Dileptons as Probes of High-Density Hadronic Matter Results from the SPS Heavy-Ion Programm
海洋学复习资料(董志南整理)
海洋学复习资料(董志南整理)个⼈观点,仅供参考,如有异议,欢迎讨论,敬请不吝赐教——董志南Water and Ocean Structure1.Why is water a polar molecule? What properties of water derive from its polar nature?Because Water structure is: one oxygen atom is in the above direction, two hydrogen atoms below are connected to the oxygen atoms. the bond angle of them is about 105 degrees,. The positively charged center of water is in the following, while the negative one is in the above. The two centers do not coincide, Polarity can not cancel each other out.Cohesion– the ability of water molecules to stick to each other, creating surface tensionAdhesion –the tendency of water molecules to stick to other materials, a good solventDissolving Property of WaterThese propertiese derive from water polar nature.2.How is heat different from temperature?Temperature is a measurement of the heat content of a body. Heat content is energy expressed in Joules or Calories. heat is thermal energy transferred from one object to another because of a temperature difference。
中国地质大学(北京)考博专业英复习材料
晶) is said to have a porphyritic texture(斑状结构). The classification of fine-grained rocks, then, is based on the proportion of minerals which form phenocrysts and these phenocrysts (斑晶)reflect the general composition of the remainder(残留) of the rock. The fine-grained portion of a porphyritic(斑岩) rock is generally referred to as the groundmass(基质) of the phenocrysts. The terms "porphyritic" and "phenocrysts" are not restricted to fine-grained rocks but may also apply to coarse-grained rocks which contain a few crystals distinctly larger than the remainder. The term obsidian(黑曜岩) refers to a glassy rock of rhyolitic(流纹岩) composition. In general, fine-grained rocks consisting of small crystals cannot readily be distinguished from③ glassy rocks in which no crystalline material is present at all. The obsidians, however, are generally easily recognized by their black and highly glossy appearanceass of the same composition as obsidian. Apparently the difference between the modes of formation of obsidian and pumice is that in pumice the entrapped water vapors have been able to escape by a frothing(起泡) process which leaves a network of interconnected pore(气孔) spaces, thus giving the rock a highly porous (多孔的)and open appearance(外观较为松散). ④ Pegmatite(结晶花岗岩) is a rock which is texturally(构造上地) the exact opposite of obsidian. ⑤ Pegmatites are generally formed as dikes associated with major bodies of granite (花岗岩) . They are characterized by extremely large individual crystals (单个晶体) ; in some pegmatites crystals up to several tens of feet in length(宽达几十英尺)have been identified, but the average size is measured in inches (英寸) . Most mineralogical museums contain a large number of spectacular(壮观的) crystals from pegmatites. Peridotite(橄榄岩) is a rock consisting primarily of olivine, though some varieties contain pyroxene(辉石) in addition. It occurs only as coarse-grained intrusives(侵入), and no extrusive(喷出的) rocks of equivalent chemical composition have ever been found. Tuff (凝灰岩)is a rock which is igneous in one sense (在某种意义上) and sedimentary in another⑥. A tuff is a rock formed from pyroclastic (火成碎 屑的)material which has been blown out of a volcano and accumulated on the ground as individual fragments called ash. Two terms(igneous and sedimentary) are useful to refer solely to the composition of igneous rocks regardless of their textures. The term silicic (硅质 的)signifies an abundance of silica-rich(富硅) and light-colored minerals(浅 色矿物), such as quartz, potassium feldspar(钾长石), and sodic plagioclase (钠长石) . The term basic (基性) signifies (意味着) an abundance of dark colored minerals relatively low in silica and high in calcium, iron, and
2023-2024学年山东省烟台市芝罘区八年级(上)期末英语试卷(五四学制)(含解析)
2023-2024学年山东省烟台市芝罘区八年级(上)期末英语试卷(五四学制)一、完形填空:本大题共10小题,共10分。
Wu Tianyi is 88 years old.As a doctor,he(1)______ in Qinghai for oversixty years.Wu came to Qinghai for work in 1958.There he saw many people have healthproblems and even die(2)______ the high altitude(海拔).At that time,noone in China studied on this area.He decided to work in this area.To find out the reasons (3)______ people got such health problems,Wu went on trips to places with a very high altitude.It was (4)______ for him.He had 14 bone fractures(骨折) during his trips.However,he never thought of(5)______ up.In the early 1990s,Wu made a hypobaric-hyperbaric chamber(高低压氧舱).The chamber played a very important(6)______ in the study of high altitude medicine.He (7)______ to be the first person to go into the chamber."I made it,and I (8)______ be the first one to try it," he said.But because the workers didn't have much experience with the chamber,Wu's hearing got damaged.He couldn't hear(9)______ from then on.Wu's study results are helpful.140,000 workers took part in the building of Qinghai-Tibet railway (青藏铁路),no one died.Today,Wu,in his(10)______,is still working hard.People say he is a guardian(守护者) of life.1.A. worked B. is working C. has worked D. will work2.A. because of B. instead of C. as for D. up to3.A. how B. why C. what D. where4.A. difficult B. easy C. exciting D. dangerous5.A. giving B. looking C. picking D. standing6.A. situation B. condition C. role D. environment7.A. volunteered B. refused C. agreed D. had8.A. can B. may C. must D. could9.A. correctly B. clearly C. exactly D. simply10.A. eighty B. eightieth C. eighty's D. eighties二、补全对话-填空:本大题共1小题,共5分。
Physical Chemistry of Solid State Electrolytes
Physical Chemistry of Solid StateElectrolytesSolid-state electrolytes (SSEs) have been studied extensively in recent years due to their potential to revolutionize energy storage technologies by enabling solid-state batteries with higher energy densities, longer cycle lives, and improved safety. Physical chemistry is an essential aspect of SSEs in understanding their fundamental properties and developing new materials with enhanced performances.Crystal Structures of SSEsThe crystal structure of SSEs is crucial for their ionic conduction properties. Most SSEs are composed of metal cations or non-metal anions arranged in a crystal lattice that forms a periodic network of voids or channels. The ionic conductivity of SSEs primarily depends on the accessibility of these channels for the movement of ions.For example, the lithium ion conductor Li10GeP2S12 (LGPS) features a tetragonal crystal structure composed of a three-dimensional network of corner-shared GeS4 tetrahedra. The large 12-coordinate Li+ ions occupy the large voids (12-fold coordination sites) between these tetrahedra, while the small 4-fold coordinated P5+ and S2- ions occupy the smaller voids (4-fold coordination sites), forming a disordered distribution pattern in the channels. This unique structure results in high lithium ion conductivity along the three crystallographic directions, achieving values up to 10^-3 S cm^-1 at room temperature.Defect Chemistry of SSEsThe presence of structural defects in SSEs can lead to enhanced ionic conductivity and electrochemical properties. Point defects (vacancies, interstitials) and line defects (dislocations, grain boundaries) can provide additional sites for charge carriers to move more easily through the material. These defects also affect the chemical stability andmechanical strength of SSEs, thus balancing the trade-off between ion conductivity and the electrolyte's structural integrity.For instance, the Li-ion conductor Li7La3Zr2O12 (LLZO) adopts a cubic garnet structure composed of alternating metal oxide layers and Li+ conducting channels. The presence of lithium and oxygen vacancies in the garnet structure can promote Li+ hopping between adjacent octahedral coordination sites, which is the rate-determining step of ionic conduction in LLZO. The introduction of excess lithium ions via Li2CO3 doping can further increase the ionic conductivity of LLZO by creating new lithium vacancies as well as enhancing the lithium-ion diffusivity.Interface Chemistry of SSEsThe interfacial behavior between the SSE and active electrode materials significantly impacts the battery's performance and stability. Understanding the interface chemistry can help design new SSE-electrode material combinations with enhanced electrochemical performance.For example, the Li-ion cathodes used in lithium-ion batteries usually feature a layered oxide structure, such as LiCoO2, which undergoes structural changes (e.g., structural phase transitions, oxygen loss) during cycling that can result in capacity fading and safety issues. The use of SSEs, such as LiPON (Li3.3PO3.8N0.2) or LLZO, as the electrolyte can suppress the side reactions and prevent the degradation of the electrode material. LiPON forms a thin, uniform, and dense interfacial layer between the cathode and electrolyte that blocks the diffusion of active species and protects the cathode from environmental degradation. LLZO, on the other hand, provides a greater degree of mechanical stability and electrochemical reliability due to its high chemical stability and compatibility with most electrodes.ConclusionThe physical chemistry of SSEs plays a critical role in determining their electrochemical properties and their interactions with other materials in energy storage devices such as batteries and supercapacitors. SSEs need to balance their ionicconductivity with thermal stability, mechanical integrity, and chemical compatibility to enable the development of solid-state batteries with better performance. Further studies on SSEs, including their crystal structures, defect chemistry, and interface chemistry, are necessary to improve the energy density, cycle life, and safety of SSE-based energy storage devices.。
TDLAS a laser diode sensor for the in situ monitoring of H2O, CO2 and their isotopes
TDLAS a laser diode sensor for the in situ monitoring of H 2O,CO 2and their isotopes in the Martian atmosphereT.Le Barbua,b,*,I.Vinogradov c ,G.Durry a,b ,O.Korablev c ,E.Chassefie`re a ,J.-L.Bertaux a aService d’Ae´ronomie du CNRS,Atmospheres Planetaires,BP 3–Reduit de Verrieres,Route des Gatines,91371Cedex Verrie `res-le-Buisson,France bGroupe de Spectrome´trie Mole ´culaire et Atmosphe ´rique,Moulin de la Housse 51687,Reims,France cSpace Research Institute (IKI),84/32Profsoyuznaya,117997Moscow,RussiaReceived 1November 2004;received in revised form 15April 2005;accepted 16April 2005AbstractWithin the framework of Pasteur-Exomars,we have proposed to measure in situ water vapor (H 2O,HDO,H 218O,H 217O)and carbon dioxide (CO 2,13C 16O 2,16O 12C 18O,16O 12C 17O)isotopes and also CO,CH 4and N 2O by absorption spectroscopy using nearinfrared laser diodes.The Service d ÕAe´ronomie has a relevant experience in trace-gas detection with laser diodes.We have devel-oped,with the support of the CNES and the CNRS,the SDLA diode laser spectrometer to measure in situ H 2O (at 1.39l m),CH 4(1.65l m)and CO 2(at 1.60l m)in the middle atmosphere from stratospheric balloons.The concentrations are obtained with a precision error of a few percent and with a high temporal resolution that ranges from 10ms to 1s.The developed laser probing technique should be also highly efficient to study the Martian atmosphere as there are much higher amounts of water vapor and carbon dioxide in the Martian atmosphere than in the lower stratosphere (H 2O:200ppmv at 6hPa on Mars,5ppmv at 10hPa in the low stratosphere (LS);CO 295%on Mars,360ppmv in the LS).Hence,we propose to adapt the laser probing technique to the Martian atmosphere.The main objectives are to determine water vapor and carbon dioxide fluxes and to study boundary layer properties.The sensor will provide in situ daily,diurnally resolved measurements of near-surface H 2O and CO 2concentrations over seasonal time scales.The additional isotopic measurements will provide quantitative constraints on the evolution of atmo-spheric composition and on the history of water on Mars.Ó2005COSPAR.Published by Elsevier Ltd.All rights reserved.Keywords:Laser diode;Absorption spectroscopy;Water vapor;Carbon dioxide;Isotopes;Mars atmosphere1.IntroductionThe laser diode probing technique is highly efficient to provide in situ trace-gas measurements at high tem-poral and spatial resolutions and with a high selectivity in the analyzed species (Durry et al.,2002a ).We have previously combined laser diodes and absorption spec-troscopy to monitor methane,carbon dioxide and water vapor in the middle atmosphere of the Earth fromballoon-borne platforms (Durry and Megie,1999).Fig.1shows an example of in situ vertical concentration profiles of H 2O,CH 4and CO 2yielded by the SDLA(Spectrome`tre a `Diodes Laser Accordables)balloon-borne diode laser spectrometer in the troposphere and the lower stratosphere.The profiles consist of a few thousands of in situ mea-surements yielded at 1s intervals with a precision error that ranges from 5%to 10%.The achieved dynamical range of the measurements is of five orders of magnitude which allows monitoring continuously H 2O in the upper troposphere and lower stratosphere despite the strong0273-1177/$30Ó2005COSPAR.Published by Elsevier Ltd.All rights reserved.doi:10.1016/j.asr.2005.04.049*Corresponding author.Tel.:+33326918812.E-mail address:tlebarbu@aerov.jussieu.fr (T.L.Barbu)./locate/asrAdvances in Space Research 38(2006)718–725concentration gradients between both regions of the Earth atmosphere (Durry et al.,2002a ).The developed laser probing technique should be also highly efficient to study the Martian atmosphere (May et al.,2001)as there are much higher amounts of water vapor and carbon dioxide in the Martian atmosphere than in the lower stratosphere (H 2O:200ppmv at 6hPa on Mars,5ppmv at 10hPa in the LS;CO 2:95%on Mars,360ppmv in the LS).Table 1shows the predicted absorption depths (i.e.,the percentage of absorbed laser energy)for the selected molecular species.Hence,we propose to adapt the laser probing tech-nique to the Martian atmosphere.With the support of the CNES,we have been developing for two years the TDLAS (Tunable Diode Laser Spectrometer)sensor that is described in this paper.The instrument is made within the framework of a collaboration between theService d ÕAe´ronomie (CNRS,Paris),the Space Research Institute (IKI,Moscow)and the Groupe de Spectrome´trie Mole´culaire et Atmosphe ´rique of the University of Reims (CNRS,Reims).The main objectives are to determine water vapor and carbon dioxide fluxes and to study boundary layer properties.The sensor will pro-vide in situ daily,diurnally resolved measurements of near-surface H 2O and CO 2concentration over seasonal time scales (Titov,2002;Tokano,2003).The additional isotopic measurements will provide quantitative con-straints on the evolution of atmospheric composition and on the history of water on Mars (Bertaux and Montmessin,2001;Krasnopolsky,2000).To reach the science objective,a precision error within a few percents in the concentration retrieval and a temporal resolution of 1s is needed for the developed sensor.2.MethodologyThe laser probing technique is based on the frequency tuning of a single mode emission laser diode over a rota-tion–vibration transition of a molecule of interest.The laser emission wavelength is scanned over the selected molecular transition by ramping of the laser driving cur-rent.The laser beam is propagated in the open atmo-sphere over an adequate absorption path length and is absorbed in situ by the ambient molecules.The absorp-tion of laser energy is related to the molecular absorp-tion by use of the Beer–Lambert law and a molecular model (Durry et al.,2002a ).The achieved detection limit is of 10À5(expressed in absorption units)for a 1-s mea-surement time (Durry et al.,2000).TDLAS is based on the use of distributed feedback (DFB)GaInSb near-infrared laser diodes emitting in the 1.5–2.1l m range.This laser technology iswell-Fig.1.(a)The SDLA balloon-borne spectrometer.(b)An example of achieved H 2O,CH 4and CO 2in situ vertical concentration profiles in the middle stratosphere.Table 1Simulation of molecular absorption (T =210K,P =9mbar)Molecule Spectral region (l m)Absorption path length Absorption (%)H 2O 200ppmv 1.88120cm 1.2CO 20.95% 1.88120cm 0.413CO 2TIR 2.04120cm 416O 12C 18O TIR 2.04120cm 0.7H 218O TIR 2.610m 0.02H 217O TIR 2.610m 0.02HDO2.610m0.04The molecular parameters are extracted from the HITRAN database.Terrestrial isotopic ratios (TIR)were used.Regarding HDO,the iso-topic ratio is found in Krasnopolsky (2000).T.L.Barbu et al./Advances in Space Research 38(2006)718–725719adapted to spectroscopic applications by its spectral emission properties;the spectral emission is monochro-matic,it is tunable over an average spectral range of 10cmÀ1,the line width is of a few MHz(much less than the average molecular line width at Martian pressure, i.e.,less than1GHz)and the output power is of a few mW.These lasers are operated at room temperature and a Peltier thermo-element is sufficient to obtain a sta-ble laser emission.Furthermore,highly sensitive and lin-ear detectors are available in the near infrared spectral range to develop compact sensors.A DFB GaInSb laser diode emitting at1877nm can be used for the simultaneous monitoring of H2O and CO2.Fig.2shows a simulated absorption spectrum un-der Martian conditions:95%of carbon dioxide and 200ppmv of water vapor for a120cm absorption path length.The absorption levels are of the same order of magnitude,despite the very different proportions,due to the line strengths(cm2moleculeÀ1cmÀ1)which are1.056·10À24for CO2and1.77·10À20for H2O accord-ing to the HITRAN databases(Rothman et al.,2003).Taking into account the limited tunability range ofthe laser used and the shape of the Martian near infraredspectrum,it is necessary to use one dedicated laser foreach selected specie and its isotopes.Hence,a second la-ser diode emitting around2042nm is used for CO2iso-topes(13C16O2and16O12C18O).In the absence of aprecise knowledge of the isotopic concentrations,itwas reasonable to take terrestrial ratio values as a start-ing point.Simulations(Fig.3),using the available linestrengths and terrestrial isotopic ratios given by HI-TRAN,show that,for a120cm absorption path length,the absorption levels(for example,7·10À3for 16O12C18O)are nearly3order of magnitude above the detection limit(detection limit of10À5expressed inabsorption units).Even with important differencewithFig.2.Simulated absorption level of CO2and H2O.Fig.3.Simulated absorption level of carbon dioxide isotopes.720T.L.Barbu et al./Advances in Space Research38(2006)718–725regards to the terrestrial values,it will be possible to make the measurements.The two laser diodes at1877and2042nm were pur-chased from Nanoplus GmbH and are presently under test in our laboratory.Regarding the water isotopes,HDO,H218O and H217O,a third laser diode is needed to reach strong molecular transitions in the2.6l m spectral range.This laser is under development with the support of the CNES by the Centre dÕElectronique et Micro-Optoe´lect-ronique de Montpellier(CEM2,CNRS,France).Water isotopes measurements require a much longer absorp-tion path length;at least10m are needed.With a10 m optical path length,simulations in Table1show that the absorptions of H217O and H218O(0.02%or2·10À4 expressed in absorption units)are roughly one order of magnitude above the detection limit.Considering lower isotopic ratios which may be encountered on Mars and water concentrationfluctuation,this length is to be con-sidered as the lower length limit.This would signifi-cantly increase the total mass of the instrument because it would make it necessary to use of a compact optical multipass cell(Durry et al.,2002b).So we can provide three versions of TDLAS accord-ing to the science objectives and size requirements.Two light versions(<500g):One version with a single laser (H2O and CO2measurements),a second version with two lasers(H2O,CO2and CO2isotopes measurements); and a third heavier version(<1kg)with the three lasers combined(H2O,CO2,13C16O2,16O12C18O,HDO, H218O,H217O).In the following section,we focus on the H2O/CO2sen-sor at1877nm.We also show the test of the available la-ser diode for carbon dioxide isotopes but the full isotopic version will be described in a further paper as soon as the needed2.6l m laser becomes available at the end boratory testsPresently,we are testing in the laboratory the spectral emission properties of the Nanoplus lasers to ensure they are monochromatic,by using Fabry–Perot confocal interferometers.A well-defined laser line shape(with no mode hops over the tunability range)is important toget boratory spectrum featuring CO2and H2O lines(see Fig.6.)with Fabry–Perot fringes used for frequency calibration;optical path69.6m, P=13.4mbar at roomtemperature.Fig.5.(Bottom)Layout for the spectroscopic study of water:PDstands for photodiode;FP for Fabry–Perot;Slow mod.for Slowmodulation;Temp.Cont.for temperature controller.(Top)For CO2study,a White type multipass optical cell is used.T.L.Barbu et al./Advances in Space Research38(2006)718–725721accurate measurements (Durry and Megie,1999)as the molecular profile is convolved with the apparatus func-tion (i.e.,the laser line shape).For example,Fig.4shows well-defined FP fringes,recorded simultaneously with the absorption spectrum of CO 2and H 2O,which indi-cate monochromatic wavelength emission over the re-gion of interest and also a good linearity in the laser frequency tuning.Furthermore,according to the Beer–Lambert law (Parvitte et al.,2002)the achieved accuracy in the con-centration retrieval is directly related to the accuracy in knowing the molecular line strength.Hence,the line strengths of CO 2and H 2O as well as carbon dioxide iso-topes are currently being revisited in our laboratory to improve accuracy.The experimental set-up is shown in Fig.5.The laser wavelength is temperature stabilized by means of a Peltier element and is driven by a low noise current supply.A low frequency ramp at 100Hz is used to scan the DFB diode over the selected absorp-tion lines by modulation of the driving current.The la-ser beam is divided into two beams.One beam is coupled with a confocal Fabry–Perot interferometer used for frequency calibration (free spectral range 0.00945cm À1).The other beam passes through an absorption cell:either a White type multipass cell of 69.6m for CO 2,or of 21.6m for its isotopes,or a sim-ple 10-cm cell for water.These absorption path lengths are only necessary for spectroscopic studies.They pro-vide strong absorption depths which enable the proper retrieval of line parameters.Once these spectroscopic parameters are accurately known,they can be used to retrieve the concentration from in the situ Martian spectra.Indeed,to record the in situ spectra in the Martian atmosphere shorter path lengths in combina-tion with differential detection technique will be used to dramatically reduce the overall weight of the sensor by simplifying the opticalscheme.boratory measurements with the laser diodes emitting at 1877nm (top)and 2042nm (bottom).722T.L.Barbu et al./Advances in Space Research 38(2006)718–725After this spectroscopic work,we will directly test the performance of TDLAS by coupling the sensor with a temperature stabilized 1m single pass cell to perform measurements at Martian low temperatures (Parvitte et al.,2002)and mixing ratios to check the matching of the achieved detection limit.The signals are sent to a digital oscilloscope and to a personal computer for data acquisition.We use the refer-ence spectrum of an empty cell to remove the sloping background (produced by the output power modulation due to the current ramping)and to extract the molecular transmission.To retrieve the coefficients of the line (intensity,pressure-broadening coefficient),we fit a Voigt profile to the molecular transmission using the known optical path lengths inside the cells,pressure,temperature and relative frequency calibration (given by FP fringes).The whole set up takes place in a closed box filled with dry nitrogen at atmospheric pressure in order to minimize the absorption by ambient water vapor.Fig.6shows laboratory measurements of the molec-ular transitions selected for TDLAS.The spectroscopic work (accurate determination of the line strengths)is under way and should be finished at the end of this year.Our tests of the spectral emission properties show that these laser diodes are suitable for trace-gas detection.4.TDLAS instrumentFig.7is a schematic diagram of the light-weight sin-gle-diode version of TDLAS which is the first step of the project.The sensor measures CO 2and H 2O simulta-neously by absorption spectroscopy using a DFB GaInSb laser diode at 1877nm.The laser emission wavelength is scanned over the selected rotation–vibra-tion transitions by modulation of the laser diode driving current at constant temperature.The temperature is measured with a thermistor bridge and regulated within±0.01°C with the proportional integral control of a thermoelectric cooler (i.e.,Peltier element).This precise control is achieved using a hybrid controller provided by Hytek Microsystems,Inc.The laser beam is propagated in the atmosphere over a 120cm folded path length and absorbed in situ by the ambient molecules (Figs.7and 8).The prototype uses the combination of a spherical mirror (focal length 30cm)and a flat mirror to achieve this folded optical path.The absorption spectra,consisting of 300sample points,are recorded at 10ms-intervals by means of a balance differential detection set-up using InGaAs pho-todiodes (Durry and Megie,1999;Durry et al.,2000).Ramping of the driving current to scan a spectral region also produces a modulation of the output power of the laser diode.The differential detection technique allows removal of this sloping background and to apply the full dynamic range of measurement (16bits)to the weak absorption signal.The electronic set up is displayed in Fig.9.The overall electronic control of the instrument is provided by a rad-hard 80C328-bit microcontroller from Atmel which is also used by the SPICAM instru-ment onboard Mars Express.The atmospheric mixing ratios are then retrieved from the in situ spectra using the Beer–Lambert law and a molecular model (Parvitte et al.,2002).The achieved precision error in the concentration re-trieval is of a few percents and can be enhanced by fur-ther co-adding successive 10-ms measurements.The detection limit is 10À5expressed in absorption unit (i.e.,0.001%of absorbed laser energy)when co-adding measurements for 1s.For instance,more details upon the performances of our detection technique are given in Durry et al.(2000),it was possible in the laboratory to reach the shot noise limit.The general characteristics of the sensor presently under development are summa-rized in Table 2.Fig.7.Schematic diagram of the single laser diode version of TDLAS.T.L.Barbu et al./Advances in Space Research 38(2006)718–725723In the usual processing way (onboard the balloon-borne instruments)the full spectrum is recorded with 256sample points taken on each channel (A,B,A–B)with a 16bit digitizer;the atmospheric spectra are then processed after the balloon flights.Regarding the Mar-tian sensor,for the processing,we intend to develop areal-time inversion model and also,if possible,a part of the raw spectra will be transmitted to the Earth.The development of a real time inversion model is facil-itated at Martian pressures because (compared to Earth)the collisional pressure-broadening effect is negligible;the Martian molecular profiles are dominated by the Doppler effect and the concentration is directly related to the absorption depth.Thus,data could be processed in situ with a simplified molecular model.Environmental effects,such as dust deposition on op-tics or frost,are also considered.With regard to dust,the laser power output is sufficient so that we can loose energy by partial occultation without significantly degrading the measurements,the atmospheric signal being balanced with the reference signal before each measurement.Of course,it would probably be necessary to implement protection hardware for extended mission scenarios.Nevertheless,the ultimate layout of the instrument will depend on the mission configuration (location on a lander,rover,or coupled with another instrument in a closed configuration with filtering and pumping system)and is therefore not further discussed.But we plan to implement a miniaturized version of the motorized shutters presently used with the SDLA to protect the mirrors Õsurfaces which would be used during intense dust activity or power offphases.And concern-ing frost,the mirror will be heated with flat Kapton resistor to avoid ice formation,similarly to what is done with SDLA.5.ConclusionPreliminary experimental results show that a high precision compact H 2O–CO 2laser sensor can be imple-mented using a DFB GaInSb laser diode emitting at 1877nm.Such instrument would give valuable informa-tion about the water and carbon cycles on a diurnal and a seasonal time scale at ground level.These kind of pre-cise in situ measurements are necessary to investigate the surface–atmosphere coupling which is of importance for a better understanding of the long-term evolution of subsurface water distribution and of carbon dioxide.AcknowledgmentThe described work was supported by Centre National d ÕEtudes Spatiales,by the Region Cham-pagne-Ardenne.ReferencesBertaux,J.L.,Montmessin,F.Isotopic fractionation through watervapour condensation:the Deuteropause,a cold trap for DeuteriumTable 2Characteristics of TDLAS sensor Mass 170g (without arm)SizeMain instrument:6cm (length);3cm (width);3cm (height),spherical mirror f =30cm;1.5cm (L)2cm (W);2cm (H)Power consumption 4–6W peakOptical path Open to the atmosphere 120cm Laser diode DFB GaInSb 1877nmOperating temperature:26°CDetectorsInGaAs photodiode (cut-offfrequency 2.2l m)Measurement time 10ms for one laser scanMinimum detectable absorption level 10À4(absorption units,one scan)10À5(1s)Precision error A few percentsData volume*600bytes/measurement (CO 2and H 2O)–Not compressed*Less if in situ processingFig.8.3D view of the instrument in the single laser diode configuration.724T.L.Barbu et al./Advances in Space Research 38(2006)718–725in the atmosphere of Mars.J.Geophys.Res.106(E12),32,879–32,884,2002.Durry,G.,Megie,G.Atmospheric CH4and H2O monitoring with near-infrared InGaAs laser diodes by the SDLA,a balloon-borne spectrometer for tropospheric and stratospheric in situ measure-ments.Appl.Opt.38,7342–7354,1999.Durry,G.,Pouchet,I.,Amarouche,N.,et al.Shot-noise-limited dual-beam detector for atmospheric trace-gas monitoring with near-infrared diode laser.Appl.Opt.39,5609–5619,2000.Durry,G.,Hauchecorne,A.,Ovarlez,J.,et al.In situ measurement of H2O and CH4with telecommunication laser diodes in the lower stratosphere:dehydration and indication of a tropical air intrusion at mid-latitudes.J.Atmos.Chem.43,175–194,2002a.Durry,G.,Danguy,T.,Pouchet,I.Open multipass absorption cell for the in situ monitoring of stratospheric trace gas with telecommu-nication laser diodes.Appl.Opt.41,3424–3433,2002b.Parvitte,B.,Zeninari,V.,Pouchet,I.,et al.Diode laser spectroscopy of H2O in the7165–7185cmÀ1range for atmospheric applications.J.Quantum Spectrosc.Radiat.Transf.75,493–507,2002. Krasnopolsky,V.On the deuterium abundance on Mars and some related problems.Icarus148,597–602,2000.May,R.D.,Forouhar,S.,Crisp,D.,et al.The MVACS tunable diode laser spectrometers.J.Geophys.Res.106,17673–17682,2001. Rothman,L.S.,Barbe, A.,Benner, D.C.,et al.The HITRAN molecular spectroscopic database:edition of2000including updates through2001.J.Quantum Spectrosc.Radiat.Transf.82, 5–44,2003.Titov,D.V.Water vapour in the atmosphere of Mars.Adv.Space Res.29,183–191,2002.Tokano,T.Spatial inhomogeneity of the Martian subsurface water distribution:implication from a global water cycle model.Icarus 164,50–78,2003.T.L.Barbu et al./Advances in Space Research38(2006)718–725725。
高考英语考前突破阅读理解能力科普类人福岛核电站地下水受到放射污染素材
福岛核电站地下水受到放射污染High levels of a toxic radioactive isotope have been found in groundwater at Japan's Fukushima nu clear plant, its operator says.福岛核电站附近的地下水中发现高剂量有毒的放射性同位素。
Tokyo Electric Power Company (Tepco) said tests showed strontium-90 was present at 30 times the legal rate.The radioactive isotope tritium has also been detected at elevated levels.The plant, crippled by the 2011 earthquake and tsunami, has recent ly see n a series of water leaks and power failures.The tsunami knocked out cooling systems to the reactors, which melted down.Water is now being pumped in to the re actors to cool them but this has left Tepco with the problem of how to safely store the cont aminated water.There have been several reports of leaks from storage tanks or pipes.Sea samplesStrontium-90 is for med as a by-product of nuclear fission. Tests showed that levels of stront ium in grou ndwater at the Fukushima plant had increased 100-fold since the end of last year, Toshihiko Fukuda, a Tepco official, told media.Mr Fukuda said Tepco believed the elevated levels originated from a lea k of contaminated water in April 2011 from one of the reactors."As it's near where the leak from reactor number two happened and taking into account the situation at the time, we believe that water left over from that time is the highest possibility," he said.Tritium, used in glow-in-the-dark watc hes, was found at eight times the allowable level.Mr Fukuda said that samples from the sea showed no rise in either substance and the company believed the groundwater was being contained by concrete foun dations."When we look at the impact that is having on the ocean, the levels seem to be within past trends and so we don't believe it's having an effect."But the discovery is another set-back for Tepco's plan to pump groundwater from the plant into the sea, correspondents say.Nuclear chemist M ichiaki Furukawa told Reuters news agency that Tepco should not release contaminated water into the ocean."They have to keep it somewhere so that it can't escape outside the plant," he said. "Tepco needs to carry out more regular testing in specific areas and disclose everything they find."The Fukushima power plant has faced a series of problems this ye ar. Early this month, radioactive water was found leaking from a storage tank.The plant also suffered three power failures in five weeks earlier this year. A leak of radioactive water from one of the plant's underground storage pools was also detected in April.。
Preparation of Novel Room-Temperature Molten Salts by Neutralization of Amines
Electrochemical capacitors and rechargeable batteries composed of nonaqueous organic liquids promise high power and energy de-vices with long life. The organic electrolytes in these devices should have excellent ionic conductivity and a wide electrochemical window over a large temperature range. Room-temperature molten salts or ionic liquids are acknowledged as the next generation of electrolytes. In spite of their excellent characteristics,chloroaluminate-type molten salts are unstable to air and decompose in the presence of water. Re-cently,nonchloroaluminate room-temperature molten salts have been studied extensively as potential electrolytes because of their low vis-cosity,lack of volatility,and greater thermal and electrochemical sta-bility than aqueous electrolytes and chloroaluminate-type ionic liq-uids.1-17Room-temperature ionic liquids have also been studied as clean aprotic solvents and reagents for organic synthesis.18-20A variety of ionic liquids,based on new anions and cations,are being studied in order to realize superior properties in various appli-cations. Ionic liquids with bis[(trifluoromethyl)sulfonyl]imide anion (TFSI-) or BF4Ϫgenerally have low melting point,low viscosity,and high ionic conductivity.5,7,12For the cation structure,quaternary ammonium,10,16,17pyridinium,11pyrazolium,15and imidazolium salts5are frequently used,producing molten salts at ambient tem-peratures. The characteristics of room-temperature molten salts are known empirically to depend strongly on the position and length of hydrocarbon constituents. Some asymmetric onium salts have a melting point below room temperature. However,the obvious corre-lation between cation structure and the capacity to form a room-tem-perature ionic liquid has never yet been reviewed.Synthesis of nonchloroaluminate molten salts requires two steps, the alkylation of a tertiary amine by alkyl halide,followed by the ex-change of the halide anion with the corresponding anion. This meth-od is very useful for hydrophobic products containing TFSIϪ,PF6Ϫ, AsF6Ϫ,or [C(SO2CF3)3]Ϫ,because the by-products can mostly be removed with water.2,4,5,17,21,22By contrast,hydrophilic ionic liq-uids are obtained by metathesis between onium halide and silver or ammonium salts with the corresponding anion.1,2,5,7,22This proce-dure has some drawbacks. It is troublesome to recover the media with high purity because of the difficulty of completely removing by-products. In addition,silver salts are expensive and are environ-mentally detrimental. Therefore it is not easy to prepare many dif-ferent kinds of molten salts and evaluate their properties.A convenient method of preparation of diverse kinds of amine salts is required in order to study the relation between cation struc-ture and physical characteristics such as ionic conductivity. Accord-ingly,tertiary amine was neutralized by various acids to form addi-tion compounds. This neutralization technique permits the resulting salts to include the corresponding anions in a single-step reaction.Also,the purification process is simple since there are no by-prod-ucts or residue. This method allows easy and inexpensive prepara-tion of various kinds of onium salt having high purity.In this article we report the synthesis of room-temperature molten salts by neutralizing21distinct tertiary amines with tetrafluo-roboric acid. The effect of cation structure on physical properties such as melting point,glass transition temperature,and ionic con-ductivity was then investigated.ExperimentalMaterials.—21 distinct tertiary amine-salts were prepared by titration of tetrafluoroboric acid in ethanol with the corresponding tertiary amines. The salts obtained are assigned numbers in the right column of Table I.Salts,from 1to 14and 21,were purified by dropwise addition to an excess of dehydrated diethyl ether. Salts 15 and 16 were washed by excess of toluene. Salts 17 and 18 were recrystallized from ace-tonitrile or methanol,respectively. Salts from 1 to 19 were dried in a vacuum at 60ЊC for 2 days. Salts20 and 21 were obtained by lyo-philization and were dried in a vacuum at room temperature. Since some of these salts were hygroscopic under air,sample preparation, conductivity measurements,and other processes were carried out in a glove box filled with dry nitrogen gas. The water content greatly affected the electrical characteristics,and the water was eliminated as much as possible by the vacuum drying as mentioned above. The water was not detected by the proton nuclear magnetic resonance (1H-NMR) measurements.Methods.—Ionic conductivity measurements were carried out using a Schlumberger Solartron 1260 impedance/gain-phase analyz-er with a frequency range from 10 Hz to 10 MHz. Impedance data were analyzed by the complex impedance method. The temperature range was from 10 to 60ЊC. All the measurements were carried out under dry nitrogen gas atmosphere.Differential scanning calorimetry (DSC) measurement was car-ried out with a DSC-120 (Seiko Instruments Inc.) in an atmosphere of nitrogen gas. The temperature varied from Ϫ150 to 200ЊC at a heating rate of 10ЊC minϪ1.The structure of the molten salts was confirmed by 1H-NMR spectroscopy (JEOL ␣-500).Results and DiscussionNeutralized amines were produced by acid-base neutralization as shown in Scheme 1. Ethanol was used for neutralization because of the high solubility involved. This reaction was carried out in a batch in an ice bath and required little time or labor. No peaks were found corresponding to the starting materials nor any trace amount of water molecules,according to 1H-NMR measurements. Neutralization ofPreparation of Novel Room-Temperature Molten Salts byNeutralization of AminesMichiko Hirao,Hiromi Sugimoto,and Hiroyuki Ohno zDepartment of Biotechnology,Tokyo University of Agriculture and Technology,Koganei,Tokyo 184-8588,JapanExamples of a new class of onium salts bearing the tetrafluoroborate anion (BF4Ϫ) were prepared by neutralization of the corre-sponding amines. This method greatly simplifies the preparation of many organic molten salts. Some of the resulting neutralized amines displayed an ionic conductivity greater than 10Ϫ2S cmϪ1at room temperature. The largest ionic conductivity was observed in 2-methyl-1-pyrroline neutralized by HBF4. In addition,the ionic conductivity above the melting point is well described by the V ogel-Tamman-Fulcher formula. There is a correlation between the ionic conductivity of neutralized amines and of the corre-sponding alkylated onium salts having the same heteroaromatic rings. These neutralized amines are convenient models of onium salts having high ionic conductivity.©2000 The Electrochemical Society. S0013-4651(00)03-120-7. All rights reserved.Manuscript submitted March 27,2000; revised manuscript received August 7,2000.z E-mail:ohnoh@cc.tuat.ac.jpamine is an excellent method for simplifying and facilitating the syn-thesis and mass production of molten salts inexpensively.We now discuss the thermal behavior and ionic conductivity ofthese neutralized amines. Then we study the effect of cation struc-ture on these properties.Thermal properties and ionic conductivity.—The glass transition temperature (Tg ),melting point (Tm ),and ionic conductivity (i ) of the neutralized amines are set out in Table I. Some neutralized amines were obtained as molten salts with a melting point below the ambient room temperature. Many neutralized amines had a higher melting point than the corresponding starting amine. This shows that not every neutralized amine becomes an ionic liquid at room temperature.The ionic conductivity is governed principally by the mobility of dissociated carrier ions. The glass transition temperature Tg is a measure of the mobility of the matrix,in that the matrix has higher mobility as Tg decreases. McEwen et al. have reported the Tg of sev-eral imidazolium salts.12The Tg of pyrrolidinium salts have been presented by MacFarlane et al.11Since the values of Tg were quite low,even below Ϫ80ЊC,it can be taken that these room-temperature molten salts had remarkable mobility. They also showed a high ionic conductivity,in some cases almost 10Ϫ2S cm Ϫ1at 25ЊC. By con-trast,low Tg values were found in some neutralized amines,specif-ically numbers 1,2,3,4,13,and 20. They showed Tg below Ϫ70ЊC,which is lower than in other neutralized amines. They should,there-fore,have high ionic conductivity,as observed in typical onium-type ionic liquids.Figure 1 shows the Arrhenius plots of ionic conductivity for these neutralized salts. The ionic conductivity of 1,2,3,4,and 13 was high,as expected. These were comparable to a well-known onium-type ionic liquid,1,3-diethyl imidazolium bis(trifluoromethylsul-fonyl) imide (shown as X in Fig. 1). Salt 21 showed a high ionic con-ductivity of over 10Ϫ2S cm Ϫ1at room temperature because it had the lowest melting point. From Table I the neutralized amines 1,2,and 3 have melting points in the range from 10 to 60ЊC. However,these salts maintained their high ionic conductivity at low tempera-tures (Fig. 1). In spite of their moderate Tm,around room tempera-ture,no drop in ionic conductivity based on the phase change was observed. We conclude that they exhibit a supercooled state below the melting point.We next investigated the relationship between ionic conductivity and Tg or Tm of neutralized amine salts,as shown in Fig. 2. It is eas-ily comprehended that the salt having lower Tm generally shows higher ionic conductivity. Since the ionic conductivity at 50ЊC was plotted in Fig. 2,the series of ionic liquids was classified into two groups,i.e.,those having Tm higher than 50ЊC and those having a lower one. It should be noted here that those salts having Tm of around 50ЊC show relatively high ionic conductivity; salt 6 has Tm at 59.6ЊC but a high ionic conductivity. These are explained by the supercooling phenomenon of the molten salts as mentioned in the discussion of Fig. 1. It is generally effective to prepare the molten salts with lower Tm for higher ionic conductivity. On the other hand,the ionic conductivity of neutralized salts decreased with increasing Tg,or in other words,with decreasing mobility of the fluid. Howev-er,salt 20 has a lower ionic conductivity of about 10Ϫ4S cm Ϫ1at ambient temperature despite its low Tg value. The mobility of the matrix is clearly not the only factor governing ionic conductivity. The basicity of starting amines is important for the electrostatic interac-tion,and this may influence the conductivity. The effect of salt struc-ture on the ionic conductivity will be analyzed in the near future.We then investigated the degree of salt dissociation as a factor influencing the ionic behavior of amine salts according to the V ogel-Tamman-Fulcher (VTF) formula,{(T ) ϭAT Ϫ1/2exp[ϪB /(T ϪT 0)]}. This formula represents the absolute-temperature dependenceScheme 1.Figure 1. Temperature dependence of ionic conductivity of neutralized amines. Structure of salts from 1 to 21,see Table I. The ionic conductivity of 1,3-diethylimidazolium TFSI salt was also plotted (X) as a reference for a typical onium-type molten salt.Figure 2. Relation between ionic conductivity and glass transition tempera-ture or melting point of neutralized amines.of the ionic conductivity of a glass-forming liquid. Here A is a pre-exponential factor,B is related to the activation energy Ea,and T0is the ideal glass transition temperature. The value of T0was compared to the observed Tg of neutralized amines [r > 0.997 for log (i T1/2) vs. 1/(T-T0)]. Their conductivities fitted the VTF equation closely,as shown in Fig. 3. According to the VTF theory,the conductivity is independent of the glass transition temperature. If Tg were the main factor governing the ionic conductivity,the VTF plots should all be identical. However,the conductivity dependence on the temperature and the B value of neutralized amines no. 1,2,3,4,5,7,13,and 20 are at variance with each other (Fig. 3 and Table II). The dominant factor on the ionic conductivity is the number of carrier ions. Since the mobility of the matrix is normalized in the VTF equation,differences in the conductivity of neutralized salts should be caused by different degrees of dissociation into ions. In other words,it can be assumed that the higher B value of the neutralized salts results from the stronger temperature dependence of the dissociation energy. Salt 20 exhibited a value for B about twice that of other neutralized amines in Table II. We suggest that the ion-conduction mechanism of salt 20 is different from the others,so that its ionic conductivity is lower even where it has a similar Tg value. Of these,salt 1had the lowest B and the highest ionic conductivity. This salt was an outstanding ionic liq-uid with high matrix mobility and dissociation into ions.Effect of amine structure on physical properties of the salts.—In reports on alkylated imidazolium,pyrrolidinium,and quaternary ammonium salts,salts with rather small asymmetry tend to be liq-uids at ambient temperature,with low Tm and Tg,and high ionic conductivity. It seems that the ionic conductivity is greatly affected by the structure of the amine. We searched for optimum conditions for the preparation of room-temperature ionic liquids. In general,the ionic conductivity decreases with increasing molecular mass be-cause the number of ions per unit mass is less. We studied the rela-tion between molecular weight of the starting amine and the ionic conductivity at 50ЊC. The molecular weight of the cation and the ionic conductivity of the salts were not correlated.Next,the effect of substituent position on the properties of neu-tralized amines was investigated. We compared the ionic conductiv-ities of 5,6,7,and 8,obtained by the neutralization of lutidines,with different substituent positions. The low-symmetry salt 5,which had -CH3at positions 2- and 4 of the lutidine ring,showed the lowest Tg and Tm and the highest ionic conductivity of its class. Salt 6,with -CH3at positions 2 and 3,had the next highest ionic conductivity. The lowest ionic conductivity was observed in the symmetric salt 8, with -CH3at positions 2- and 6,together with the highest values of Tg and Tm. For indolium salts,the ionic conductivity of 11,prepared by the neutralization of 1-methylindole,was quite low and could not be detected at room temperature. Salts 15 and 16 were obtained as powder samples and showed high Tm and correspondingly low ionic conductivity,as for 11. On the other hand,salt 3,obtained from 1,2-dimethylindole,showed the lowest Tg at about Ϫ75ЊC,had a Tm of 24.5ЊC,and the highest ionic conductivity of nearly 10Ϫ2S cmϪ1at room temperature. We suggest that neutralized amines with sub-stituents at both 1- and 2- positions tend to be room-temperature molten salts. Neutralized amines from indole derivatives have the capability of being room-temperature molten salts with high ionic conductivity. We expect neutralized carbazole to have a high ionic conductivity,since carbazole is considered to be an indole derivative. The neutralized carbazolium salt 18 had a Tg of approximately 60ЊC, and almost no conductivity was observed over the whole tempera-ture range of measurement. Against this,salt 4,synthesized from 1-ethylcarbazole,had Tg of Ϫ68.0 and a high ionic conductivity of 2.210Ϫ3S cmϪ1at room temperature.From a comparison of these results,room-temperature molten salts with low Tg,and Tm and high ionic conductivity are best pre-pared by starting with low-symmetry heterocyclic amines having alkylated substituents at positions 1- and 2 of their ring.Model of alkylated room-temperature molten salts.—We now turn to the relation of the ionic conductivity for neutralized and alkylated imidazolium ionic liquids containing BF4Ϫ. Salt 19,obtained by the reaction of 1-methylimidazole and tetrafluoroboric acid,had relative-ly low ionic conductivity below its melting point of 36.9ЊC (Table I, Fig. 1). However,the ionic conductivity of this salt above its melting point was high at 2.8 ϫ10Ϫ3S cmϪ1at 50ЊC. Alkylated imidazoli-um salts should also have high ionic conductivity above their melting points. The melting point and ionic conductivity of 1-ethyl-3-methylimidazolium tetrafluoroborate (EtMeImBF4),which is a typi-cal room-temperature molten imidazolium salt,are reported to be 15ЊC and 1.4 ϫ10Ϫ2S cmϪ1at 25ЊC.7We also prepared several di-alkylated imidazolium salts using the standard method.1,2,4,5,7,17,21,22 We determined the ionic conductivity of EtMeImBF4to be about 2.0ϫ10Ϫ2S cmϪ1at 50ЊC.The high ionic conductivity of EtMeImBF4confirms that neu-tralized amines have the potential to be excellent models for quater-nized onium salts. Accordingly,alkylated amine salts such as 1,2,3, 4,13,and 21 are expected to form ionic liquids and have high ionic conductivities at room temperature. In fact,alkylated pyrrolidinium salts having not BF4Ϫbut TFSIϪas counteranion have been reported to be room-temperature molten salts with high ionic conductivity.11ConclusionWe have investigated the ionic conductivity and thermal proper-ties of 21 types of amine salt obtained by neutralization with tetra-fluoroboric acid. Those salts deriving from 2-methyl-1-pyrroline,1-ethyl-2-phenylindole,1,2-dimethylindole,1-ethylcarbazole,1-methylpyrazole,and 1-methylpyrrolidine have lower glass transition temperatures and melting points,and higher ionic conductivities, than other neutralized amines. The temperature dependence of their ionic conductivity was well fitted by the VTF formula. The neutral-ized 2-methyl-1-pyrroline dissociated more easily into ions than the other salts prepared. Cation structure also has an effect on ionic con-ductivity,and heterocyclic amines with alkylated substituents at both 1- and 2- positions were excellent starting materials for synthesizing room-temperature molten salts with desirable properties. In compar-ison of ionic conductivity between corresponding alkylated and neu-tralized ionic liquids,the neutralized amines proved to be effective as model compounds for the analogous alkylated amines. The prop-erties of alkylated amines are elucidated by the properties of the cor-responding neutralized amines,which are relatively easy to prepare.Figure 3. VTF plot of ionic conductivity for neutralized amines.AcknowledgmentThis study was supported by the Grant-in-Aid for Scientific Research from the Ministry of Education,Science,Sports,and Cul-ture of Japan (no. 11555250).Tokyo University of Agriculture and Technology assisted in meeting the publication costs of this article.References1.J. S. Wilkes and M. J. Zaworotko,J. Chem. Soc.,Chem. 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1941克林贝尔The Permeability Of Porous Media To Liquids And Gases
THE PERMEABILITY OF POROUS MEDIA TO LIQUIDS AND GASES
air might be of no significance or even definitely misleading. The question to be discussed here, however, is whether porous media in which no changes in the internal structure take place will show different permeability constants to different fluids. I t has been a point of much discussion in the literature' whether the walls of small capillaries, a s they occur in porous media, are able to adsorb molecules to such a n extent a s to build up more or less .rigid layers several molecules thick. Such adsorbed layers would reduce the effective pore diameter to a different degree for different liquids and, a s a consequence, the permeability of a porous mass would depend on the nature of the liquid. Some authors8 prefer to speak about an increase in viscosity of the liquid with a decreasing distance to the solid wall-which amounts, of course, to the same thing.
铁碳核壳纳米棒
Fe 3O 4/carbon core e shell nanotubes as promising anode materials for lithium-ion batteriesHui Xia a ,*,Yunhai Wan a ,Guoliang Yuan a ,Yongsheng Fu b ,Xin Wang b ,**a School of Materials Science and Engineering,Nanjing University of Science and Technology,Xiaolingwei 200,Nanjing,Jiangsu 210094,ChinabKey Laboratory of Soft Chemistry and Functional Materials,Nanjing University of Science and Technology,Ministry of Education,Nanjing 210094,Chinah i g h l i g h t sg r a p h i c a l a b s t r a c tFe 3O 4/carbon core e shell nanotubes have been successfully synthesized. The hybrid electrode shows a large reversible capacity up to 938mAh g À1. The hybrid electrode also shows excellent cycling stability and ratecapability.a r t i c l e i n f oArticle history:Received 13November 2012Received in revised form 23April 2013Accepted 25April 2013Available online 14May 2013Keywords:Magnetite Hematite Core e shell Nanotube AnodeLithium-ion batteriesa b s t r a c tMagnetite (Fe 3O 4)/carbon core e shell nanotubes have been successfully synthesized by partial reduction of monodispersed hematite (Fe 2O 3)nanotubes with carbon coating.Fe 2O 3is completely converted to Fe 3O 4during the reduction process and a thin carbon layer is continuously coated on the surface of Fe 3O 4with the nanotube morphology reserved.The Fe 3O 4/carbon core e shell nanotubes exhibit superior electrochemical properties as anode material for lithium-ion batteries compared with the Fe 2O 3and Fe 3O 4nanotubes.The Fe 3O 4/carbon core e shell nanotubes electrode shows a large reversible capacity up to 938mAh g À1as well as improved cycling stability and excellent rate capability.The promising anode performance of the Fe 3O 4/carbon core e shell nanotubes can be attributed to their tubular morphology and continuous carbon coating,which provide improved structural stability and fast charge transport.Ó2013Elsevier B.V.All rights reserved.1.IntroductionDuring the past few decades,rechargeable lithium-ion batteries (LIBs)with high energy density,light weight,long cycle life,andenvironmental friendliness have been widely used as power sources for various portable electronic devices such as cellular phones,laptop computers,digital cameras and etc [1,2].More recently,they have attracted growing attention as power supplies for hybrid,plug-in hybrid,and all electric vehicles.To meet the ever increasing de-mands for larger energy density and power density,intensive research has been invested to develop new electrode materials with improved electrochemical performance.For instance,transition metal oxides such as Fe 2O 3,Fe 3O 4,Co 3O 4,and MnO 2have attracted a*Corresponding author.Tel.:þ862584315606;fax:þ862584315159.**Corresponding author.Tel.:þ862584305667;fax:þ862584315054.E-mail addresses:xiahui@ ,jasonxiahui@ (H.Xia),wxin@ (X.Wang).Contents lists available at SciVerse ScienceDirectJournal of Power Sourcesjournal ho mep age:www.elsevi /locate/jpowsour0378-7753/$e see front matter Ó2013Elsevier B.V.All rights reserved./10.1016/j.jpowsour.2013.04.126Journal of Power Sources 241(2013)486e 493lot of interest as anode materials for LIBs due to their higher theo-retical capacities than that of commercial graphite anode[3e11]. Among these anode materials,Fe3O4(magnetite)has many advan-tages in terms of relatively high electronic conductivity,low cost, and environmental benignity,thus has attracted considerable attention[12e14].However,like other transition metal oxides, Fe3O4still suffers from rapid capacity fading during the cycling process due to the electrode pulverization,which leads to loss of contact between electrode materials and current collectors.It has been well demonstrated that the cycling stability of Fe3O4 could be partially solved in nanostructured electrode materials due to their large surface-to-volume ratio and small dimensions,which can alleviate the mechanical stress associated with Li insertion/ extraction[15,16].By far,various nanostructures of Fe3O4,including nanoparticles,nanoflakes,nanorods,and nanobelts,have been synthesized and tested in lithium-ion batteries[17e20].However, Fe3O4nanotubes,which could be ideal for accommodating large volume changes,have very limited reports for their electrochemical performance as anode materials for LIBs[21].Although nanotubes of a wide range of materials in various types have been prepared by different strategies,it remains a challenge to synthesize nanotubes of metal oxides with isotropic crystal structure.Nanotubes of various metal oxides are usually prepared by a template method. Previously,Jia,Sun and Yan et al.firstly reported the synthesis of Fe2O3nanotubes by a hydrothermal method[22,23].Recently,Liu et al.[24]prepared Fe2O3nanotube arrays by a sacrificial template-accelerated hydrolysis approach and Wang et al.[25]prepared polycrystalline Fe2O3nanotubes by one-step template-engaged precipitation of Fe(OH)x followed by thermal annealing.Both Fe2O3 nanotube samples exhibit promising cycling stability as anodes for lithium-ion batteries.Nevertheless,the high surface area of nano-structured electrode materials raises the risk of solid electrolyte interphase(SEI)layer formation,which could cause a high level of irreversibility and poor cycle life[26].Therefore,surface modifi-cation should be considered for nanostructured transition metal oxides as anode materials for LIBs.Carbon coating is one of the most widely used surface modifi-cation techniques and has been used for anode materials as it may serve as perfect barrier to protect inner active material and main-tain its high capacity[27e29].Recently,carbon coated Fe2O3and Fe3O4are extensively studied as anode materials for lithium-ion batteries[27e37].For example,carbon-decorated single crystal-line Fe3O4nanowires[7],Fe3O4/carbon core e shell nanorods[15], and carbon coated Fe3O4nanospindles[26],have been prepared to improve the electrochemical performance of the pure Fe3O4elec-trodes.In this work,Fe2O3nanotubes were synthesized by a simple hydrothermal treatment without using template.A thin carbon layer was coated on the Fe2O3nanotubes by another hydrothermal treatment using glucose.The carbon-coated Fe2O3nanotubes were easily converted to carbon-coated Fe3O4nanotubes by thermal annealing in Ar atmosphere.It was found that the Fe3O4/carbon core e shell nanotubes exhibit large reversible capacity (938mAh gÀ1),significantly improved cycling stability,and high rate capability compared with the bare Fe2O3and Fe3O4nanotubes.2.Experimental2.1.Synthesis of Fe2O3and Fe3O4nanotubesThe Fe2O3nanotubes were synthesized by a simple hydrother-mal treatment reported in Fan’s work[38].In a typical synthesis procedure,0.4320g FeCl3$6H2O and0.0066g NH4H2PO4were added to80mL distilled water with vigorous stirring.After stirring for10min,the mixture was transferred into a Teflon-lined stain-less-steel autoclave with a capacity of100mL.The autoclave was then put into an electric oven for hydrothermal treatment at200 C for96h.The autoclave was cooled down to room temperature naturally and the red precipitate was separated by centrifugation, washed with distilled water,and dried under vacuum at80 C.The obtained samples were Fe2O3nanotubes.The Fe3O4nanotubes were synthesized according to a previous work[39].In a typical synthesis procedure,0.3g of Fe2O3nanotubes were heated in a horizontal quartz tube furnace at420 C for120min under a constantflow of5%H2/95%Ar at800sccm.After that,the furnace was cooled down to room temperature without changing the at-mosphere and black Fe3O4product was collected from the small quartz.2.2.Synthesis of Fe3O4/carbon core e shell nanotubes0.20g Fe2O3nanotubes were dispersed in20mL distilled water by ultrasonication for1h to form a suspension.In the next step, 0.31g glucose(C6H12O6$3H2O)was dissolved in the above sus-pension and5mL ethanol was added to the suspension with gentle stirring.After stirring for10min,the mixed solution was trans-ferred to a30mL Teflon-lined autoclave for hydrothermal treat-ment at180 C for12h.After the autoclave cooled down to room temperature,the carbon precursor-coated Fe2O3nanotubes were harvested by centrifugation and washed with distilled water,then dried in an electric oven at80 C.The resulting samplefilled in an alumina crucible was heated at600 C in an electric furnace under Ar atmosphere for6h for carrying out the carbon-thermal reduc-tion to obtain thefinal Fe3O4/carbon core e shell nanotubes.2.3.Structural and morphology characterizationThe crystallographic information and composition of the prod-ucts were investigated by X-ray diffraction(XRD,Shimadzu X-ray diffractometer6000,Cu K a radiation),Raman spectroscopy(Jobin-Yvon T6400Micro-Raman system),inductively coupled plasma-optical emission spectroscopy(ICP,Thermo Elemental IRIS1000), and X-ray photoelectron spectroscopy(XPS,PHI Quantera SXM Scanning X-ray Microprobe).Raman spectroscopy measurements were carried out using a Jobin-Yvon T64000micro-Raman system equipped with a charge-coupled device detector.XPS analysis was performed on the thinfilm with a VG ESCALAB MK spectrometer using Al K radiation(1486.6eV).An analyzer with a pass energy of 20eV was adopted,and a C1s peak at284.6eV due to adventitious carbon was used as an internal reference.The carbon content of the composite was also characterized by thermogravimetric analysis (TGA,Shimadzu DTG-60H).The morphology and structure of the products were investigated byfield emission scanning electron microscopy(FESEM,Hitachi S4300),transmission electron micro-scopy(TEM,JEOL,JEM-2010)and high resolution transmission electron microscopy(HRTEM).2.4.Electrochemical measurementsTo prepare the working electrodes,slurries were prepared by mixing80wt%active material(Fe2O3nanotubes,Fe3O4nanotubes and Fe3O4/carbon core e shell nanotubes),10wt%acetylene black (Super-P),and10wt%polyvinylidenefluoride(PVDF)binder in N-methyl-2-pyrrolidinone(NMP).The slurries were coated on the Cu foils and dried at120 C for2h to remove the solvent.The dried electrodes were pressed and cut into small disks(10mm in diameter).The small disks were further dried at80 C in a vacuum oven for12h before battery tests.Half cells using Li foil as both counter and reference electrodes were assembled with Lab-made Swagelok cells for the electrochemical measurements.1M LiPF6 in ethylene carbonate and diethyl carbonate(EC/DEC,v/v¼1:1)H.Xia et al./Journal of Power Sources241(2013)486e493487solution was used as the electrolyte and Celgard 2400was used as the separator.Galvanostatic charge and discharge measurements were carried out in the voltage range between 0.01and 3V at different current densities using LAND CT2001A electrochemical workstation at room temperature.3.Results and discussionThe phase purity and crystal structure of the products were investigated by XRD.As shown in Fig.1b,all of the diffraction peaks can be exclusively indexed to the trigonal a -Fe 2O 3(JCPDS No.87-1165),and no other impurities are observed.When the Fe 2O 3nanotubes were coated with carbon and heated in Ar atmosphere at 600 C,a phase transition took place in the iron oxide as Fig.1a shows a completely different XRD pattern.All diffraction peaks in Fig.1a can be indexed to face centered Fe 3O 4(JCPDS No.65-3107).No XRD peaks corresponding to graphite are found in the XRD pattern of the Fe 3O 4/carbon core e shell nanotubes,which indicates the carbon coatings are probably in amorphous state [27].It is noticed that the XRD pattern of Fe 3O 4is quite similar to that of g -Fe 2O 3.The existence of g -Fe 2O 3in the products can be ruled out because g -Fe 2O 3cannot withstand heat-treatment as it converts to a -Fe 2O 3at about 400 C [26].The XRD pattern of the bare Fe 3O 4nanotubes obtained from the reduction of Fe 2O 3nanotubes is exactly the same as that of the Fe 3O 4/carbon nanotubes,which is not shown here.Raman spectroscopy was further performed to investigate the structure and phase composition of the products.Fig.2a shows the Raman spectrum of the carbon precursor-coated Fe 2O 3nanotubes.As hematite belongs to the D 63d crystal space group with two A 1g modes and five E g modes,two peaks at 225and 486cm À1are assigned to the A 1g modes and three peaks at 290,401,and 597cm À1are assigned to E g modes [40].Another two peaks at 1300and 1587cm À1can be assigned to the D and G bands for carbon [41].The G band,corresponding to the first order scattering of the E 2g mode observed for sp 2domains,is characteristic for graphitic sheets,whereas the D band can be attributed to the presence of sp 3defects within the carbon [42].Fig.2b shows the Raman spectrum of the Fe 3O 4/carbon core e shell nanotubes.A strong peak at 670cm À1and two small peaks at 538and 300cm À1can be assigned to the A 1g ,T 2g ,and E g modes of Fe 3O 4,respectively [40].Another two peaks at 1335and 1594cm À1correspond to the D and G bands for carbon.The intensity ratio of the D and G band (I D /I G )is indic-ative of the degree of graphitization [43].The ratio value for the Fe 3O 4/carbon core e shell nanotubes is 0.97,whereas it is 1.25for the carbon precursor-coated Fe 2O 3nanotubes,which indicates thatthe degree of graphitization of the carbon within Fe 3O 4/carbon core e shell nanotubes is strongly enhanced.The surface morphology and microstructure of the a -Fe 2O 3nanotubes and the Fe 3O 4/carbon core e shell nanotubes were characterized by FESEM and TEM.Fig.3a shows the FESEM image of the as-prepared a -Fe 2O 3nanotubes.It can be seen that large-scale hollow structured Fe 2O 3nanocrystals with uniform size and tubular morphology have been fabricated by the hydrothermal treatment.The average length of these nanotubes is about 250nm and the average outer diameter of these nanotubes is about 90nm.After reduction,the obtain Fe 3O 4nanotubes preserved the similar morphology as the Fe 2O 3nanotubes.Fig.3b shows the FESEM image of the Fe 3O 4/carbon core e shell nanotubes.It can be seen that there is no signi ficant change in morphology,indicating the tubular structure is stable under hydrothermal treatment and heat-treatment.Fig.3c and d shows the TEM images of the as-prepared Fe 2O 3nanotubes.The obvious electron-density differ-ences between the dark edge and pale center further con firm the hollow and tubular structure clearly.As shown in Fig.3d,the wall thickness for the nanotube is about 10e 20nm.The inserted selective-area electron diffraction pattern indicates the single crystal nature of the Fe 2O 3nanotubes.Fig.3e shows a typical HRTEM image that was taken from the open-end region of the single Fe 2O 3nanotube in Fig.3d.The lattice spacing about 0.45nm for (0003)plane of the trigonal Fe 2O 3[38]can be clearly resolved.Fig.3f and g shows the TEM images of the Fe 3O 4/carbon core e shell nanotubes.It is clear to see that a thin and continuous carbon layer is coated on the surface of Fe 3O 4nanotubes.As shown in the inset in Fig.3g,a magni fied TEM image that was taken from the wall of the Fe 3O 4nanotube indicates carbon coating takes place at both outer side and inner side surfaces of the tube,building a Fe 3O 4/carbon core e shell nanotube heteroarchitecture.The thickness of the carbon layer coated on the Fe 3O 4nanotubes ranges between 2and 5nm.Fig.3h shows an HRTEM image that was taken from the wall region of the single Fe 3O 4/carbon nanotube in Fig.3g.The well-resolved lattice fringes with an interplane distance of 0.48nm come from the (111)plane of Fe 3O 4.The chemical composition and electronic structure of the Fe 3O 4/carbon core e shell nanotubes were further investigated by XPS.Fig.4a shows the survey-scan XPS spectrum for the Fe 3O 4/carbon core e shell nanotubes.All obvious peaks are labeled and can be ascribed to Fe,O,and C.Fig.4b shows the narrow scan XPS spec-trum of Fe 2p of the Fe 3O 4/carbon core e shell nanotubes.Two main peaks,located at 710.8and 724.0eV,correspond to Fe 2p 3/2and Fe 2p 1/2,respectively.The Fe 2p 3/2peak can be best fitted with two components with a major one at 710.6eV and a minor one at 712.1eV,which can be ascribed to Fe 2þand Fe 3þ,respectively.Moreover,no shakeup satellite peak situated at w 719eV,whichisFig.1.XRD patterns of (a)the Fe 3O 4/carbon core e shell nanotubes and (b)the a -Fe 2O 3nanotubes.Fig.2.Raman spectra of (a)the carbon precursor-coated a -Fe 2O 3nanotubes and (b)the Fe 3O 4/carbon core e shell nanotubes.H.Xia et al./Journal of Power Sources 241(2013)486e 493488the fingerprint of the electronic structures of Fe 2O 3[44],con firms no Fe 2O 3exist in the Fe 3O 4/carbon core e shell nanotubes.As shown in Fig.4c,the O 1s spectrum is broad and could be deconvoluted into three peaks at 529.9,531.1,and 533.3eV,respectively.The peak at 529.9eV is a typical state of O 2Àspecies corresponding to Fe 3O 4,while the rest two peaks could be attributed to the presence of residual oxygen-containing groups (such as e OH and e COOH)bonded with carbon atoms in the carbon layer of the Fe 3O 4/carbon core e shell nanotubes.The C 1s core-level spectrum shown in Fig.4d can be deconvoluted into three peaks at 284.3,285.7,and 288.8eV,respectively.The main peak at 284.3eV is due to the sp 2-hybridized carbon [45].The peak at 285.7eV can be assigned to carbon atoms singly coordinated to an oxygen atom as in phenols or ethers (C e OR)[45].The small peak at 288.8eV is attributed to the presence of carbonyl (C ]O)groups [45].ICP was used to quantify the chemical composition of the composite.The results showed that the composites have a chemical composition of 92.8wt%Fe 3O 4and 7.2wt%carbon.The Fe 3O 4/carbon core e shell nanotube heteroarchitecture could be a promising anode material for LIBs.In the present study,gal-vanostatic charge/discharge measurements were carried out on the Fe 3O 4/carbon core e shell nanotube electrodes,the pure Fe 3O 4,and the pure Fe 2O 3nanotube electrodes.Fig.5a shows the charge/discharge curves of the Fe 2O 3nanotube electrode at various cycle numbers at a constant current density of 100mA g À1in the voltagerange between 0.01and 3.0V.The first discharge curve of the Fe 2O 3nanotube electrode exhibits two distinguished voltage plateaus at 1.6and 0.8V,respectively,which agrees well with literature reports for the Fe 2O 3electrodes [24e 26].The first plateau can be ascribed to the formation of cubic Li 2Fe 2O 3,and the second plateau can be ascribed to the formation of Fe/Li 2O composite.The first charge curve of the Fe 2O 3nanotube electrode exhibits a quasi voltage plateau at about 1.6V,corresponding to the oxidation from Fe 0to Fe 3þ.The electrochemical reversible reaction mechanism of lithium storage in Fe 2O 3during the charge/discharge processes can be described asFe 2O 3þ6e Àþ6Li þ52Fe 0þ3Li 2O(1)In theory,Fe 2O 3can have an uptake of 6Li þ,corresponding to 1005mAh g À1theoretical speci fic capacity.It was found that electrochemical lithiation typically leads to formation of nanometer-scale metal clusters embedded in a Li 2O matrix,accompanying a large volume expansion.The high strain associated with the large volume change could lead to the pulverization of the electrode,which induces loss of electrical contact between the electrode material and the current collector,thus resulting in fast capacity fade for the cycling.As shown in Fig.5b and c,the Fe 3O 4nanotube electrode and the Fe 3O 4/carbon core e shell nanotube electrode exhibit similar charge/discharge curves.For both elec-trodes,the first discharge curves (Fig.5b and c)exhibit onlyoneFig.3.FESEM images of the Fe 2O 3nanotubes (a)and the Fe 3O 4/carbon core e shell nanotubes (b).(c,d)TEM images of the Fe 2O 3nanotubes.(e)HRTEM of a single Fe 2O 3nanotube.(f,g)TEM images of the Fe 3O 4/carbon core e shell nanotubes.(h)HRTEM of a single Fe 3O 4/carbon core e shell nanotube.Inset in Fig.3d shows the selective-area electron diffraction pattern of a single Fe 2O 3nanotube.Inset in Fig.3g shows the magni fied TEM of the wall region of a single Fe 3O 4/carbon core e shell nanotube.H.Xia et al./Journal of Power Sources 241(2013)486e 493489well-de fined plateau at about 0.8V,corresponding to the reduction of Fe 3þ/Fe 2þto Fe 0,which agrees well with literature reports for the Fe 3O 4electrodes [26,29].The electrochemical reversible reaction mechanism of lithium storage in Fe 3O 4during the charge/discharge processes can be described asFe 3O 4þ8e Àþ8Li þ53Fe 0þ4Li 2O(2)However,Zhang et al.found that Fe 3O 4was not directly reduced to Fe 0during the initial discharge process with the formation of an intermediate phase of Li x Fe 3O 4[46,47].To investigate the inter-mediate reaction,ex situ XRD analysis was carried out for the Fe 3O 4/carbon nanotube electrode.Fig.5d shows the ex situ XRD patterns of the Fe 3O 4/carbon nanotube electrode at various discharge states.When the electrode was first discharged to 0.85V,the diffraction peaks of Fe 3O 4disappeared while some new peaks appeared.The new diffraction peaks can be attributed to Li x Fe 3O 4[46],which agree well with the previous report,indicating the formation of intermediate phase during the initial discharge process.When the electrode was further discharged to 0.8V,the diffraction peaks of Li x Fe 3O 4disappeared while a peak ascribed to Li 2O appeared,indicating the intermediate phase was further reduced to Fe 0.When the electrode was discharge to 0.01V,no diffraction peaks from the electrode material can be observed,which could be ascribed to the nanoparticle nature of the electrochemically formed species.There could be some reasons to explain why XRD cannot detect the Li x Fe 3O 4signals after the first cycle.First,there is an irreversible capacity loss between charge and discharge for the first cycle,which means not all Li inserted during the first discharge can be extracted during the first charge and Fe 3O 4could not be reformed after the first cycle.For the second discharge,Li is not intercalated into Fe 3O 4but kind of FeO x /Li 2O composite,which maynot result in the formation of Li x Fe 3O 4intermediate phase.Second,when the Fe 3O 4is deeply discharged to 0.01V and then charged to 3V,the conversion reaction associated with large volume change could result in the formation of nanocrystallines with nanometer-scale particle size.XRD may not be able to detect such small par-ticles [48].If Fe 3O 4can have an uptake of 8Li þ,a theoretical ca-pacity of 922mAh g À1could be obtained.The voltage plateau at about 1.6V for the first charge curve of the Fe 3O 4/carbon core e shell nanotube electrode corresponds to the reversible oxidation of Fe 0to Fe 3þ/Fe 2þ.For the Fe 2O 3nanotube electrode,the first discharge and charge capacities are 1419and 1049mAh g À1,respectively,giving a coulombic ef ficiency of about 74%.After the first cycle,the charge and discharge are highly reversible with negligible irre-versible capacity.The irreversible capacity loss of the Fe 2O 3nano-tube electrode for the first cycle is probably due to incomplete conversion reaction and the solid electrolyte interphase layer for-mation at the electrode/electrolyte interface caused by the reduc-tion of electrolyte.Although the charge/discharge capacities of the Fe 2O 3nanotube electrode fade quickly,the fading rate is much slower compared to the Fe 2O 3spindles with similar size [26].The improvement of the cycling stability of the Fe 2O 3nanotube elec-trode could be attributed to the hollow tubular structure,which can accommodate larger volume changes during the charge/discharge processes.For the Fe 3O 4nanotube electrode,the first discharge and charge capacities are 1250and 912mAh g À1,respectively,giving a coulombic ef ficiency of about 73%.For the Fe 3O 4/carbon core e shell nanotube electrode,the first discharge and charge capacities are 1213and 938mAh g À1,respectively,with a coulombic ef ficiency of about 77%.It is clear to see that the carbon coating on Fe 3O 4nanotubes signi ficantly enhances the reversibility of the electrode.As discussed by Guo et al.,carbon coating on the Fe 3O 4particlesFig.4.(a)XPS survey scan spectrum,(b)Fe 2p narrow scan XPS spectrum,(c)O 1s narrow scan XPS spectrum,and (d)C 1s narrow scan XPS spectrum of the Fe 3O 4/carbon core e shell nanotubes.H.Xia et al./Journal of Power Sources 241(2013)486e 493490could not only suppress the formation of SEI films but also stabilize the formed SEI films,thus leading to an improved initial coulombic ef ficiency and better cycling stability [26].In addition to the for-mation of the SEI layer,the irreversible capacity for the first cycle is highly dependent on the mobility of Li þand e Àduring Li extraction process.The uniformly coated carbon layer on the surface of Fe 3O 4nanotubes can greatly improve the electrical conductivity of the electrode.As discussed by Li et al.,Li extraction reaction stops at a depth where the carriers cannot be suf ficiently transported through the metal oxide phase in the time scale of the experiment [49].Li þand e Àtransport could be greatly enhanced as the particle size is reduced from micrometer to nanometer.A hollow tube nanostructure could further enhance the reversible capacity of the electrode as the Li þand e Àdiffusion paths can be further reduced due to the thin tube walls.As a result,the first reversible capacity of the Fe 3O 4/carbon core e shell nanotubes is much larger than that of the Fe 3O 4/carbon nanospindles with similar particle size (749mAh g À1)[26].Fig.5e shows the charge/discharge cycle per-formance of the Fe 2O 3nanotube,the Fe 3O 4nanotube,and the Fe 3O 4/carbon core e shell nanotube electrodes at a current densityof 100mA g À1for 20cycles.It is obvious that the Fe 3O 4/carbon core e shell nanotube electrode exhibits much better cyclability compared to both the Fe 2O 3and Fe 3O 4nanotube electrodes.After 20cycles,the Fe 3O 4/carbon core e shell nanotube electrode can deliver a reversible capacity of 808mAh g À1,corresponding to 86%capacity retention of the initial reversible capacity.By contrast,the reversible capacities of the Fe 2O 3nanotube and Fe 3O 4nanotube electrodes are only 534mAh g À1and 591mAh g À1,respectively,after 20cycles.The corresponding capacity retentions of the initial reversible capacities for the Fe 2O 3and Fe 3O 4nanotube electrodes are 53%and 65%,respectively.The superior cycling stability of the Fe 3O 4/carbon core e shell nanotube electrode can be attributed to the carbon coating.The coated carbon layer formed a shell that tightly attached to the Fe 3O 4nanotube,which not only improved the electrical conductivity of the electrode but also greatly enhanced the structural stability.The carbon shell can work as a buffer layer that can effectively suppresses the volume change of Fe 3O 4and reduces the loss of electrical contact of the pulverized Fe 3O 4particles during the cycling,thus leading to greatly improved cycling stability.The cycle performance of the Fe 3O 4/carbon core eFig.5.The charge/discharge curves of (a)the Fe 2O 3nanotube electrode,(b)the Fe 3O 4nanotube electrode,and (c)the Fe 3O 4/carbon core e shell nanotube electrode at a current density of 100mA g À1.(d)ex situ XRD patterns of the Fe 3O 4/carbon nanotube electrode at various discharge states.(e)Cycle performance of the Fe 2O 3nanotube electrode,the Fe 3O 4nanotube electrode,and the Fe 3O 4/carbon core e shell nanotube electrode at a current density of 100mA g À1for 20cycles.(f)Cycle performance of the Fe 3O 4/carbon core e shell nanotube electrode at a current density of 500mA g À1for 100cycles.H.Xia et al./Journal of Power Sources 241(2013)486e 493491。
材料科学与工程基础(英文)_南京航空航天大学中国大学mooc课后章节答案期末考试题库2023年
材料科学与工程基础(英文)_南京航空航天大学中国大学mooc课后章节答案期末考试题库2023年1.The driving force for steady-state diffusion is the __________.答案:concentration gradient2.Diffusion coefficient is with the increasing diffusion temperature.答案:exponentially increased;3.Due to , alloys are usually than pure metals of the solvent.答案:solid solution strengthening, stronger;4.The finer the grains, the larger the , and .答案:strength, hardness, toughness;5.With plastic deformation,the increase of dislocationdensity will result in .答案:higher strength;6.In general, Brinell Hardness test is to measure thematerial’s hardness.答案:relatively softer7.Yield strength is corresponding to the occurrenceof deformation.答案:noticeable plastic8.Strain Hardening is also named as .答案:work hardening9.Vacancy diffusion is usually interstitial one.答案:slower than10.Edge and screw dislocations differ in what way?答案:angle between Burgers vector and line direction.11. A ____ may form when impurity atoms are added to a solid, in which case theoriginal crystal structure is retained and no new phases are formed.答案:solid solution12.One explanation for why graphite powder acts so well as a “solid lubricant”is .答案:carbon atoms in graphite are covalently bonded within planar layers but have weaker secondary bonds between layers13.Substitutional atom (impurity) is an example of ______.答案:point defect14.Interstitial solid solution belongs to .答案:finite solid solution;15.The atomic packing factor for FCC is .答案:0.7416.The coordination number of BCC crystal structure is .答案:817.The crystal structure of Cu is ?答案:FCC18.How many atoms does the face centered cubic unit cell contain?答案:Four19.If the electron configuration of Fe is 1s2 2s2 2p6 3s2 3p6 3d6 4s2, then theelectron configurations for the Fe3+ is 1s2 2s2 2p6 3s2 _____.答案:3p6 3d520.Bonds in most metals are referred to as ______.答案:Non-directional21.Covalent bonding occurs as a result of _________ sharing.答案:electron22.Which of the following is NOT an example of primary bonding?答案:Van der Waals23.Atomic weight (A) of an element corresponds to the weighted average of theatomic masses of the atom’s naturally occurring ___________.答案:isotopes24.The point on a phase diagram where the maximum number of allowablephases are in equilibrium is .答案:eutectic point25.Sterling silver (92.5%Ag/7.5%Cu) is an example of ___________.答案:Solid solution26.Engineering stress-strain curve and true stress-strain curve are equal up to .答案:Yeild point27.Among thefollowingtypical transformations of austenite in steels,____________transformation is diffusionless.答案:martensitic28.The heat-treatable aluminum alloy can be strengthened by .答案:Both of above29.In the as-quenched state, martensite is very hard and so brittle that a heattreatment known as must be accomplished sequently.答案:tempering30.During heat treatment of steel, austenite transforms into martensite by .答案:quenching31.Which of the following plane has the highest planar density for fcc.答案:(111)32.Which of the following describes recrystallization?答案:Diffusion dependent with no change in phase composition33.Heating the cold-worked metal progresses in three stages: .答案:recovery, recrystallization, grain growth;34.Strength is increased by making dislocation motion .答案:difficult35.The boundary above which only liquid phase exist is called _________.答案:liquidus36.We have an annealed carbon steel which has hardness of 150HBS. Supposewe know the hardness of Pearlite is 200HBS and the hardness of Ferrite is 80HBS, determine the carbon amount of this steel.答案:0.45%37.The maximum solubility of C in γ-austenite - solid solution is .答案:2.1438.In a plain steel that contains 0.2 percentage carbon, we should expect: .答案:a 25% pearlite and 75% pro-eutectoid ferrite39. A copper-nickel alloy is high-temperature heat treated; the diffusion of Cuinto Ni and Ni into Cu regions is referred to as _____________________.答案:Inter-diffusion40.The phase diagram of Sn-Pb alloy is called .答案:Eutectic phase diagram。
Measurements of High Density Matter at RHIC
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pmjacobs@
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1 Introduction
At high temperature or baryon density, hadronic matter dissolves into a soup of its constituent quarks and gluons. For an asymptotically free field theory such as QCD, the state of matter at high energy density is simple1: long range (low momentum) interactions are screened, and short range (high momentum) interactions are weak, leading to an ideal gas equation of state in the high energy density limit. At temperature T ≫ ΛQCD matter is a gas of deconfined, weakly interacting quarks and gluons (the fined and matter consists of strongly interacting hadrons. “Quark-Gluon Plasma”, or QGP), whereas at T ≪ ΛQCD quarks and gluons are con-
temperature QCD can only be carried out numerically on the lattice.3 Fig. 2 shows a recent lattice calculation of the energy density ǫ as function of temperature for twoand three-flavor QCD. ǫ exhibits a sharp rise in the vicinity of the critical temperature TC , indicating a rapid change in the density of underlying degrees of freedom. The ideal gas Stefan-Boltzmann limit ǫSB has not yet been achieved at T ∼ 4TC . Putting in physGeV/fm3 . This value should be kept in mind for comparison to conditions achieved in laboratory experiments. The order of the deconfinement phase transition can be determined in some limiting cases.3 It is first order for pure gauge and for three light quarks, second order for two light and one heavy quark. For physical quark masses the order of the transition, or 2 ical values, TC ∼ 175 MeV, resulting in critical energy density ǫC = (6 ± 2)TC 4 ∼ 1
微电子技术英语考试参考翻译
第一章1页1.1.1 Solid-state…固态材料可分为三种:绝缘体、半导体和导体。
图1-1给出了在三种材料中一些重要材料相关的电阻值(相应电导率)。
绝缘体如熔融石英和玻璃具有很低电导率,在10^-18到10^-8S/cm之间。
导体如铝和银有高的电导率,典型值从104到106S/cm;而半导体具有的电导率介乎于两者之间。
半导体的电导率一般对温度、光照、磁场和小的杂志原子非常敏感。
在电导率上的敏感变化使得半导体材料称为在电学应用上为最重要的材料。
3页1.1.2 The semiconductor…我们研究的半导体材料是单晶,也就是说,原子是按照三维周期形式排列。
在晶体中原子的周期排列称为晶格。
在晶体里,一个原子从不远离它确定位置。
与原子相关的热运动也是围绕在其位置附近。
对于给定的半导体,存在代表整个晶格的晶胞,通过在晶体中重复晶胞组成晶格。
6页1.1.3 As discussed…如1.1.2节所述,在金刚石结构的每个原子被4个相邻原子所包围。
每个原子在外轨道具有4个电子,并且每个电子与相邻原子共享价电子;每对电子组成一个共价键。
共价键存在于同种原子之间或具有相同外层电子结构的不同元素的原子间。
每个电子与每个原子核达到平衡需要相同时间。
然而,所有电子需要很多时间在两个原子核间达到平衡。
两个原子核对电子的吸引力保证两个原子在一起。
对于闪锌矿机构如砷化镓主要的价键引力主要来自于共价键。
当然,砷化镓也具有小的离子键引力即Ga+离子与四周As-离子,或As离子和四周Ga+离子。
7页1.1.4 The detailed…结晶固体的详细能带结构能够用量子理论计算而得。
图1-3是孤立硅原子的金刚石结构晶体形成的原理图。
每个孤立原子有不连续能带(在右图给出的两个能级)。
如原子间隔的减少,每个简并能级将分裂产生带。
在空间更多减少将导致能带从不连续能级到失去其特性并合并起来,产生一个简单的带。
当原子间距离接近金刚石结构的平衡原子间距(対硅而言晶格常数0.543nm),这个带分为两个带区。
翻译
翻译1.电极电位决定离子浓度Electrode potential depends on the concentration of the ions.2.探索矿物中汞浓度的绝对因素被发现The determination of trace concentrations of mercury in mineral is describe.3.由于目前高品质的矿石可能耗尽,富集过程是十分重要的A concentration process is important now that the depletion of high grade ores is possibility.4.用这种加工方法会浪费一些材料The machining of forgings by this method entails some loss of material.5.阿基米德最先发现固体排水的原理Archimedes first discovered the principle that water is displaced by solid bodies.6.火箭被发明应用于宇宙勘探Rocket have found application for the exploration of the universe.5.要特别注意软管,确保不被磨损Particular attention should be given to ensure that chafing does not occur.7.所有动植物的生长都需要碳All plant and animals need for growth.8.加热可以提高液体温度The temperature of the liquid is raised by the application of heat.9.夯锤由压缩空气驱动的可提高生产率Rammers driven by compressed air can increase the production rates.10.今天计算机广泛应用于解决数学问题,这些问题与天气预报和卫星送入轨道有关Today the electronic computer is widely used in solving mathematical problems having to do with weather forecasting and putting satellites into orbit.11.生产中少量产品时,数控机是极为有用的,录用生产零件必须资料的磁带可以存放起来,需要时还可重新使用和修改Numerical control machines are most useful when quantities of products to be produced are low or medium;the tape containing the information required to produce the part can be stored ,reused or modified when required.12.如果没有吸引力,电子会以直线方向飞离质子If there were no attraction,the electron would fly away from the proton in a straight line13.如果飞机速度降到一定水平以下就会突然失去升力A sudden loss lift will be experienced in case the aircraft speed falls below a certain level.14.假如油泵失灵,运转部件就会过热In case of an oil-pump failure,the moving parts will be overheat.15.万一有雾,飞机可以由指挥塔引导降落至跑道In the event of fog ,aircraft can be guided down to the runway from the control tower16.这部发动机可以高速运转,条件是把震动降低The engine can be run at very high speeds on condition the vibration can be damped out17.让水冷却十分钟再测温度Allow the water to cool for10minutes and the make the temperature.18不能行走的机器人能学会做工并孜孜不倦的工作,今天在世界各地的工厂里得到了使用Non-mobile robots,capable of learning to perform an industrial task and then of being left to perform it tirelessly,are even now in use in industrial plants all over the world.20.由于未能记住这些符号,使许多学生无法掌握他们选修的课程Failure to fix these symbols in mind keeps students from mastering the mathematical subject they take up.21假如速率或方向改变了,速度也会随之改变Velocity changes if either speed or the direction changes.22石油和天然气仍将是我们燃料的主要来源Oil and gas will continue to be our chief source of fuel23驱动这个机器的发动机是50马力的感应电动机The power unit for driving the machine is a 50-hp induction motor24一个物体的速度不会超过光速A material object can not have a speed greater than the speed of light.半导体器件,称为晶体管,在许多应用中是更换管Semiconductor device,called transistors,are replacing tubes in many applications严禁乱拆,以免损坏零件It is forbidden to dismantle it without permission so as to avoid any damage to its parts25.需要明确是磁力和电力是不同的It should be realized that magnetic forces and electric forces are not the same26 .除去水中的矿物质叫做软化The removal of minerals from water is called softening27.只有爱因斯坦的相对论能解释这种现象Einstein’s relativity theory is the only one which can explain such phenomena。
湿法磷酸选择性除杂制工业级磷酸二氢铵
Vol.53 No.4Apr.,2021第 53 卷 第 4 期2021 年 4 月无机盐工业INORGANIC CHEMICALS INDUSTRY湿法磷酸选择性除杂制工业级磷酸二氢铵王智娟(曲靖师范学院化学与环境科学学院,云南曲靖655000)摘 要:以湿法磷酸为原料,通过氟化钠选择性沉淀金属离子,使其以NaMgAl (F,OH )6-H 2O 和XMgAlF e (X 二Na +、K +、NH 4+)非含磷沉淀析岀,再通氨中和制得工业级磷酸二氢铵。
分析了氟化钠加入量对杂质脱除(Na 、K 、Al 、Mg 、 Fe 和Ca 等金属阳离子)及液相氟残留的影响,结果表明氟化钠与磷酸质量比(m NaF /叫陀)为2.5%时,效果较好,此条件下制得的磷酸二氢铵纯度和五氧化二磷收率分别达到98.53%和86.2%o关键词:湿法磷酸;磷酸二氢铵;除杂中图分类号:TQ126.35 文献标识码:A 文章编号:1006-4990(2021)04-0048-04Fabrication of industrial grade ammonium dihydrogen phosphate via selective removal ofimpurities from wet-process phosphoric acidWang Zhijuan(Faculty of Chemistry and Environment Science , Qujing Normal University ,Qujing 655000, China)Abstract : Ammonium dihydrogen phosphate with high purity can be used as water-soluble fertilizer ,flame retardant ,feed andfood additives and recently it has been studied for preparation of phosphate optical glass , cathode materials for lithium batter ies and nonlinear optical materials.Due to its broad application prospect in the fields of agriculture , fire protection , food and materials , the demand for high purity ammonium dihydrogen phosphate is increasing.High purity ammonium dihydrogen phosphate can be fabricated via thermal phosphoric acid and extraction-purified wet-process phosphoric acid route.The former route is simple and can get high quality of product , but it is restricted to the influence of resources , energy and environment.While the latter route is complex and needs large investment.Hence , more researchers focus on the direct preparing high puri ty ammonium dihydrogen phosphate with raw wet-process phosphoric acid.But the lower P 2O 5 yield of product (25%~40%) inhibited its development due to the formation of a large amount of phosphorus-containing precipitates (e.g., metallic phospha te ) during ammoniation.Therefore , herein modified-process with sodium fluoride was used to selectively precipitate metalcations to compounds containing no phosphorus (e.g., (NH 4)x (Mg )y (Al )z F 6(OH )6・2H 2O ,NaMgAlF 6送出。
2-D spectroscopy and modeling of the biconical ionized gas in NGC 4388
a r X i v :a s t r o -p h /0301110v 1 7 J a n 2003Astronomy &Astrophysics manuscript no.H3965February 2,2008(DOI:will be inserted by hand later)2-D spectroscopy and modeling of the biconical ionized gas inNGC 4388⋆S.Ciroi 1,M.Contini 1,2,P.Rafanelli 1,and G.M.Richter 31Dipartimento di Astronomia,Vicolo dell’Osservatorio 2,I-35122Padova,Italy e-mail:ciroi@pd.astro.it,piraf@pd.astro.it2School of Physics and Astronomy,Tel-Aviv University,Ramat-Aviv,Tel-Aviv,69978Israel e-mail:contini@post.tau.ac.il3Astrophysikalisches Institut Potsdam,An der Sternwarte 16,D-14482Potsdam,Germany e-mail:gmrichter@aip.deReceived 9September 2002;accepted 23December 2002Abstract.We present recent results from spectroscopic data and modeling of the biconical ionized gas in the Seyfert-2galaxyNGC 4388.A field of ∼2.6×2.4kpc centered on the nucleus has been observed by means of the modern technique of integral field spectroscopy.The analysis of more than two hundred spectra allowed to study the physical characteristics of the gas in the surroundings of the active nucleus.The South-West ionization cone,revealed by the [O III]λ5007/H βexcitation map,shows high emission line ratios not completely supported by simple posite models which account for the combined e ffects of photoionization and shock show that such high [O III]/H βline ratios are emitted by low density (n 0=30cm −3)gas inside large (D >1pc)shocked clouds (V s =100km s −1)reached by a relatively low flux from the active nucleus.The data of the VEELR in the North-East cone by Yoshida et al.(2002)have been modeled.The results confirm that photoionization is the prevailing mechanism,but nontheless weak shocks are under way between colliding clouds with small (<1pc)sizes and low densities n 0≤100cm −3,moving outward at relatively low velocities (V s =100km s −1).Key words.Techniques:spectroscopic –Galaxies:nuclei –Galaxies:Seyfert –Shock Waves –Galaxies:individual:NGC43881.IntroductionThe prevailing picture of an AGN structure,the so-called Unified Model,provides for a central supermassive Black-Hole (BH),whose gravitational potential energy is the ultimate source of the AGN luminosity.Matter falling into the BH loses angular momentum through viscous and turbulent processes in an accretion disk,resulting into emission of photons in the ultraviolet,soft-X and hard-X ray wavelength domains (Urry &Padovani 1995).According to the Unified Model the central source is sur-rounded by a dense obscuring thick torus which is able to restrict the emergent radiation from the nucleus to a bipolar cone with an opening angle determined by the torus geometry (Pogge 1989).Imaging in optical emission lines shows in some cases high ionization regions with a conical and /or biconical morphology.These so-called ionization cones are direct evidence that radiation escapes anisotropically (Mulchaey et al.1994).In this frame we have carried out an observational campaign to study the circumnuclear and extranuclear environment of a spectroscopically selected sample of Seyfert galaxies2S.Ciroi et al.:2-D spectroscopy and modeling of the biconical ionized gas in NGC4388Fig.1.The position of the spectrograph over the galaxy.The×symbol indicates the assumed position of the central engine.the central power-law continuum as the principal excitation mechanism(Pogge1988;Petitjean&Durret1993).Kinematic data obtained with Fabry-Perot Interferometer (Veilleux et al.1999b)revealed non-rotational blueshifted ve-locities in the extraplanar gas northeast of the nucleus,likely produced by a bipolar outflow.Using deep narrow-band imaging obtained with the Suprime-Cam mounted at the Subaru Telescope,Yoshida et al.(2002; hereafter YOS02)have recently found a very large emission line region(VEELR)extended up to∼35kpc northeast of the nucleus.It consists of many gas clouds orfilaments,part of which(within12kpc)are clearly ionized by the nuclear radi-ation.They claim that the most plausible origin of this ionized gas is tidal debris due a past interaction with a gas-rich dwarf galaxy.Moreover at radio wavelengths NGC4388shows a two sided, asymmetric structure with aflat spectrum central component, offset by∆α=1.2′′and∆δ=2.6′′from the apparent optical nucleus,a diffuse blob to the North and an elongated feature to the South with a compact blob in it(Hummel&Saikia1991). Several radio maps have shown that this feature is clearly asso-ciated with the S-W ionization cone,suggesting the possibility of an interaction between the radio jet and clouds of the ion-ized gas(Falcke et al.1998).Such interaction generates shock fronts,which cannot be neglected in the interpretation of the spectra.In this paper we investigate the physical conditions in the extended biconical ionized gas of NGC4388through the mod-eling of the optical emission line and continuum spectra ob-served in different regions.Both the ionizing radiation from the active nucleus and the shock effects are consistently accounted for.In Sect.2the observations and modeling of the S-W cone are presented.In Sect.3the N-E cone is considered and the VEELR is modeled on the basis of YOS02data.The contin-uum SED is discussed in Sect.4.Concluding remarks follow in Sect.5.2.The South-West cone2.1.Observations and data reductionNGC4388was observed in March1998at the6-m telescope of the Special Astrophysical Observatory(Russia)with the MultiPupil Fiber Spectrograph(MPFS),an integralfield unit made by an array of16×15microlenses coupled with a close-packed bundle of opticalfibers,which carry the incoming sig-nal to the spectrograph.Each of the240elements was coveringS.Ciroi et al.:2-D spectroscopy and modeling of the biconical ionized gas in NGC43883 a region of1′′×1′′corresponding to a totalfield of view ofabout2.6×2.4kpc(assuming H0=75km s−1Mpc−1).Two600sec exposures were taken using a TK-1024CCD,whichhas a pixel size of24µm,and orienting the largest side of thearray at P.A.∼34◦(Fig.1).The grating was chosen to give aspectral range of∼4400–7100Å,with a resolution of10Åanda dispersion of5.3Å/px.The reduction of the data was carried out by means of asoftware package,developed within our group,and running un-der IRAF1environment.After the usual steps of bias and dark subtraction,all the frameswere cross-correlated,in order to compensate for the shifts be-tween them caused by mechanicalflexions of the instrument.Then aflatfield was chosen as reference image to obtain thegeometrical scheme of the spectra arrangement:the position,width and layout along the dispersion direction of every spec-trum stored in it were defined and the resulting scheme wassubsequently applied to all the images in order to extract foreach of them the2401-D spectra.The dispersion solution forwavelength calibration was determined byfitting the line posi-tions of He-Ne-Ar lamp exposures with low order Chebyshevpolynomial functions.The sky subtraction was performed byaveraging the output of8fibers devoted to the night sky obser-vation and placed at a distance of4.5′from the center of thefield of view.Then the data wereflux calibrated by observingthe spectrophotometric standard star HZ44:all itsflat-fielded,wavelength calibrated and sky subtracted spectra were summedtogether in order to collect the total incomingflux,to obtainthe function necessary to convert counts in physical units andto account for the sensitivity response of the system at differentwavelengths.Finally,cosmic rays were removed by combiningcorresponding spectra of the two exposures of NGC4388anda correction for Galactic extinction(A V=0.08)was applied.Fig.2shows some examples of the reduced spectra chosen withdifferent signal-to-noise ratio in thefield of view.The positions,widths andfluxes of all the emission linesdetectable3σover the continuum were measured using theIRAF task SPLOT.In case of close blending like Hα+[N II]λλ6548,6583or[S II]λλ6717,6731,better results in perform-ing an interactive multigaussianfit of the total profile could beobtained by using the MIDAS package ALICE,whose inputparameters(afirst estimate of amplitude,center and sigma ofthefitting gaussian)are independentlyfixable.2.2.Data analysisIn order to get accurate estimate of linefluxes and ratios it isnecessary to take into account that emission lines in galaxiesare generally affected,and in some cases even dominated,bythe underlying starlight contribution.It is possibile to removethe stellar features by subtracting an absorption-line”tem-plate”galaxy spectrum built by means of spectral synthesistechniques(see e.g.Bonatto et al.(1989)),or directly obtained4S.Ciroi et al.:2-D spectroscopy and modeling of the biconical ionized gas in NGC4388correction was considered satisfactory(an example is given in Fig.3).The metallic lines(Mg Iλ5175,Fe Iλ5269and Na I λ5892)were almost always canceled out after the subtraction. Only in some cases the stellar features of the template have been strengthened to better match the Hβabsorption,produc-ing an overcorrection of the metallic absorptions.This can hap-pen since stellar populations cannot be omogeneus everywhere in thefield of view.The resulting variations of line intensities have been estimated weak(<10%for Hβ)in spectra with very bright emission lines,significant(∼10−30%)in most of the spectra and very important in few spectra(up to60%).The emission linefluxes,measured after the starlight contamination removal,were corrected for internal redden-ing by means of the theoretical Balmer decrement value Hα/Hβ= 2.86for Case B recombination at electronic temperature T e=104K and assuming the reddening law by Miller&Mathews(1972).Several images of the galaxy within thefield of view were reconstructed at different wavelengths,as for instance the map of the visible continuum at5500Å.The position of its maxi-mum intensity is located to the N-W of the observed peak of the emission line maps,which we have decided to assume as position of the photoionization source(hereafter nucleus).We do not confirm the large offset between the location of the radio source withflat spectrum and the visible continuum peak indi-cated in Hummel&Saikia(1991)and references therein:the radio source,the visible continuum and the emission lines have their maxima intensities close to each other(separation∼1′′). We have discarded the idea to adopt the position of the radio source,which should indicate the real location of the AGN,as nucleus in ourfield of view since the spatial resolution of our data is only1′′/px and an accurate astrometric calibration of the integralfield images is very hard to obtain.The map of the[O III]λ5007/Hβemission line ratios re-vealed part of the S-W ionization cone(Fig.4).The cone has the axis at P.A.∼200◦and an aperture angle of∼70◦,less than the value measured by Pogge(1988),probably due to our smallerfield of view.The gaseous regions within the ionization cone have been investigated.Their intrinsic FWHM,estimated from the gaus-sian analysis of the emission lines after having removed the instrumental component(∼10Å),range in the interval ∼200–700km s−1,with a median value of∼480km s−1,ve-locities usually observed in the Narrow Line Regions of Seyfert galaxies.The diagnostic emission line ratios[N II]λ6583/Hα,[O I]λ6300/Hα,[S II]λλ6716+6731/Hαand [O III]λ5007/Hβ(Veilleux&Osterbrock1987),show the typ-ical properties of gas ionized by a non-thermal source(Fig.5).Moreover the spatial distribution of the ionization degree within the cone,evaluated by means of the[O III]λ5007/Hβra-tio as a function of the distance from the nucleus,indicates that the gas is highly ionized even at large distances from the AGN. In order to understand if the AGN could account for such ob-served ionization,the Hαluminosity of each spectrum was cal-culated from the reddening corrected Hαfluxes.Then the num-ber of ionizing photons needed to produce such luminosities, Q ion=7.3×1011L(Hα)photons sec−1(Kennicutt1998),was evaluated and later compared with Q⋆nuc=Q nucΩ/4π,where Q nuc is the number of photons coming from the nucleus,di-luted by the covering factorΩ/4π,andΩis the solid angle of a region seen from the nucleus.By assuming that the nuclear source is an isotropic emitter of radiation occulted along our line of sight,we attempted to estimate Q nuc by taking the average of the calculated number of photons ionizing the regions surrounding the nucleus,after having removed the effect of the covering factor(Q ion4π/Ω).A value of Q nuc∼4.87×1052photons sec−1was obtained,in good agreement with the4.98×1052photons sec−1computed by Colina(1992)using the IUE spectrum of the galaxy and the flux at912Å.The resulting Q ion/Q⋆nuc ratio concentrates around a value of 2.5.This indicates that the active nucleus is the dominant ioniz-ing source for the regions within ourfield of view,in agreement with what observed in the VO diagrams.In spite of that,the ionization parameter U=Q nuc/4πcr2N H,calculated within the cone as a function of the distance r0from the nucleus,ranges between10−5.0and10−2.8,a result clearly in contrast with the already pointed out high ionization level of almost all the re-gions.A total hydrogen density N H=3×102cm−3is assumed, on the basis of the the electron density values estimated over the wholefield,using the[S II]λλ6717/6731ratio and assum-ing T=104K(except where the sulphur lines were not visible or extremely blended).The problem of the missing data has been solved taking the average value of independent linear interpo-lations of the[S II]ratios along the two orthogonal directions of the spectral array.The resulting N e distribution presented values<103cm−3,with a median of∼300cm−3.Of course due to the uncertainties of the[S II]emission line strengths,the es-Fig.4.The ionization cone obtained by the reconstructed map of the[O III]/Hβemission line ratios.The×symbol indicates the position of the assumed nucleus(as in Fig.1),OC is the maximum intensity of the optical continuum at5500Å,and RS is the approximate location of the radio source withflat spectrum.S.Ciroi et al.:2-D spectroscopy and modeling of the biconical ionized gas in NGC 43885Fig.5.Diagnostic diagrams of the emission line regions inside the ionization cone.The typical uncertainties of the ratios are indicated by the error bars in the bottom-right corner of each plot.timation of the electron density is not very accurate and just a simple decrease by a factor of 10can account for the ionization parameter in the regions far from the nucleus.2.3.The modelsThe contribution of the shocks to the line intensities is tested bycomparing calculated with observed spectra.The code SUMA (Contini &Viegas 2001,and references therein),which accounts consistently for the photoionization flux from an external source and for the shocks is adopted.The general model assumes matter bound gaseous and dusty clouds,which move outwards from the source and emit the line and continuum spectra.A shock front forms on the outer edge of the clouds,while the inner edge is reached by the radiation flux from the source.The input parameters are :the radiation flux intensity,F H (in photons cm −2s −1eV −1at 1Ryd),the spectral index,α(=1.5for all models),the shock velocity,V s ,the preshock density,n 0,the preshock magnetic field,B 0(=10−4gauss),the dust-to-gas ratio,d /g,and the geometrical thickness,D,of the emitting clouds.Cosmic relative abundances (Allen 1973)are adopted.Composite models lead to a complex distribution of the temperature and the density throughout the clouds.In radiation dominated (RD)models the e ffect of the flux from the active center (AC)prevails on the shock,while in shock dominated (SD)models the flux is absent (F H =0).When shocks and pho-toionizing fluxes act on the opposite sides of the cloud,two regions of relative high temperature appear near the edges (see Sect.2.4).Higher temperatures correspond to higher shock ve-locities (T ∝V s 2),while the radiation flux cannot heat the gas to >2-3104K.This temperature leads to high O +2/O oxygen fractional abundance,so the [OIII]line strength depends on F H .The cooling rate (∝n 2,where n is the density of the gas)increases with compression downstream of the shock leading to cool gas in the internal region of the cloud.The larger the cool region the strongest the low ionization level lines.The relative sizes of the hot and cool gas regions depend,therefore,on the shock velocity,on the intensity of the flux from the AC,onthe preshock density,and on the geometrical thickness of the clouds.A large grid of models is calculated in order to select the most suitable parameters to the observational evidences for each region in the galaxy.Recall that a first choice is roughly obtained considering that the [O III]λ5007line flux depends on the intensity of the nuclear radiation flux,the [S II]λλ6717/6731line ratio depends on the density,as seen before,and the intensity ratios of high to low ionization lines depend on the geometrical thickness of the clouds and on the shock ve-locity (see Contini &Viegas 2001).The input parameters are then changed consistently in order to obtain the best fit of all the observed data.2.4.[O III ]/H βand [O I ]/H βThe observations cover the SW cone providing line ra-tios in many di fferent regions.We focus on [O III]λλ4959+5007/H βand [O I]λλ6300+6363/H βline ratios,be-cause [O III]lines are generally strong in Seyfert 2galaxies and are emitted by gas ionized by the radiation flux from the active nucleus,while [O I]lines are emitted from gas at lower temper-atures and are generally strong in the presence of shocks.Moreover,Veilleux et al.(1999a)claim that dynamical pro-cesses such as entrainment by AGN-powered radio jets gen-erally have a stronger e ffect on the kinematics of the highly ionized [O III]emitting gas than on those of the low-ionization H αemitting material.Therefore,by modeling the observed spectra it is possible to determine the distribution of the radiation flux intensity andFig.6.Contour map of the visible continuum at 5500Å.The isointensities correspond to the values:1.2,1.5,1.8,2.2,2.5,2.8,3.0,3.15,3.25(×1.e-15erg cm −2s −1).Filled circles corre-spond to the values of the observed [O III]λλ4959+5007/H βra-tios.The small ”squared window”located at (6,9)indicates the assumed position of the ionization source.The map is orien-tated like in Fig.4.6S.Ciroi et al.:2-D spectroscopy and modeling of the biconical ionized gas in NGC4388Fig.7.The comparison of model calculation with ob-servations (filled triangles)for [O III]λλ4959+5007/H βvs [O I]λλ6300+6363/H β.See text for a detailed description.of other parameters,e.g.the shock velocity of the gas,the den-sity,and the geometrical thickness of the clouds in the observed region.The reliability of the models is checked comparing the observed spectral energy distribution (SED)of the continuum with model results (see Sect.4).The observed [O III]/H βline ratios overlaid to the contin-uum of the galaxy at 5500Åare shown in Fig.6in a syn-thetic representation.The [O III]/H βdistribution is not smooth.Particularly,high [O III]/H βratios appear in some regions far from the active center.This suggest that the clouds in those re-gions have abnormal intrinsic conditions.In Fig.7[O III]/H βversus [O I]/H βfrom the observations (black triangles)is compared with model calculations.All the models correspond to V s =100km s −1.Higher velocities are less fitting,and velocities lower by a factor <2lead to similar results.The thick solid line refers to shock dominated models with line ratios increasing with decreasing D and n 0.The bulk of the data,however,is scattered throughout a region of the diagram better fitted by radiation dominated models.The thin solid line determines roughly the right edge of this region.The numbers in Fig.7refer to Table 1,where the models are de-scribed.The dashed lines connect models calculated with dif-ferent D (increasing from left to right)but all corresponding to the same flux intensity F H ,while the dotted lines connect mod-els calculated with di fferent F H (increasing from left to right)and corresponding to the same D.Fig.7shows that the trend of both types of models is di fferent from the observed one,i.e.[O III]/H βincreasing with [O I]/H β.The increasing trend of the line ratios can be explained ei-ther by a slightly larger D and stronger F H (models 1in Table 1)or by very large clouds (D ≥1pc,models 2in Table 1),corre-sponding to a lower density,and a flux intensity not exceedingTable 1.The models in Fig.7.150.9,10,12 1.5230.30,40,500.9350.7.0.7,1.0,1.2450.5,6,7 1.550. 3.5,4,50.76100.0.60.8,1.0,1.27100.0.40.6,0.8,0.98100.0.2,0.25,0.30.6S.Ciroi et al.:2-D spectroscopy and modeling of the biconical ionized gas in NGC 43887metric to have a comparable view of the two sides of the cloud.The shock front is on the left and the radiation flux from the source reaches the rightedge.Fig.9.The case of a small D and relatively low F H .The distri-bution of the temperatures and densities (upper panels)and of the most significant ion fractional abundances (lower pannels)throughout the clouds for di fferent models (seetext).Fig.10.The same as forFig.9in the case of a large D and low n 0.The geometrical thickness D is a crucial parameter to low-level and,particularly,to neutral lines,because they are emitted from rather cold gas.Therefore,in the bottom pannels the dis-tribution of the fractional abundance of O +0/O (dotted line),O +1/O (short-dash line),O +2/O (long-dash line),and H +1/H (solid line)have been plotted.Fig.9corresponds to D =31016cm (0.01pc)and Fig.10to D =41018cm (1.3pc).It can be noticed that two zones of gas emit the [O III]lines,one from the side of the shock,where collisional ionization prevails,and the other from gas ionized by radiation.The ionization rate due to the photoionization flux from the nuclear source,dominates in a large region of the cloud,particularly in models calculated with V s =100km s −1,where the gas density and optical thick-ness are rather low.A large region of cool gas appears inside clouds corresponding to a large geometrical thickness and low density,leading to relatively strong [O I]lines.2.5.[S II ]/H βFig.11shows [S II]λλ6717+6731/H βversus [S II]λλ6717/6731.The low ionization lines are strongly af-fected by shocks.For models accounting for the shock a large range of electron densities follows from compression in the downstream region.The lines,calculated integrating through the geometrical thickness of the clouds,account for the di fferent conditions of the gas (see section 2.4).Some significant models,which are the same as those adopted to explain the [O III]/H βratios in Fig.7,are indicated by open circles.They show a good agreement to the observed [S II]λλ6717/6731line ratio between 1and 1.3in Fig.11.The low density model gives [S II]λλ6717/6731≤1.4.Notice,however,that the [S II]λλ6717+6731/H βratios are higher by a factor <2than the data for most models,indicating that the S /H relative abundance is lower than cosmic.This is a common characteristic to Seyfert 2galaxies where sulphur is depletedFig.11.The same as for Fig.7for [S II]λλ6716+6731/H βvs [S II]λλ6716/6731.8S.Ciroi et al.:2-D spectroscopy and modeling of the biconical ionized gas in NGC4388 from the gaseous phase.The models are calculated adoptingd/g(by number)=10−14-10−13,indicating that dust is indeedpresent in the NGC4388cone region.Reminding that compression increases with V s,models cal-culated with higher densities and velocities(V s=300km s−1)fit the data corresponding to low[S II]λλ6717/6731(<1),al-though their observed errors are large.Finally,models withV s=500km s−1hardlyfit any data,suggesting that high ve-locity clouds are relatively few(see Sect.4).The results show that the bulk of the shock velocities islower than the velocities corresponding to the FWHM of theemission lines(200-700km s−1),indicating that strong shocksdo not form in the observed region of NGC4388,but ratherlow shock velocities V s=100km s−1and low densities n0≤100cm−3dominate.3.The North-East coneWe now consider the N-E cone and the very extended emission-line region(VEELR)discovered by YOS02in order to have a larger view of the ionization conditions in NGC4388.The nuclear region of the galaxy has been successfully investigated by Petitjean&Durret(1993),but only a few emission lines were observed at21′′,25′′,and38′′from the nucleus.YOS02observed the[O III]λ5007and Hα+[N II]λλ6548,6583fluxes from different clouds in the VEELR, which extends northeastward of the galaxy,very far outside the galaxy disk.The ionization cone is traced by the N-E plume and a high ionization cloud located at10′′-15′′northwest of the nucleus.They claim that there is a sudden change in the excitation state of the gas around the line at P.A.65◦,which coincides with the extrapolation of the northern edge line of the S-W cone.Notice that these authors assume as distance of NGC4388,the distance of the Virgo cluster(16.7Mpc),which is different from that one used by us for the S-W cone(33.6 Mpc).Therefore,all the distances should be scaled by a factor of2.In Figs.12,13,and14we compare the results of models calculated with the code SUMA with the YOS02data.The errorbars refer to the typical uncertainty of20%estimated by YOS02.In all the diagrams thefluxes of[O III]versus Hα+[N II](in erg cm−2s−1)are presented.Recall that models are calculated at the emitting nebula,while data are observed at Earth.Therefore,we have multiplied the data by d2/r2,where r is the distance of each cloud from the center of the galaxy and d is the distance of NGC4388from Earth.All models are calculated adopting a geometrical thickness, D=3pc,and B0=10−5gauss,which is similar to the magnetic field in the ISM(B0=10−6-10−5gauss).Shock dominated models,calculated considering only heat-ing and ionization of the clouds by the shock(F H=0),are pre-sented in Fig.12.The models are labeled by the shock veloc-ity in km s−rge squares correspond to n0=10cm−3,small squares to n0=2cm−3.Relatively low preshock densities lead to the best agreement with the data,however,the SD models give a poorfit to the observed trend.This confirms YOS02sugges-tion that gas excitation depends also on theflux from the active nucleus even at such large distances.We have used,therefore,Fig.12.The comparison of model results(corresponding to F H=0.)with the observations for[O III]λ5007(erg cm−2s−1) versus[N II]+Hα(erg cm−2s−1)in the VEELR.Symbols are given in thetext.Fig.13.The same as for Fig.12for composite models calcu-lated with n0=10cm−3.RD models tofit the data.Recall that RD models are also com-posed because they account for the shock,even if the effect of the photoionizingflux prevails.We present in Figs.13and14radiation dominated models calculated with different velocities andfluxes,adopting n0=10 cm−3and2cm−3,respectively.Higher densities do notfit.In Fig.13black triangles indicate models calculated with V s=50S.Ciroi et al.:2-D spectroscopy and modeling of the biconical ionized gas in NGC 43889Fig.14.The same as forFig.13for composite models calcu-lated with n 0=2cm −3.Fig.15.The comparison of selected model results with the observations for [O III]λ5007(erg cm −2s −1)versus [N II]+H α(erg cm −2s −1)in the VEELR (see text).km s −1,white triangles in the left side of the diagram corre-sponding to V s =30km s −1and at the right to V s =70-90km s −1.The models are labeled by the values of log(F H ).The maxi-mum [N II]+H αvalue is explained by V s =150km s −1.Dotted lines join the results of models calculated with V s =90km s −1.Table 2.The best fitting models.M1M2M3M4M5Notice that,roughly,all the data can be reached by the models represented by the grid.In Fig.14the models are calculated with V s =50km s −1(black triangles),V s =70km s −1(small white triangles),and V s =100km s −1(large white triangles).The adopted fluxes range between log F H =7.and 9.It can be noticed that the cal-culated trends do not correspond to the observed one,however,some data are well reproduced by the models.In particular,the maximum and minimum observed [N II]+H αare not explained by these models.We have chosen the best fitting models from Figs.13and 14and we present in Fig.15consistent modeling of the entire dataset.The selected models represented by open circles are described in Table 2.The fluxes of [O III]and H α+[N II]are given in Fig.16as function of distance from the center.The data refer to the fluxes observed at the clouds.Fig.16shows that the line fluxes decrease with distance,however,di fferent conditions coexist in the VEELR leading to the large scattering.The emission line flux from the cloud,identified by YOS02(see their Fig.3)as C20,located at the extreme northern edge of the cone,is explained by a low flux (log F H =6.5),n 0=2cm −3,and a low shock velocity (35km s −1).The largest H α+[N II]flux is emitted by the cloud identified as C26,locatedFig.16.The fluxes of [O III](filled triangles)and [N II]+H α(asterisks)observed at the clouds are plotted as function of the cloud distance from the center.。
法布里珀罗基模共振英文
法布里珀罗基模共振英文The Fabryperot ResonanceOptics, the study of light and its properties, has been a subject of fascination for scientists and researchers for centuries. One of the fundamental phenomena in optics is the Fabry-Perot resonance, named after the French physicists Charles Fabry and Alfred Perot, who first described it in the late 19th century. This resonance effect has numerous applications in various fields, ranging from telecommunications to quantum physics, and its understanding is crucial in the development of advanced optical technologies.The Fabry-Perot resonance occurs when light is reflected multiple times between two parallel, partially reflective surfaces, known as mirrors. This creates a standing wave pattern within the cavity formed by the mirrors, where the light waves interfere constructively and destructively to produce a series of sharp peaks and valleys in the transmitted and reflected light intensity. The specific wavelengths at which the constructive interference occurs are known as the resonant wavelengths of the Fabry-Perot cavity.The resonant wavelengths of a Fabry-Perot cavity are determined bythe distance between the mirrors, the refractive index of the material within the cavity, and the wavelength of the incident light. When the optical path length, which is the product of the refractive index and the physical distance between the mirrors, is an integer multiple of the wavelength of the incident light, the light waves interfere constructively, resulting in a high-intensity transmission through the cavity. Conversely, when the optical path length is not an integer multiple of the wavelength, the light waves interfere destructively, leading to a low-intensity transmission.The sharpness of the resonant peaks in a Fabry-Perot cavity is determined by the reflectivity of the mirrors. Highly reflective mirrors result in a higher finesse, which is a measure of the ratio of the spacing between the resonant peaks to their width. This high finesse allows for the creation of narrow-linewidth, high-resolution optical filters and laser cavities, which are essential components in various optical systems.One of the key applications of the Fabry-Perot resonance is in the field of optical telecommunications. Fiber-optic communication systems often utilize Fabry-Perot filters to select specific wavelength channels for data transmission, enabling the efficient use of the available bandwidth in fiber-optic networks. These filters can be tuned by adjusting the mirror separation or the refractive index of the cavity, allowing for dynamic wavelength selection andreconfiguration of the communication system.Another important application of the Fabry-Perot resonance is in the field of laser technology. Fabry-Perot cavities are commonly used as the optical resonator in various types of lasers, providing the necessary feedback to sustain the lasing process. The high finesse of the Fabry-Perot cavity allows for the generation of highly monochromatic and coherent light, which is crucial for applications such as spectroscopy, interferometry, and precision metrology.In the realm of quantum physics, the Fabry-Perot resonance plays a crucial role in the study of cavity quantum electrodynamics (cQED). In cQED, atoms or other quantum systems are placed inside a Fabry-Perot cavity, where the strong interaction between the atoms and the confined electromagnetic field can lead to the observation of fascinating quantum phenomena, such as the Purcell effect, vacuum Rabi oscillations, and the generation of nonclassical states of light.Furthermore, the Fabry-Perot resonance has found applications in the field of optical sensing, where it is used to detect small changes in physical parameters, such as displacement, pressure, or temperature. The high sensitivity and stability of Fabry-Perot interferometers make them valuable tools in various sensing and measurement applications, ranging from seismic monitoring to the detection of gravitational waves.The Fabry-Perot resonance is a fundamental concept in optics that has enabled the development of numerous advanced optical technologies. Its versatility and importance in various fields of science and engineering have made it a subject of continuous research and innovation. As the field of optics continues to advance, the Fabry-Perot resonance will undoubtedly play an increasingly crucial role in shaping the future of optical systems and applications.。
光速不变原理的英文
光速不变原理的英文The Principle of the Constancy of the Speed of Light.The principle of the constancy of the speed of light, also known as the special theory of relativity, is a fundamental concept in physics that revolutionized our understanding of space and time. This theory, proposed by Albert Einstein in 1905, states that the speed of light ina vacuum is constant and independent of the motion of the observer or the source of light.Before delving into the intricacies of this principle,it's crucial to understand what light is and how it behaves. Light is a form of electromagnetic radiation that travels through space as waves. These waves oscillateperpendicularly to their direction of propagation, andtheir speed is determined by the properties of the medium through which they travel. In a vacuum, light travels at a constant speed, denoted by the symbol 'c', approximately equal to 299,792,458 meters per second.The significance of the principle of the constancy of the speed of light lies in its implications for physics and cosmology. According to this principle, the speed of lightis the same for all observers, regardless of their relative motion. This means that if two observers are movingrelative to each other, they will measure the speed oflight to be the same, even though their measurements of distance and time will differ.This principle challenges the classical concepts of absolute space and time, introducing the idea of relativity. In the classical view, space and time were considered absolute and unchanging, with all observers agreeing on the measurements of distance and time. However, Einstein's theory suggests that space and time are relative and can be affected by the motion of observers.One of the consequences of the principle of the constancy of the speed of light is time dilation. This phenomenon occurs when time appears to slow down for an observer moving relative to another observer. For example,if an astronaut travels in a spacecraft at a high speed, the time they experience will be slower than the time experienced by someone on Earth. This is because the astronaut's frame of reference is moving relative to the Earth, and the principle of the constancy of the speed of light dictates that the speed of light remains constant regardless of the observer's motion.Another consequence is length contraction. This refers to the phenomenon where an object moving relative to an observer appears to be shorter than it actually is. This is because the moving object's length in the direction of motion is reduced due to the relative motion between the object and the observer.The principle of the constancy of the speed of light has far-reaching implications in physics and cosmology. It underpins many theories and experiments, including the famous Michelson-Morley experiment, which aimed to detect the existence of an ether, a hypothetical medium through which light travels. The negative results of this experiment led to the development of special relativity andthe abandonment of the ether theory.The principle of the constancy of the speed of light also forms the foundation of Einstein's general theory of relativity, which extends the ideas of special relativity to include gravity. General relativity suggests thatgravity is a manifestation of the curvature of spacetime caused by the presence of matter and energy.In conclusion, the principle of the constancy of the speed of light is a fundamental concept in physics that has revolutionized our understanding of space and time. It challenges the classical view of absolute space and time, introducing the idea of relativity and revolutionizing our understanding of the universe. The implications of this principle are vast and far-reaching, touching upon areas such as time dilation, length contraction, and the curvature of spacetime.。
高密度电法不同装置的勘探效果对比-物探装备
2009年2月 物 探 装 备第19卷 第1期・重磁电技术・高密度电法不同装置的勘探效果对比马志飞3 刘鸿福 叶 章 杨建军(太原理工大学矿业工程学院,山西太原030024)摘 要马志飞,刘鸿福,叶章,杨建军.高密度不同装置的勘探效果对比.物探装备,2009,19(1):52~55,67 高密度电法由于自身的优势而在工程地质勘察等领域得到越来越广泛的应用。
其工作装置有很多种,在实践中应根据各种跑极方式的特点来选取最合适的装置模式。
通过野外实验研究,温纳装置的垂向分辨率相对较高,施伦贝尔1装置对地质体的水平分辨率很高,温施1装置在测深方面具有明显优势。
为了保证物探数据的准确性,野外数据的采集最好采用两种或两种以上的装置,以便于资料的对比和室内解释。
关键词 高密度电法 温纳装置 施伦贝尔1装置 温施1装置ABSTRACTMa Zhifei,Liu H ongfu,Ye Zh ang and Yang parison of exploration effect for different devices of high2den2 sity electrical prospecting.EGP,2009,19(1):52~55,67 High2density electrical prospecting has been more and more widely used in the region of engineering geological exploration since own superiority.There are many varieties of work devices,and more appropriate device pattern should be selected according to different electrode arrangement in practice.Through experimental study in the field, the Wenner device is characters of higher vertical resolution;Schlumbeger21device is characters of higher lateral res2 olution of geologic body;Wenner2Schlumberger21device has clear superiority in sounding.In order to ensure the ac2 curacy of geophysical prospecting data,it is best to use two or more than two devices for acquisition of field data, ensuring the data correlation and indoor interpretation.K ey w ords high2density electrical prospecting,Wenner device,Schlumbeger21device,Wenner2Schlumberger21device0 引言在众多的直流电阻率测深方法中,高密度电阻率法凭借其工作效率高、反映的地电信息量大、工作成本低、测量简便等突出优势,在煤矿采空区调查、水库大坝的坝体稳定性评价、坝基渗漏勘查、堤坝裂缝检测、建筑选址的地基勘探、涵洞和溶洞位置勘查、岩溶塌陷和地裂缝探测、寻找地下水、管线探测以及岩土工程勘察等方面,发挥着越来越重要的作用[1]。
Angew. Chem. Int. Ed. 2000, 39, 3772
1.IntroductionIn general,an ionic liquid is a liquid that consists only of ions.However,this term includes an additional special definition to distinguish it from the classical definition of a molten salt.[1]While a molten salt is generally thought to refer to a high-melting,highly viscous and very corrosive medium, ionic liquids are already liquid at low temperatures(<1008C) and have relatively low viscosity.The apparently somewhat arbitrary line drawn between molten salts and ionic liquids at a melt temperature of1008C can be justified by the abrupt improvement in the range of applications for liquid salts below this temperature.Even though some examples are known in which high-temperature salt melts have been successfully used as reaction media for synthetic applica-tions,[2]only a liquid range below1008C can enable the versatile substitution of conventional,organic solvents by ionic liquids.The development of ionic liquids goes back to1914.First research efforts dealt with the synthesis of ethylammonium nitrate.[3]This salt is liquid at room temperature but usually contains a small amount of water(200±600ppm).[4]The first ionic liquids with chloroaluminate ions were developed in1948by Hurley and Wier at the Rice Institute in Texas as bath solutions for electroplating aluminum.[5]How-ever,these systems were not studied further until the late 1970s when the groups of Osteryoung and Wilkes rediscov-ered them.For the first time,they succeeded in preparing room±temperature liquid chloroaluminate melts.[6]Research and development concentrated mainly on electrochemical applications at this time.As early as1967,a publication by Swain et al described the use of tetra-n-hexylammonium benzoate as a solvent for kinetic and electrochemical investigations.[7]Even though the liquid salt was a hemihydrate at room temperature,this research work had a pioneering significance because it already contained a quantitative determination of the ioniza-tion strength of the ionic medium.In the early1980s the groups of Seddon and Hussey began to use chloroaluminate melts as nonaqueous,polar solvents for the investigation of transition metal complexes.The investigations generally started with the electrochemical aspects of the relevant transition metal complexes;[8]spectro-scopic and complex chemistry experiments followed.[9]It is specially thanks to Seddon s work that ionic liquids became more familiar to a broad public.The first publications in which ionic liquids were described as new reaction media and catalysts for organic synthesis appeared at the end of the1980s.Acidic ionic liquids with chloroaluminate ions proved to be effective Friedel±Crafts catalysts;[10]phosphonium halide melts were used successfully in nucleophilic aromatic substitution reactions.[11]The use of ionic liquids as solvents for homogeneous transition metal catalysts was described for the first time inIonic LiquidsÐNewªSolutionsºfor Transition Metal CatalysisPeter Wa sserscheid*a nd WilhelmKeim[*]Dr.P.Wasserscheid,Prof.W.KeimInstitut für Technische Chemie undMakromolekulare Chemie der RWTH AachenWorringer Weg1,52074Aachen(Germany)Fax:( 49)241-8888177E-mail:Wasserscheidp@itc.rwth-aachen.deREVIEWSREVIEWS P.Wasserscheid and W.Keim1990by Chauvin et al.and by Wilkes et al.Chauvin s group dissolved nickel catalysts in weakly acidic chloroaluminate melts and investigated the resulting ionic catalyst solutions for the dimerization of propene.[12]Wilkes et ed also weekly acidic chloroaluminate melts and studied therein the ethylene polymerization with Ziegler±Natta catalysts.[13]The concept of ionic liquids received a substantial boost by the work of Wilkes s group when they described in1992the synthesis of systems with significantly enhanced stability against hydrolysis,for example low melting tetrafluoroborate melts.[14]In contrast to chloroaluminate ionic liquids,these systems offer high tolerance versus functional groups which opens up a much larger range of applications especially for transition metal catalysis.Ionic liquids with tetrafluoroborate ions have been successfully used,for example,in the rodium-catalyzed hydroformylation of olefins.[15]Based on Wilkes s work,it became clearly apparent that ionic liuids were by no means limited to chloroaluminate melts,quite to the contrary,a whole range of cation/anion combinations can form low-melting salts.The most recent publications are concerned with the synthesis of new ionic liquids,[16]with the systematic inves-tigation of their physical and chemical properties,[17]and with further applications as solvents and catalysts.[18]Two excellent reviews by Welton[19]and by Seddon and Holbrey[20]have been already published describing in special detail the use of chloroaluminate ionic liquids in synthetic and catalytic applications.Electrochemical[21]and complex chem-istry[22]investigations in ionic liquids have already been reviewed,too.The aim of our review is to describe the synthesis,proper-ties,and potential of ionic liquids with respect to their application as solvent in transition metal catalysis.In this context,we would like to offer especially to the chemist working in the field of homogeneous catalysis a set of criteria to identify suitable candidates out of the large number of ionic liquids(some authors speak about1018possible cation/anion combinations[20]).This section will be followed by a selection of examples which demonstrate that ionic liquids can be successful alternativeªsolutionsºfor many applications. Hereby,we will focus our attention on recently published work describing transition metal catalysis inªnon-chloroalu-minateºsystems.2.Ionic Liquid SynthesisThe initial step in the synthesis of ionic liquids is the quaternization,of an amine or phosphane for example,to form the cation.[6c,22]The most important,reported cation types are shown in Scheme1.Salts with different anionsareScheme1.Important types of cations in ionic liquids.obtained by the quaternization reaction depending on the alkylation reagent.Interestingly,melting points under1008C can be obtained for a series of cation/anion combinations in this way(Table1).REVIEWS Ionic LiquidsIn cases where it is not possible to form the desired anion directly by the quaternization reaction,a further step follows (synthesis steps IIa or IIb in Scheme 2).For example,starting from an ammonium halide [R 'R 3N] X À,two different paths to vary the anion are possible.First,the halide [R 'R 3N] X Àcan be treated with a Lewis acid MX y .This leads to an ionic liquid of the type [R 'R 3N] [MX y 1]À(synthesis step IIa,Scheme2).Scheme 2.Synthesis paths for the preparation of ionic liquids examplified for an ammonium salt.Alternatively it is possible to exchange the halide ion X Àfor the desired anion.This can be done by the addition of a metal salt M [A]À(with precipitation of M X À)over an ion exchanger or by displacement of the halide ion by a strong acid H [A]À(with the release of H X À)(synthesis step IIb,Scheme 2).In the first case,several anion species are often present in equilibrium,which depends on the ratio of the two compo-nents [R 'R 3N] X Àand MX y [Eq.(1)].With an excess of the Lewis acid MX y additional anion species can be formed from further acid ±base reactions with the already present anion.Such behavior is displayed by chloroaluminate melts,for example [Eq.(2)and (3)].[26]Theformation of different anions occurs as a function of the chloride/AlCl 3ratio.From Figure 1it can be seen that addition of aluminum trichloride to the chloride initially results in the formation of the AlCl 4Àion.With an aluminum trichloride mole fraction of exactly 0.5,this is essentially the only anion present.In systems with x (AlCl 3)>0.5multi-nuclear chloroaluminate anions are formed which are in equilibrium with each other,the AlCl 4Àion and,at very high AlCl 3contents,with dimeric aluminum trichloride.[26]Figure 1.Mole fraction x m of different anion species Xn in chloroalumi-nate melts (X1 Cl À;X4 AlCl 4À;X7 Al 2Cl 7À;X10 Al 3Cl 10À;X13 Al 4Cl 13À;X6 Al 2Cl 6).Chloroaluminates are the best known but not the only ionic liquids that can be prepared by the reaction of a halide with a Lewis acid.Further examples are shown in Table 2.When the anion is varied by anion exchange ionic liquids of the type [cation] [A]Àare formed (synthesis step IIb,Scheme 2),which contain only one anion species when the exchange reaction has proceeded to completion (Table 3).At this point it should be noted that the synthesis of highly pure,binary ionic liquids places particular demands on the Table 1.Examples of ionic liquids that can be formed by direct quater-nization.Ionic liqiud Alkylation reagent M.p.[8C]Ref.[EMIM]CF 3SO 3[a]methyl triflate À9[16a][BMIM]CF 3SO 3[b]methyl triflate 16[16a][Ph 3POc]OTs [c]OcOTs 70±71[24][Bu 3NMe]OTs MeOTs 62[25][BMIM]Cl chlorobutane 65±69[6c][a]EMIM 1-ethyl-3-methylimidazolium;CF 3SO 3 triflate anion.[b]BMIM 1-n -butyl-3-methylimidazolium.[c]Oc octyl;Ts H 3CC 6H 4-SO 2(tosyl).Table 2.Examples of ionic liquids that can be generated by the reaction of a halide with a Lewis acid.Ionic liquid [a]Established anion Ref.[cation]Cl/AlCl 3Cl À,AlCl 4À,Al 2Cl 7À,Al 3Cl 10À[27][cation]Cl/AlEtCl 2AlEtCl 3À,Al 2Et 2Cl 5À[28][cation]Cl/BCl 3Cl À,BCl 4À[29][cation]Cl/CuCl CuCl 2À,Cu 2Cl 3À,Cu 3Cl 4À[30][cation]Cl/SnCl 2SnCl 3À,Sn 2Cl 5À[31][a]cation pyridinium,imidazolium ion.Table 3.Examples of ionic liquids that can be prepared by anion exchange.Ionic liquid [a]Ref.[cation]BF 4[14,32][cation]PF 6[32,33][cation]SbF 6[30][cation]NO 3[14][cation]CH 3CO 2[14][cation]HSO 4[16f][cation]B(Et 3Hex)[34][a]cation pyridinium,imidazolium,ammonium ion.REVIEWSP .Wasserscheid and W.Keim preparative work.The purity of the system is essential for many solvent applications and for the characterization of their physical and chemical properties.Whereas organic solvents are usually purified by distillation before use,this method is not suitable to clean up ionic liquids due to their nonvolatile character.For this reason,the highest purity possible must be attained during the synthesis itself.For example,during the exchange of chloride ions for the desired anions,it must be ensured that no halide ions remain in the system.Also traces of the acid used in the synthesis can lead to unwanted chemical reactivity.High purity in the synthesis of binary ionic liquids is usually achieved by anion exchange over an ion exchanger.The described methods can,of course,also be used to prepare previously unknown combinations of cations and anions which could also result in low-melting salts.In addition there is the possibility to obtain ionic liquids with new properties by the mixture of several different salts.[35]3.Characteristic Properties of Ionic LiquidsThe physical and chemical properties of ionic liquids can be specifically varied over a wide range by the selection of suitable cations and anions.The possibility arises to optimize the ionic reaction medium for a specific application by stepwise tuning the relevant solvent properties.For this reason ionic liquids have been referred to as ªdesigner solventsºin several publications.[36]In the following section,we attempt to illustrate the relationships between the structural features of an ionic liquid and its important physical and chemical properties,on the basis of a few selected examples.3.1.Melting PointThe key criterion for the evaluation of an ionic liquid is,by definition,its melting point.Of particular significance is therefore the question of the relationship between the structure and chemical composition of an ionic liquid and its melting parison of the melting points of different chloride salts illustrates the influence of the cation clearly:High melting points are characteristic for alkali metal chlorides,whereas chlorides with suitable organic cations melt at temperatures below 1508C (Table 4).[6c,37]In the literature,the following features are discussed for cations of low-melting salts:low symmetry,[1]weak intermo-lecular interactions (such as the avoidance of hydrogen bonding),[16a,38]and a good distribution of charge in the cation.[39]Besides the cation,the anion influences the melting point,parison of the melting points of different salts with the 1-ethyl-3-methylimidazolium (EMIM)ion emphasizes that,in most cases,an increasing size of the anion with the same charge leads to a further decrease in the melting point (Table 5).For ionic liquids prepared by reaction of a halide [cati-on] X Àwith a Lewis acid MX y ,the molar ratio of the two reactants influences the melting points (Figure 2).[40]As already shown in Figure 1,a quasi-binary system with the AlCl 4Àion only exists for exact 1:1mixtures in the system [EMIM]Cl/AlCl 3.The fact that a local maximum in melting temperature is observed at exactly this composition indicates that the presence of several anions in the ionic liquid has the effect of decreasing the meltingpoint.Figure 2.Experimental phase diagram in the system [EMIM]Cl/AlCl 3(EMIM 1-ethyl-3-methylimidazolium ion).3.2.Vapor Pressure and Thermal Stability Ionic liquids have no measurable vapor pressure.This is a great advantage from a process engineering viewpoint,since separation by distillation of a reaction mixture becomes more effective as a method of product isolation.The well-known problem of azeotrope formation between the solvent and the products does not arise.The thermal stability of ionic liquids is limited by the strength of their heteroatom Àcarbon and their heteroa-tom Àhydrogen bonds,respectively.Ionic liquids synthesized by direct protonation of an amine or phosphane show,for Table 4.Melting points of various chlorides.Salt M.p.[8C]NaCl 803KCl772R R ' methyl ([MMIM]Cl)[a]125R methyl,R ' ethyl ([EMIM]Cl)87R methyl,R ' n -butyl ([BMIM]Cl)65[a]MMIM 1,3-dimethylimidazolium.Table 5.Influence of different anions on the melting point of imidazolium salts.Imidazolium salt M.p.[8C]Ref.[EMIM]Cl 87[6c][EMIM]NO 255[14][EMIM]NO 338[14][EMIM]AlCl 47[40][EMIM]BF 46[a][17d][EMIM]CF 3SO 3À9[16a][EMIM]CF 3CO 2À14[16a][a]Glass transition.REVIEWS Ionic Liquidsexample,significantly restricted thermal stability.Many melts with trialkylammonium ions already decompose at a temper-ature below808C in vacuo(depending on the boiling point of the related amine or acid).For ionic liquids obtained by alkylation of an amine or phosphane the tendency to undergo thermally induced transalkylation or dealkylation reactions (retro-quaternization reaction)is strongly related to the nature of their anion.While1508C has to be considered as maximum working temperature for most of the quaternary ammonium chloride salts,1-ethyl-3-methylimidazolium (EMIM)tetrafluoroborate,for example,has been reported to be stable to about3008C[41]and[EMIM][(CF3SO2)2N] (m.p.À38C)is stable up to even more than4008C.[16a] Consequently,some ionic liquids have,in contrast to water and most organic solvents,a liquid range of up to more than 4008C.3.3.DensityThe dependence of the density of an ionic liquid on the type of cation and anion can be illustrated clearly by the example of chloroaluminate and bromoaluminate melts.A comparison of chloroaluminate melts with different cations reveals an almost linear relationship between the density and the length of the N-alkyl chain on the imidazolium cation(Figure3).[40]Figure3.Dependence of the density1of1,3-dialkylimidazolium tetra-chloroaluminate melts on the type of both alkyl groups;measurement temperature at608C,x(AlCl3) 0.5.More generally,it can be concluded that the density of comparable ionic liquids decreases as the bulkiness of the organic cation increases.Slight structural changes in the cation allow a fine adjustment of the density.Varying the anion results in more obvious effects in several cases.With bromoaluminate melts for example,it was possible to achieve densities unusual for normal organic solvents(Figure4).[42]Density measurements of ionic liquids with triflate or trifluoroacetate ions confirmed the more general result that a certain density range is established by the choice of anion,within which a fine adjustment is possible by careful choice of the cation.[16a]3.4.ViscosityThe viscosity of ionic liquids is essentially determined by their tendency to form hydrogen bonding and by the strength of their van der Waals interactions.[16a]Figure4.Dependence of the density1of two1-ethyl-3-methylimidazo-lium tetrahaloaluminate melts on the mole fraction of aluminum trihalide at608C.The effect of hydrogen bonding becomes clear when,for example,the viscosities of chloroaluminate melts of different compositions are compared(Figure5).[40]The increase in viscosity of more than a factor of ten in ionic liquidswithFigure5.Dependence of the dynamic viscosity h[cP]of two1,3-dialkylimidazolium tetrachloroaluminate melts on the mole fraction of aluminum trichloride at258C.x(AlCl3)<0.5is a result of the formation of hydrogen bonds between the hydrogen atoms of the imidazolium cation and the basic chloride ion.This statement is supported by IR[43] and X-ray spectroscopy,[44]ROESY-NMR,and theoretical calculations.[45]In acidic mixtures,however,the anions AlCl4Àand Al2Cl7Àare present,in which the negative charge is much better distributed.This leads to the formation of weaker hydrogen bonds and a much lower viscosity. Comparison of the viscosity of different,hydrophobic ionic liquids with1-n-butyl-3-methylimidazolium(BMIM)ions emphasizes,in addition,the interplay between van der Waals interactions and hydrogen bonding(Table6).[16a]The transi-tion from the triflate ion to the n-C4F9SO3Àion,and from the trifluoroacetate ion to the n-C3F7COOÀion reveals anTable6.Dynamic viscosities h of various1-n-butyl-3-methylimidazolium (BMIM)salts at208C.Anion[A]Àh[cP]CF3SO3À90n-C4F9SO3À373CF3COOÀ73n-C3F7COOÀ182(CF3SO2)2NÀ52REVIEWS P.Wasserscheid and W.Keimobvious increase in viscosity.It is apparent that the stronger van der Waals interactions in the case of the n-C4F9SO3Àand n-C3F7COOÀions result in a higher viscosity of the ionic parison of the viscosities of[BMIM]CF3SO3with [BMIM](CF3SO2)2N,reveals a lower viscosity despite stron-ger van der Waals interactions for ionic liquids with the (CF3SO2)2NÀion.In this case,the almost complete suppres-sion of hydrogen bonding overcompensates for the expected increase in viscosity.[16a]The structure of the cation also influences the viscosity of the ionic liquid.The lowest viscosities are usually obtained for melts with the1-ethyl-3-methylimidazolium(EMIM)ion,in which a side chain with sufficient mobility is combined with a low molar mass.Longer or fluorinated alkyl chains result in higher viscosities because of stronger van der Waals inter-actions.[16a]The viscosity of ionic liquids can be lowered,drastically in some cases,by only slight increases in temperature[40,46]or by the addition of small amounts of organic cosolvents.[47]3.5.Solvation Strength and Solubility CharacteristicsThe tuning of solubility properties of an ionic liquid by the careful choice of cation and anion deserves particular attention.The influence of the cation,for example,is shown by investigations of the solubility of1-octene in different tosylate melts(Figure6).[25]It can be seen that with increasing nonpolar character of the cation,the solubility of1-octene in the melt increases markedly.In methyl-tri-n-octylammo-nium tosylate a single-phase reaction mixture is obtained.This example shows that stepwise variation of the solubility properties can be achieved by variation of the alkyl group on the cation.The influence of the anion on the solubility characteristics of ionic liquids can be demonstrated in an impressive fashion by the example of the water solubility of different melts containing the BMIM ion.While[BMIM]Br,[BMIM]-CF3COO,and[BMIM]CF3SO3are highly water-soluble,ionic liquids with the same cation but with a PF6Àor(CF3SO2)2NÀion form biphasic mixtures with water.The water content of the ionic liquid[BMIM](CF3SO2)2N at208C is only1.4weight percent.[16a]Several ionic liquids showing a miscibility gap with water have been considered as interesting candidates for separation processes by liquid±liquid extraction.Rogers et al.inves-tigated,for example,the solubility of different acids and bases in water/[BMIM]PF6at different pH values of the aqueous phase.[48]Interestingly,their results reveal a higher solubility of neutral substrates in the ionic liquid,while ionic species dissolve preferentially in the aqueous layer.The authors conclude that the solubility properties of[BMIM]PF6versus water show high similarity to organic solvents.The substitu-tion of volatile organic solvents by ionic liquids in extractive separation processes may therefore be an interesting option. Many ionic liquids are completely miscible with organic solvents if their dielectric constants exceed a characteristic limit.This limit appears to be specific for each cation/anion combination(Table7).[16a]The solubility of supercritical CO2in[BMIM]PF6that has recently been investigated by Brennecke s group is remark-able,too.[49]In the biphasic system scCO2/[BMIM]PF6 60mol%of CO2dissolve in the ionic liquid at80bar CO2 pressure.Hereby,the volume of the ionic liquidincreases only by10±20%,however.As a firstapplication of this interesting biphasic system,theauthors investigated the extraction of naphthalenefrom the ionic liquid.They succeeded in recoveringthe naphthalene quantitatively without any detect-able contamination of the extract by the ionic liquid.Without doubt,the key to the successful use ofionic liquids lies in the skillful exploitation of theirexceptional solubility characteristics.Further system-atic investigations are necessary,however,to take fulladvantage of this huge potential.One very promising possibility is,for example,theinvestigation of the polarity of ionic liquids.Thepolarity of a solvent is usually determined in a purelyempirical fashion.A well-understood,easily measur-able and strongly solvent-dependent process is deter-Figure6.Solubility of1-octene in four different tri-n-alkylmethylammonium tosylatemelts at808C.n(C) number of C atoms of the alkyl residue.Table7.Miscibility of various ionic liquids with the1-ethyl-3-methylimidazolium(EMIM)ion in organic solvents with the dielectric constant e.[a] Solvent e[EMIM]CF3SO3[EMIM]CF3COO[EMIM]n-C3F7COO[BMIM]CF3COO[b][BMIM]n-C3F7COO CH2Cl28.93m m m m mTHF7.58m m m m methyl acetate 6.02m pm pm m mtoluene 2.38im im im im im1,4-dioxane 2.01im im im im im[a]m:miscible;pm:partially miscible;im:immiscible.REVIEWS Ionic Liquids mined in a large number of different solvents,for example the spectral absorption of a solvatochromic dye.Empirical solvent polarity parameters are derived from the measured absorption maxima,which reflect the solvating ability of a solvent much more comprehensively than the individual physical constants.[50]Amongst the many empiri-cal polarity scales,the E (T)(30)scale introduced by Dimroth et al.in 1963[51]and further devel-oped by Reichhardt et al.in 1971has proven successful,and is based on the solvatochromism of a pyridinium-N -phenolate betaine dye.[52]This method has also been used successfully to determine the polarity of a small number of ionic liquids.The results obtained confirm the considerable width of variation of solvent polarity of ionic liquids.While,for example,tetra-n -hexylammonium benzoate with an E (T)(30)value of 0.41lies within the polarity range of DMF,[53]an E (T)(30)value of 0.95was determined for ethyl-ammonium nitrate corresponding to a polarity between CF 3CH 2OH and water.[4,54][BMIM]PF 6was investigated by using the same method and its E (T)(30)value was found to correspond to a polarity in the range of methanol.[55]However,recent work by Armstrong et al.gave rise to the question whether the chemical nature of the solvatochromic dye influences the result of the polarity determination of an ionic liquid.These authors coated GC columns with several ionic liquids and compared the retention times of a large number of substances.[56]The results of their study indicate different polarity of ionic liquids depending on the nature of the tested compounds.While [BMIM]PF 6,for example,acts like an unpolar stationary phase versus unpolar molecules (like n -octane),very long retention times are observed with proton-donor compounds.The authors attribute a dual polarity behavior to the ionic liquids under investigation.Unfortunately the number of systematic investigations concerning the polarity of ionic liquids is still very limited.More research in this field should be encouraged in order to establish efficient criteria to determine the right ionic liquid candidate for a given solvent application.3.6.Acidity and Coordination AbilityThe acidity and coordination properties of an ionic liquid are essentially determined by the nature of its anion.Many intermediate levels between ªstrongly basic/strongly coordi-natingºand ªstrongly acidic/practically noncoordinatingºcan be realized by careful choice of the anion (Table 8).[30]In this context,those ionic liquids have to be mentioned which form a neutral anion (e.g.AlCl 4À)or an acidic anion (e.g.Al 2Cl 7À)from a basic anion (e.g.Cl À)by addition of a Lewis acid (e.g.AlCl 3).In Scheme 3this behavior is illustrated by the example of a EMIM chloroaluminate melt.Chloroaluminate melts are designated as basic when the molar ratio of AlCl 3is smaller than 0.5.A neutral melt is referred to at an AlCl 3ratio of exactly 0.5,where essentially only the anion AlCl 4Àis present.[22a]Finally,an acidic chloroaluminate melt is one in which the AlCl 3ratio is larger than 0.5.In such acidic melts,the anions Al 2Cl 7Àand Al 3Cl 10Àexist,which act as very strong Lewis acids.[27]Two further phenomena in the field of acid/base chemistry of ionic liquids deserve to be mentioned.These are the so-called ªlatent acidityºand ªsuperacidityºof protons in ionic liquids.The latent acidity of ionic liquids arises when weak bases are added to buffered neutral chloroaluminate melts.Such melts are formed when,for example,excess alkali metal chloride (MCl)is added to an acidic chloroaluminate melt.[57]The alkali metal chloride MCl reacts according to Equa-tion (4)with the acidic chloroaluminate dimers until themelt becomes neutral.A buffered melt is one in which the neutrality of the melt is maintained by reaction of excess alkali metal chloride when acid AlCl 3is added.The latent acidity of this neutral system becomes noticeable when a weak base (B)such as N ,N -dimethylaniline,pyrrole,or acetylferro-cene is added.[58]An adduct is formed between the added base and AlCl 3with precipitation of the alkali chloride MCl [Eq.(5)].This reaction is not observed in the absence of excess alkali metal cations.The latent acidity of different ionic liquids has already been quantitatively measured.[59]In our group,ionic liquids with latent acidity have been successfully used as solvents in the Ni-catalyzed oligomerization of 1-butene (see Section 4.8).[60]The superacidity of protons in several ionic liquids is also worth mentioning.It has been observed when strong mineral acids were dissolved in acidic chloroaluminate ionic liquids.[61]Smith and co-workers investigated the acidity of such protons in ionic liquids by the protonation of aryl compounds with a solution of HCl gas in acidic [EMIM]Cl/AlCl 3melts.The acidity of the protons in the melt were measured quantita-Table 8.Coordinative characteristics of various anions.Acidity/coordination basic/strongly coordinating neutral/weakly coordinating acidic/non-coordinatingCl ÀAlCl 4ÀAl 2Cl 7ÀAc ÀCuCl 2ÀAl 3Cl 10ÀNO 3ÀSbF 6ÀSO 42ÀBF 4ÀCu 2Cl 3ÀPF 6ÀCu 3Cl 4ÀScheme 3.Control of the acidity of ionic liquids by the ratio of halide to Lewis acid examplified for 1-ethyl-3-methylimidazolium (EMIM)chloroaluminate melt.。
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a rXiv:n ucl-e x /99123v17D ec1999Dileptons as Probes ofHigh-Density Hadronic Matter:Results from the SPS Heavy-Ion Programme Itzhak Tserruya 1Weizmann Institute of Science,Rehovot,Israel Abstract The most recent results on dileptons obtained in the CERN heavy-ion programme are reviewed.The emphasis is on the excess of low-mass lepton pairs observed in the CERES,HELIOS-3and NA38/50experiments which seems to point at modifications of the vector meson properties,and in particular the ρmeson,in a high density baryonic medium.Recent results on intermediate mass dileptons are also presented.1Introduction The heavy-ion programme at the CERN SPS started in 1986with the acceler-ation of O beams at an energy of 200GeV/c per nucleon followed soon after by a S beam at the same energy.Since 1994the programme uses a Pb beam of 158GeV/c per nucleon.Among the vast amount of experimental results that have been gathered the observation of an excess emission of low-mass dilepton pairs appears as one of the most notable and intriguing achievements of the programme along with the J/ψsuppression and strangeness enhancement [1].Dileptons emitted in ultra-relativistic heavy-ion collisions are considered unique probes in the study of hadronic matter under extreme conditions of temperature and baryon density and in particular the conjectured deconfine-ment and chiral phase transitions.These penetrating probes have a relativelylarge mean free path and consequently can leave the interaction region without final state interaction,carrying information about the conditions and proper-ties of the matter at the time of their production and in particular of the earlystages of the collision when temperature and energy density have their largest values2.A prominent topic of interest is the identification of thermal radiation emit-ted from the collision system.This radiation should tell us about the nature of the matter formed,a quark-gluon plasma(QGP)or a high-density hadron gas(HG).The elementary processes involved are well known:q2The same argument is in principle valid for real photons,since real and virtual(dileptons) photons are expected to carry the same physics information.However,the physics background for real photons is larger by orders of magnitude as compared to dileptons,making the measurement of photons much less sensitive to a new source.2over a very broad range of invariant masses.The enhancement is particularly pronounced in the continuum at low-masses(0.2<m<0.7GeV/c2)but it is also significant in the continuum at intermediate masses(1.5<m<3.0GeV/c2) and in theφmeson yield.The low-mass pair enhancement has triggered a huge amount of theoretical activity mainly stimulated by interpretations based on in-medium modifications of the vector mesons and in particular a decrease of theρ-meson mass as a precursor of chiral symmetry restoration.Table1.List of Dilepton Measurements at the CERN SPS Experiment System Mass7,8 CERES S-Au200GeV/u0–1.410-12µ+µ− 3.65-4.913 (completed)““HELIOS-3p-W,S-W200GeV/u0.3–4.0µ+µ− 3.0-4.015 NA50Pb-Pb158GeV/u0.3–7.0are displayed in Fig.1.On the positive side,one notes that the results appear consistent with each other within their error bars.The level of agreement is remarkable if one keeps in mind the huge filtering of the data 3,the fact that these are two different data sets,and that they have been analyzed with the same strategy but with a somewhat different technique 4.1010101010m ee (GeV/c 2)(d2N e e/d ηd me e ) /(d Nc h/d η)(100 M e V /c2)-1Figure 1:Inclusive e +e −mass spectrum measured by CERES in 158A GeV Pb–Au collisions in the ’95and ’96runs.The figure also shows the summed (solid line)and individual (dotted lines)contributions from hadronic sources in a thermal model [12].The predictions from the pp cocktail previously used by CERES [7]are shown by the dashed line.As previously observed with the S beam [9],the e +e −pair yield is clearlyenhanced in the mass range above∼200MeV/c2and below theρ/ωpeak,with respect to the expected yield from known hadronic sources.The solid line shows the total expected yield based on a generator[12]which uses measuredparticle production ratios whenever available or ratios calculated with a thermalmodel which describes well all these ratios[20].With respect to this cocktail the measured yield in the mass region m=0.25-0.7GeV/c2is enhanced bya factor of2.6±0.5(stat.)±0.6(syst.).For comparison thefigure also shows(dashed line)the standard pp cocktail previously used in the presentation of the CERES results[7]and which is based on yields directly measured in ppcollisions,scaled to the nuclear case with the charged particle rapidity density. The two generators predict closely similar results.The total yield of the thermalmodel is∼30%larger than the pp cocktail for masses m>200MeV/c2,themain difference occuring in the region of theφmeson.CERES has further characterized the properties of the low-mass excess bystudying its p t and multiplicity dependences,which indicate that the excess ismainly due to soft pair p t and increases faster than linearly with the charged particle density[10,11,12].An enhancement of low-mass dileptons has also been observed in the di-muon experiments HELIOS-3[14]and NA38[15]with the S beam.NA38hasan interesting set of results including p-U,S-S and S-U collisions at200A GeV.Whereas the p-U data are well reproduced by a cocktail of hadronic sources (with the somewhat uncertain extrapolation of the Drell-Yan contribution intolow masses),the S data shows an enhancement of low-mass pairs.The enhance-ment is most apparent in the S-U collision system and there it clearly extends over the intermediate mass region as illustrated in Fig.2.There is a striking difference in the shape of the low-mass dilepton spectrum as measured by CERES and NA38.A pronounced structure due to the reso-nance decays is clearly visible in the NA38spectrum,whereas in the CERESresults the structure is completely washed out(see Fig.1),raising the question of consistency between the two experiments.Resolution effects can be readilyruled out since the low-mass spectrum in p-Be and p-Au collisions measured byCERES with the same apparatus clearly shows theρ/ωpeak[7].We also note that the two experiments cover nearly symmetric ranges around mid-rapidity(η=2.1–2.65andη=3–4in CERES and NA38respectively).But CERES hasa relatively low p t cut of200MeV/c on each track whereas NA38is restricted to m t>0.9+2(y lab−3.55)2GeV/c2.Moreover,NA38has no centrality selec-tion in the trigger whereas the CERES data corresponds to the top30%of the geometrical cross section.These two factors are likely to explain the apparentdiscrepancy since,as noted previously,the excess observed by CERES is morepronounced at low pair p t and increases stronger than linearly with multiplic-511010101010M (GeV)A *d σ/d M (n b /50 M e V )Figure 2:Inclusive µ+µ−mass spectra measured by NA38in 200A GeV S-U collisions.The thick line represents the summed yield of all known sources.The individual contributions are also shown [15].ity.Given enough statistics it should be fairly easy for the two experiments to apply common m t and centrality cuts thereby making possible a direct and meaningful comparison between their results.3Low-mass Dileptons:Theoretical Evaluation The enhancement of low-mass dileptons has triggered a wealth of theoretical activity.Dozens of articles have been published on the subject and clearly it is not possible to review them here.I present thus a summary of the current leading approaches.There is a consensus that an additional source beyond a simple superposition of pp collisions is needed.Furthermore,it is commonly recognized that the pion annihilation channel (π+π−→l +l −),obviously not present in pp collisions,has to be taken into account.This channel accounts for a large fraction of the observed enhancement however it is not sufficient to reproduce the data in the mass region 0.2<m e +e −<0.5GeV/c 2.These data have been quantitatively explained by taking into account in-medium modifica-6tions of the vector mesons.Li,Ko and Brown[21]were the first to propose and use a decrease of the ρ-meson mass in the hot and dense fireball as a precursor of chiral symmetry restoration,following the original Brown-Rho scaling [22].With this approach,an excellent agreement with the CERES dat is achieved as demonstrated by the solid line in Fig.3(taken from [6]).101010101000.20.40.60.81 1.2 1.4m ee (GeV/c 2)(d 2N e e /d ηd m e e ) / (d N c h /d η) (100 M e V /c 2)-1Figure 3:CERES results compared to calculations using dropping ρmass (Brown-Rho scaling),in-medium ρ-meson broadening and RBUU transport model.The dash-dotted line represents the yield from hadrons after freeze-out as in Figure 1.Another avenue based on effective Lagrangians uses a ρ-meson spectral func-tion which takes into account the ρpropagation in hot and dense matter,in-cluding in particular the pion modification in the nuclear medium and the scattering of ρmesons offbaryons [23,24].This leads to a large broadening of the ρ-meson line shape and consequently to a considerable enhancement of low-mass dileptons.These calculations achieve also an excellent reproduction of the CERES results as illustrated by the dashed line in Fig.3.Although the two approaches are different in the underlying physical picture (in the Brown-Rho scaling the constituent quarks are the relevant degrees of freedom whereas ref.[23]relies on a hadronic description),it turns out that the dilepton pro-duction rates calculated via hadronic and partonic models are very similar at SPS conditions [6]thus explaining the similar results of the two approaches.7Several issues remain controversial.Both approaches rely on a high baryondensity for the dropping mass or the enlarged width of theρmeson but the role of baryons is still a question open to debate.Calculations based on chiralreduction formulae,although similar in principle to those of ref.[23],find verylittle effect due to baryons and are in fact low compared to the data[25].The RBUU transport calculations of Koch[26]find also very little effect due tothe baryons and come to a reasonably close description of the data as shownin Fig.3by the dash-dotted line.This could be due to an overestimation of theωDalitz decay yield as a consequence of an increasedωyield directlyreflected in thefigure at m∼800MeV,which is dominated by theω→e+e−decay.Finally,I wish to point out the discrepancy between transport[24]andhydrodynamic calculations[27]in treating the time evolution of thefireball,the former yielding a factor of2-3higher yields.4Intermediate-mass DileptonsThe results of HELIOS-3[14]and NA38/50[15,16]clearly show an excess of dileptons in the intermediate mass region1.5<m<3.0GeV/c2(see Figs.2and4).The excess refers to the expected yield from Drell-Yan and semi-leptonic charm decay which are the two main contributions in this mass region. The shape of the excess is very similar to the open charm contribution and infact doubling the latter nicely accounts for the excess.This is the basis for thehypothesis of enhanced charm production made by NA38/50[16].However it is very unlikely that at the SPS energies charm production could be enhanced bysuch a large factor[28].HELIOS-3points into a different direction.The excess plotted as a function of the dimuon transverse mass can befitted by a singleexponential shape below and above the vector mesons[14],suggesting a com-mon origin of the excess in the low and intermediate mass regions.Following this line,Li and Gale[29]calculated the invariant dimuon spectrum in centralS-W collisions at200A GeV.On top of the physics background of Drell-Yanand open charm pairs,they considered the thermal radiation of muon pairs resulting from secondary meson interactions including higher resonances andin particular theπa1→l+l−.The calculations are based on the same rela-tivisticfireball model used to calculate the low-mass dileptons discussed in theprevious section[21].Their results are presented in Fig.4showing the totalyield(physics background+thermal yield)with the assumption of free masses (dotted line)and dropping vector meson masses(solid line).The latter leads toa much better agreement with the data at low masses(from0.3to0.7GeV/c2),as already mentioned in the previous section,whereas in the intermediate mass region the difference between free and in-medium meson masses with respect8Figure4:HELIOS-3dimuon data compared to calculations with free and in-medium meson masses[29].to the data is not so large.The calculations with free masses slightly overes-timate the data whereas with dropping masses the situation is reversed.The intermediate mass region alone cannot be used to validate the dropping mass model,however it is important that the model can explain simultaneously the low and intermediate mass regions.5Summary and OutlookThe measurements of dileptons both at low and intermediate masses have pro-vided very intriguing results.The outstanding physics question is to further elucidate the origin of the observed excess and its possible relation to chiral symmetry restoration.There are a number of open questions on the theoretical front:the role of baryons,the difference between transport and hydrodynamic calculations,the approach to chiral restoration(do masses drop to zero and/or do their width increase to infinity?),With the present accuracy of the data it is not possible to discriminate between the various models.Major new steps are foreseen in the near future.First,CERES is planning to dramatically improve the mass resolution to achieveδm/m=1%,by the ad-dition of a TPC downstream of the present double RICH spectrometer.With this resolution,which is of the order of the natural line width of theωmeson,9it should be possible to directly measure the yield of all three vector mesons ρ,ωandφincluding any possible changes in their properties(mass shift or in-creased width)thereby providing a better experimental tool to reveal possible in-medium modifications of the vector mesons.Second,a measurement is pro-posed at the lowest energy attainable at the SPS,at about40GeV/nucleon, where the effect of baryon density on the vector meson masses is expected to be st but not least,RHIC start of operations is behind the corner of-fering the possibility to extend these studies under better conditions of energy density and lifetime and to explore a new domain where temperature rather than baryon density is expected to be the dominant factor. 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