sample configuration for ultrahigh-pressure XRDstudies,XRDdiagnostics for low Z materials,and related issues in data interpretation and pressure calibration.Webelieve that these methods can be readily extended to other low Z materials and can pave the way for studying the crystal structure of hydrogen at higher pressures,eventually testing structural models of metallic hydrogen.
基金support from the Key Technology R&D Program of China(2011BAD11B05)the National Nonprofit Institute Research Grant of Chinese Academy of Agricultural Sciences(2011-28,2013-17)+3 种基金supported by the National Basic Research Program of China(973 Program,2003CB615701)the National Natural Science Foundation of China(20576059,20676067,31572204)the China Petroleum&Chemical Corporation(SINOPEC Foundation,X505002)the China National Petroleum Corporation(CNPC)InnovationFoundation(05051143)
文摘Polyimide（PI） is a type of important membrane material. A soluble polymer was synthesized from 4,4′-（hexafluoroisopropylidene） diphthalic anhydride（6FDA） and 2,2-bis[4-（4-aminophenoxy） phenyl] hexafluoropropane（BDAF） by the two-step polymerization method. The polymer was proved to be polyimide 6FDA-BDAF by the Fourier transform infrared（FT-IR）, the 1H-NMR and ^（19）F-NMR spectra. An asymmetric membrane was prepared with the synthesized polyimide 6FDA-BDAF, it was porous in the 50 μm height bulk and dense in a 3–5 μm height surface. The membrane was used to separate n-heptane/thiophene mixtures by pervaporation with sulfur（S） contents from 50 to 900 μg g^（–1）. The total flux was enlarged from 7.96 to 37.61 kg m^（–2） h^（–1） with temperature increasing from 50 to 90°C. The membrane＇s enrichments factor for thiophene were about 3.13 and dependent on the experimental conditions. The experimental results demonstrated that polyimide 6FDA-BDAF would be a potential membrane material for desulfurization and controlled release of the S-containing fertilizer.
基金supported by the Joint Funds of the National Natural Science Foundation of China(Grant No.U1530402)the National Natural Science Foundation of China(Grant No.11004163)+2 种基金the Fundamental Research Funds for the Central Universities,China(Grant No.2682014ZT31)the Department of Energy National Nuclear Security Administration(Grant No.DE-NA0001974)the Department of Energy Basic Energy Sciences(Grant Nos.DE-FG02-99ER45775and DE-AC02-06CH11357)
文摘Two kinds of glassy sulfurs are synthesized by thrapid compression method from liquid sulfur at temperatures below and above the X-transition point. The glassy sulfur has different colors and transparencies, depending on temperature, which may inherit some structural information from the transition. Raman spectrum studies of these samples show that a large fraction of polymeric chains exist in the glassy sulfur, even in the one solidified from T 〈 Tλ. We find that a higher compression rate instead of a higher temperature of the parent liquid captures more polymeric chains. Pressure-induced glassy sulfur presents high thermal stability compared with temperature quenched glassy sulfur and could transform into liquid sulfur directly without crystallization through an abnormal exothermic melting course. High energy x-ray diffraction is utilized to study the local order of the pressure-induced glassy sulfur.
基金supported in part by the NASA JWST Interdisciplinary Scientist grant NAG5-12460 from GSFC
文摘We present a large sample of candidate galaxies at z ≈ 7 - 10, selected in the Hubble Ultra Deep Field using the new observations of the Wide Field Camera 3 that was recently installed on the Hubble Space Telescope. Our sample is composed of 20 z850-dropouts （four new discoveries）, 15 Y105-dropouts （nine new discoveries） and 20 J125-dropouts （all new discoveries）. The surface densities of the Z850-dropouts are close to what was predicted by earlier studies, however, those of the Y105- and J125-dropouts are quite unexpected. While no Y105- or J125-dropouts have been found at AB ≤ 28.0 mag, their surface densities seem to increase sharply at fainter levels. While some of these candidates seem to be close to foreground galaxies and thus could possibly be gravitationally lensed, the overall surface densities after excluding such cases are still much higher than what would be expected if the luminosity function does not evolve from z ～ 7 to 10. Motivated by such steep increases, we tentatively propose a set of Schechter function parameters to describe the luminosity functions at z ≈8 and 10. As compared to their counterpart at z ≈ 7, here L^＊ decreases by a factor of ～ 6.5 and Ф^＊ increases by a factor of 17-90. Although such parameters are not yet demanded by the existing observations, they are allowed and seem to agree with the data better than other alternatives. If these luminosity functions are still valid beyond our current detection limit, this would imply a sudden emergence of a large number of low-luminosity galaxies when looking back in time to z ≈ 10, which, while seemingly exotic, would naturally fit in the picture of the cosmic hydrogen reionization. These early galaxies could easily account for the ionizing photon budget required by the reionization, and they would imply that the global star formation rate density might start from a very high value at z ≈ 10, rapidly reach the minimum at z≈ 7, and start to rise again towards z ≈ 6. In this scenario, the majority of the stellar mass that the universe assembled through the reionization epoch seems still undetected by current observations at z ≈ 6.
